impact modified composition and manufactured article

专利摘要:
modified impact composition and manufactured article impact modified compositions having good impact performance can be prepared from a thermoplastic (for example, poly (alpha-olefin) such as polypropylene or hdpe) and an interpolymer in ethylene / alpha- multiblocks olefin. the compositions are easily molded and are often useful in the manufacture of automotive instruments, parts and other household items.
公开号:BR112012024303B1
申请号:R112012024303
申请日:2011-03-21
公开日:2020-02-04
发明作者:R Marchand Gary；l walton Kim；Kapur Mridula；Wu Shaofu；Dhodapkar Shrikant
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

“MODIFIED COMPOSITION FOR IMPACT AND MANUFACTURED ARTICLE
Field of the invention [001] This invention relates to the modification for improved impact of thermoplastic polymers and polymer mixtures. History and summary of the invention [002] Many different materials and polymers have been added in polymeric compositions in an attempt to improve the impact resistance or maintain the impact resistance of the composition while improving others
properties. Per example, the U.S. patent no. 5,118,753 (Hikasa et al.), discloses compositions of elastomer thermoplastic what says Tue low hardness and excellent properties mechanical and flexibility consisting essentially in an copolymer rubber olefinic
diluted in oil and an olefinic plastic. The olefinic plastic is polypropylene or a polypropylene copolymer and an alphaolefin of 2 or more carbon atoms. Modern Plastics Encyclopedia / 89, published in mid-October 1988, volume 65, number 11, pages 110-117, also discusses the use of various thermoplastic elastomers (TPEs) useful for impact modification. These include: TPEs of elastomeric alloys, engineering TPEs, olefinic TPEs (also known as thermoplastic olefins or TPOs), polyurethane TPEs and styrenic TPEs.
[003] Thermoplastic olefins (TPOS) are often produced from mixtures of an elastomeric material such as ethylene / propylene rubber (EPM) or ethylene / propylene / diene terpolymer (EPDM) and a more rigid material such as isotactic polypropylene. Other materials or components can be added to the formulation depending on the
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2/161 application, including oil, fillers, and crosslinking agents. Frequently, TPOs are characterized by a balance of stiffness (modulus) and low temperature impact, good chemical resistance and wide usage temperatures. Because of features such as these, TPOs are used in many applications including automotive instruments, and wire and cable operations, rigid packaging, molded articles, instrument panels, and the like.
[004] Union Carbide Chemicals and Plastics Inc. announced in 1990 that it had developed a new cost-effective class of polyolefins commercially called FLEXOMER ™ polyolefins that could replace expensive EPM or EPDM rubbers. These new polyolefins are said to bridge the gap between rubbers and polyethylene, with modules between the two bands. However, the rubber and formulation modules are not the only criteria for evaluating a TPO formulation. Low temperature impact performance, sometimes measured by Gardner impact at -30 ° C is also sometimes important for TPO composition performance. According to the data contained in Figure 4 of the report “FLEXOMER ™ Polyolefins: A Bridge Between Polyethylene and Rubbers by M.R. Rifi, H.K. Ficker and MA Corwin, more than one FLEXOMER ™ polyolefin needs to be added to the TPO formulation in order to achieve the same levels of Gardner impact performance at low temperature as standard EPM rubber, thus negating the benefits of lower cost somewhat. replacement of EPM / EPDM. For example, using the data in Figure 4 of the report by Rifi et al., About 20% by weight of polypropylene EPM gives a Gardner impact of about 22 J at -30 ° C, while
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3/161 same amount of FLEXOMER ™ polyolefin gives a Gardner impact at -30 ° C of about 13 J.
[005] In a paper presented on September 24, 1991, at SPO '91 (1991 Specialty Polyolefins Conference) (pp. 4355) in Houston, Texas, Michael P. Jeffries (Exxpol Ethylene Polymers Venture Manager of Exxon Chemical Company) also reports that Exxon EXACT ™ polymers and plastomers can be mixed with polypropylene for impact modification. Exxon Chemical Company in the preliminary runs of Polyolefins VII International Conference, pages 45-66, February 24-27, 1994, also disclose that narrow molecular weight distribution (NMWD) resins produced by its EXXPOL ™ technology have higher melt viscosity and lower melt strength than conventional Ziegler resins at the same melt index. In another recent publication, Exxon Chemical Company also teaches that NMWD polymers prepared using single site catalyst create the potential for melt fracture (“New Specialty Linear Polymers (SLP) For Power Cables, by Monica Hendewerk and Lawrence Spenadel, presented at a meeting of IEEE in Dallas, Texas in September 1991).
[006] It is well known that linear polymers of narrow molecular weight distribution have an unfavorably low shear sensitivity or low I ₁₀ / I _{2 value} , which limits the extrusion capacity of such polymers. In addition, such polymers have low melt elasticity, causing melt making problems such as film forming processes or blow molding processes (for example, holding a bubble in the expanded film process, or bending in the casting process).
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4/161 blow molding, etc.). Finally, such resins also experience melt surface fracture properties at relatively low extrusion rates, thus processing unacceptably and causing surface irregularities in the finished product.
[007] Consequently, although the development of new smaller modulus polymers such as FLEXOMER ™ polyolefins from Union Carbide or EXACT ™ polymers from Exxon has helped the TPO market, there remains a need for other more advanced cost-effective polymers to combine with thermoplastics example, polyolefins such as polypropylene or HDPE) to improve or maintain modulus and / or impact performance at a temperature less than or equal to room temperature.
[008] Compositions formulated having this combination of modulus and low temperature impact performance have now been discovered. In one aspect, the impact modified compositions comprise: (A) a thermoplastic polymer composition; and (B) an amount of impact modification of an interpolymer in ethylene / a-olefin multiblocks comprising hard segments and soft segments, the quantity of the hard segments being at least 30 weight percent, based on the total weight of the ethylene / a-olefin multiblock interpolymer, and the ethylene / a-olefin multiblock interpolymer: (a) has an M _w / M _n of about 1.7 to about 3.5, at least one point melting point, T _m , in ° C and density, d, in g / cm ³ , with the numerical values of T _{m and} d corresponding to the relationship: T _m > -2002.9 + 4538.5 (d) - 2422, 2 (d) 2; or (b) has M _w / M _n of about 1.7 to about 3.5, and is distinguished by a heat of fusion, Δη in J / g, and a
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5/161 delta quantity, Δτ, in ° C, defined as the temperature difference between the maximum DSC peak and the maximum CRYSTAF peak, with the numerical values of Δτ and ΔH having the following relationships: Δτ> -0, 1299 (ΔΗ) + 62.81 for ΔH greater than zero and up to 130 J / g; Δτ> 48 ° C for ΔH greater than 130 J / g, with the peak of CRYSTAF being determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature will be 30 ° C; or (c) it is distinguished by a percentage elastic recovery, Re, in deformation of 300 percent, and 1 cycle, measured with a film molded by compression of the interpolymer in ethylene / aolefin multiblocks, and having a density, d, in grams per cubic centimeter, the numerical values of Re ed satisfying the following relationship when the ethylene / α-olefin interpolymer is substantially free of a crosslinked phase: Re> 1481 - 1629 (d); or (d) it has a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, characterized by having a comonomer molar content of at least 5 percent, greater than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, the said comparable random ethylene interpolymer having the same comonomers and having a melting index, density, and molar comonomer content (based on the entire polymer) within the 10 percent range of that of the interpolymer in ethylene / aolefin multiblocks; or (e) it has at least one molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, distinguished by the fact that the fraction has a block index of at least 0.5 and up to about 1; or (f) has an average block index
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6/161 greater than zero and up to about 1.0 and a molecular weight distribution, M _w / M _n , greater than about 1.3; or (g) has a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° C, G' (100 ° C), with the ratio G '(25 ° C) ) for G '(100 ° C) is in the range of about 1: 1 to about 9: 1.
[009] In some embodiments, the amount of hard segments in the interpolymer in ethylene / a-olefin multiblocks disclosed here is about 35 weight percent to about 80 weight percent, based on the total weight of the interpolymer in ethylene / a-olefin multiblocks.
[010] In other embodiments, the amount of α-olefin monomer in the soft segment of the interpolymer in ethylene / a-olefin multiblocks disclosed here is about 12 mol% to about 35 mol%, based on the total amount in moles of a-olefin monomer and ethylene monomer in the soft segment.
[011] In certain embodiments, the thermoplastic polymer composition comprises one or more polymers selected from the group consisting of polyurethanes, poly (vinyl chlorides), styrenics, hydrogenated styrenics, polynorbornene, poly (ethylene-co-norbornene), poly (4 -methyl-pentene) with one or more pre-grafted functional monomers, polyolefins, polycarbonates, thermoplastic polyester, polyamides, polyacetals, and polysulfones. In other embodiments, the thermoplastic polymer composition comprises polypropylene. In additional embodiments, the thermoplastic polymer composition comprises high density polyethylene.
[012] In some embodiments, the interpolymer in ethylene / a-olefin multiblocks is an interpolymer of
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7/161 multiple blocks. In other embodiments, the aolefin monomer is 1-butene, 1-hexene or 1-octene. In additional embodiments, the interpolymer in ethylene / aolefin multiblocks has a density of about 0.85 to about 0.93 g / cm3.
[013] In certain embodiments, the impact modified compositions disclosed herein further comprise at least one additive selected from the group consisting of glidants, non-stick agents, adhesion agents, plasticizers, oils, waxes, antioxidants, UV stabilizers, dyes or pigments, fillers, flow aids, coupling agents, crosslinking agents, surfactants, solvents, lubricants, anti-fog agents, nucleating agents, flame retardants, antistatic agents and combinations thereof.
[014] In some embodiments, the thermoplastic polymer composition comprises at least one propylene polymer, in which the amount of the interpolymer in ethylene / α-olefin multiblocks is from about 10 weight percent to about 40 weight percent by weight, based on the total weight of the composition. In other embodiments, the Izod notch impact strength at 20 ° C is at least 5% higher, at least 10% higher or at least 15% higher when compared to the same propylene polymer composition without the interpolymer in multiblocks of ethylene / a-olefin.
[015] In certain embodiments, the thermoplastic polymer composition comprises at least one high density polyethylene, and in which the amount of the interpolymer in ethylene / α-olefin multiblocks is about 10 weight percent at about 40 percent weight percent, based on weight
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8/161 total of the composition. In other embodiments, the Izod notch impact strength at 20 ° C is at least 5% higher, at least 10% higher or at least 15% higher when compared to the same high density polyethylene composition without the multiblock interpolymer ethylene / αolefin.
[016] In one aspect, here are manufactured articles prepared with the impact modified compositions disclosed herein.
Brief description of the drawings [017] Figure 1 shows the melting point / density ratio for the inventive polymers (represented by diamonds) when compared with traditional random copolymers (represented by circles) and with Ziegler-Natta copolymers (represented by triangles) ;
[018] Figure 2 shows delta graphics DSC-CRYSTAF
as a occupation in enthalpy of DSC merger for several polymers Diamonds represent copolymer random in ethylene / octene; the squares represent examples in polymers 1-4; the triangles represent examples in polymers 5-9; and the circles represent examples in polymers 10-19. The symbols “X  represent examples in polymers A * -F * ·[019] Figure 3 shows the effect of density on The
elastic recovery for non-oriented films prepared with the inventive interpolymers (represented by squares and circles) and with traditional copolymers (represented by the triangles that are various AFFINITY ^® polymers from Dow). The squares represent inventive ethylene / butene copolymers, and the circles represent copolymers
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9/161 inventories of ethylene / octene;
[020] Figure 4 is a graph of the octene content of ethylene / 1-octene copolymer fractions fractionated by TREF against fraction eluting TREF temperature for the polymer of Example 5 (represented by the circles) and for the comparative polymers E and F (represented by the X symbols). The lozenges represent traditional random copolymers of ethylene / octene;
[021] Figure 5 is a graph of octene content of ethylene / 1-octene copolymer fractions fractionated by TREF against fraction eluting temperature of TREF for the polymer of Example 5 (curve 1) and for the comparative polymer F (curve 2). The squares represent Comparative Example F *, and the triangles represent Example 5;
[022] Figure 6 is a graph of storage module log as a function of temperature for the comparative ethylene / 1-octene copolymer (curve 3) and for propylene / ethylene copolymer (curve 3) and for two copolymers in ethylene / 1-octene blocks of the invention prepared with different amounts of chain exchange agent (curves 1);
[023] Figure 7 shows a graph of TMA (1 mm) against flexural modulus for some inventive polymers (represented by diamonds), when compared with some known polymers. The triangles represent Dow's VERSIFY® polymers, the circles represent several random ethylene / styrene copolymers, and the squares represent several Dow AFFINITY® polymers;
[024] Figures 8A and 8B show an overlap of DSC: mixtures of HDPE DMDH 6400 + Example A;
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10/161 [025] Figure 9 shows an overlap of GPC: mixtures of HDPE DMDH 6400 + Example A;
[026] Figure 10 shows a comparison of melt strength: mixtures of HDPE DMDH 6400 + Example A;
[027] Figure 11 shows DSC curves of Inventive and Comparative Samples;
[028] Figure 13 shows dependence on Izod impact notch on temperature;
[029] Figure 14 is a transmission electron micrograph of a mixture of polypropylene and an ethylene / octene block copolymer;
[030] Figure 15 is a transmission electron micrograph of a mixture of polypropylene and a random ethylene / octene copolymer;
[031] THE Figure 16 is an micrography electronics in streaming of a mixture in polypropylene, copolymer in block in ethylene / octene, and a copolymer en bloc in
ethylene / octene.
Detailed description of the invention
General definitions [032] Polymer means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term polymer includes the terms homopolymer, copolymer, terpolymer as well as interpolymer.
[033] Interpolymer means a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer includes the term copolymer (usually used to refer to a polymer prepared from two different monomers),
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11/161 as well as the term terpolymer (usually used to refer to a polymer prepared from three different monomers). It also covers polymers prepared by polymerizing four or more types of monomers.
[034] In general, the term ethylene / aolefin interpolymer refers to polymers comprising ethylene and an α-olefin having 3 or more carbon atoms. Preferably, ethylene comprises the major molar fraction of the entire polymer, i.e., ethylene comprises at least 50 molar percent of the entire polymer. More preferably, ethylene comprises at least about 60 mole percent, at least about 70 mole percent, or at least about 80 mole percent, with the substantial remainder of all polymer comprising at least one other comonomer that is preferably an α-olefin having 3 or more carbon atoms. For many ethylene / octene copolymers, the preferred composition comprises an ethylene content greater than about 80 mole percent of the entire polymer and an octene content of about 10 to about 15, preferably about 15 to about 20 mole percent of all polymer. In some embodiments, ethylene / a-olefin interpolymers do not include those produced in low yields or in a smaller quantity or as a by-product of a chemical process. Although the ethylene / a-olefin interpolymers can be mixed with one or more polymers, the ethylene / aolefin interpolymers are substantially pure and often comprise a major component of the reaction product of a polymerization process.
[035] Ethylene / a-olefin interpolymers comprise
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12/161 ethylene and one or more copolymerizable α-olefinic comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, ethylene / α-olefin interpolymers are block interpolymers, preferably copolymers or multiblock interpolymers. Here, the terms interpolymer and copolymer are used to allow for exchange and / or substitution. In some incorporations, the multi-block copolymer can be represented by the following formula:
(AB) n where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 , or greater. A represents a hard block or segment and B represents a soft block or segment. Preferably blocks A and blocks B connect in a substantially linear manner, as opposed to a substantially branched or substantially star-shaped method. In other incorporations, blocks A and blocks B are randomly distributed along the polymeric chain. In other words, block copolymers usually do not have a structure as follows.
AAA-AA-BBB-BB [036] In other embodiments, block copolymers usually do not have a third type of block, which comprises a different comonomer (s). In other embodiments, each block A and each block B have monomers or comonomers substantially randomly distributed within the block. In other words, neither block A nor
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Block B comprises two or more sub-segments (or sub-blocks) of different composition, such as an end segment, which has a substantially different composition from the rest of the block.
[037] Multiblock polymers typically comprise various amounts of hard and soft blocks or segments. Blocks or hard segments refer to blocks of polymerized units in which ethylene is present in an amount greater than about 95 weight percent, and preferably greater than about 98 weight percent based on the weight of the polymer. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than 5 weight percent, and preferably less than 2 weight percent based on the weight of the polymer. In some incorporations, the hard segments comprise substantially all ethylene.
[038] On the other hand, soft segments refer to blocks of polymerized units in which the content of comonomers (content of monomers other than ethylene) is greater than about 5 percent by weight, preferably greater than about 8 percent by weight, greater than about 10 weight percent, or greater than 15 weight percent based on the weight of the polymer. In some embodiments, the comonomer content in the soft segments can be greater than about 20 percent by weight, greater than about 25 percent by weight, greater than about 30 percent by weight, greater than about 35 percent in weight, greater than about 40 weight percent, greater than about 45 weight percent, greater than about 50 weight percent, or greater than about 60 percent.
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14/161 [039] In some embodiments, the a-olefin content (content of monomers other than ethylene) in the soft segments of the ethylene / a-olefin interpolymers here
disclosed is in fence in 5 per percent molar The fence in 50 per percent molar, in fence in 8 per percent molar The fence in 45 per percent molar, in fence in 10 per percent molar The fence in 40 per percent molar, in fence in 12 per percent molar The fence in 35 per percent molar, or of fence in 15 molar percent the fence in 30
molar percent, based on the total molar amount of aolefin and ethylene in the soft segments.
[040] In other embodiments, the a-olefin content (content of monomers other than ethylene) in the soft segments of the ethylene / a-olefin interpolymers disclosed here is about 35 weight percent to about 75 percent by weight, from about 40 weight percent to about 70 weight percent, from about 45 weight percent to about 65 weight percent, from about 50 weight percent to about 60 percent weight percent, or from about 53 weight percent to about 58 weight percent, based on the total weight of the soft segment polymer.
[041] In certain embodiments, the amount of soft segments in the ethylene / a-olefin multiblock interpolymer disclosed herein is from about 1 weight percent to about 99 weight percent, from about 5 weight percent about 95 percent by weight, from about 10 percent by weight to about 90 percent by weight, from about 15 percent by weight to about 85 percent by weight, from about 20 percent by weight to about 80 weight percent, from about 25 weight percent to about 75 weight percent, from about 30 weight percent to about 70 weight
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15/161 percent by weight, from about 35 percent by weight to about 65 percent by weight, from about 40 percent by weight to about 60 percent by weight, or about 45 percent by weight at about 55 weight percent, based on the total weight of the interpolymer in ethylene / α-olefin multiblocks.
[042] In some embodiments, the amount of hard segments in the interpolymer in ethylene / a-olefin multiblocks disclosed here is about 25 weight percent to about 95 weight percent, about 25 weight percent about 90 weight percent, about 30 weight percent to about 80 weight percent, about 35 weight percent to about 80 weight percent, about 35 percent weight weight to about 75 weight percent, from about 35 weight percent to about 70 weight percent, from about 35 weight percent to about 65 weight percent, about 35 percent by weight to about 60 weight percent, or from about 35 weight percent to about 50 weight percent, based on the total weight of the ethylene / α-olefin multiblock interpolymer.
[043] In other embodiments, the number of hard segments in the interpolymer in ethylene / a-olefin multiblocks disclosed here is greater than 30 weight percent, greater than 35 weight percent, greater than 40 weight percent, greater than 45 percent by weight, greater than 50 percent by weight, greater than 55 percent by weight, greater than 60 percent by weight, greater than 65 percent by weight, greater than 70 percent by weight, greater than 75 weight percent, greater than 80 weight percent, greater than 85 weight percent, greater than 90 weight percent, greater than 95 weight percent, greater than 97.5 weight percent, or greater than 99 percent by weight, with
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16/161 basis on the total weight of the interpolymer in ethylene / a-olefin multiblocks.
[044] The percentage by weight of soft segments and the percentage by weight of hard segments can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed in US Patent Application Publication No. 2006/0199930, filed as US Serial Patent Application No. 11 / 376,835, entitled Ethylene / a-Olefin Block Interpolymers, filed on March 15, 2006, Colin LP Shan, Lonnie Hazlitt, et al., and assigned to Dow Global Technologies Inc.
[045] If used, the term crystalline refers to a polymer that has a crystalline melting point or first order transition (T _m ) determined by differential scanning calorimetry (DSC) or equivalent technique. The term can be used interchangeably with the term semicrystalline. The term amorphous refers to a polymer without a crystalline melting point determined by differential scanning calorimetry (DSC) or equivalent technique.
[046] The term multi-block copolymer or segmented copolymer refers to a polymer comprising two or more chemically distinct segments or regions (also referred to as blocks) that preferably join in a linear fashion, i.e. a polymer comprising chemically differentiated units that come together end-to-end with respect to polymerized ethylene functionality, rather than in pending or grafted mode. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated in them, density, amount of
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17/161 crystallinity, crystallite size attributable to a polymer of such a composition, type and degree of tacticity (isotactic or syndiotactic), regularity or regioirregularity, amount of branching, including long-chain or hyper-branching branching, homogeneity, or any other chemical or physical property. Multiblock copolymers are characterized by unique polydispersity index distributions (PDI or Mw / Mn), block length distribution, and / or block number distribution due to the unique process of preparing copolymers. More specifically, when produced in a continuous process, the polymers desirably have PDI of 1.7 to 2.9, preferably 1.8 to 2.5, more preferably 1.8 to 2.2, and most preferably 1, 8 to 2.1. When produced in a batch or semi-batch process, polymers have PDI of 1.0 to 2.9, preferably 1.3 to 2.5, more preferably 1.4 to 2.0, and most preferably 1, 4 to 1.8.
[047] “Modifying amount for interpolymer impact in ethylene / a-olefin multiblocks is an amount of interpolymer in ethylene / aolefin multiblocks added to a given polymeric composition such that the Izod impact resistance in the notch of the composition at a lower temperature or equal to the ambient temperature is maintained or increased when compared to said notched Izod impact resistance of said composition at the same temperature without the addition of the interpolymer in ethylene / a-olefin multiblocks.
[048] In the following description, all figures published here are approximate values regardless of whether you use the
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18/161
term “fence or “approximate together with they. They may change in 1 percent, 2 percent, 5 per percent, or, sometimes , 10 to 20 per cent O. When to advertise an numeric range with a limit lower R ^L and a limit upper, R ^U , any number what fall in gives banner it is specifically disclosed. In particular, the numbers
following within the range are specifically disclosed: R = R ^l + k * (R ^U - R ^l ), in which k is a variable ranging from 1 percent to 100 percent with an increase of 1 percent, that is, in k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, 50 percent, 51 percent, 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 Percent. In addition, any numerical range defined by two R numbers as defined above is also specifically disclosed.
Ethylene / a-olefin interpolymers [049] The ethylene / a-olefin interpolymers used in embodiments of the invention (also referred to as an "inventive interpolymer or" inventive polymer) comprise ethylene and one or more copolymerizable a-olefinic comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), preferably a multi-block copolymer. Ethylene / aolefin interpolymers are characterized by one or more of the aspects described as follows.
[050] In one aspect, the ethylene / a-olefin interpolymers used in embodiments of the invention have M _w / M _n from about 1.7 to about 3.5 and at least one melting point, T _m , in ° C, and
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19/161 a density, d, in g / cm ³ , with the numerical values of
^T m ^e d correspond to the relation: T _m > -2002.9 + 4538.5 (d) - 2422, 2 (d) ² , and preferably Tm> -6288.1 + 13141 (d) - 6720, 3 (d) ² , and most preferably Tm > 858, 91 - 1825, 3 (d) + 1112, 8 (d) ² . [051] THE Figure 1 illustrates such relationship of point in
melting / density. Unlike traditional random ethylene / a-olefin copolymers whose melting points decrease with decreasing densities, inventive interpolymers (represented by diamonds) exhibit melting points substantially independent of density, particularly when the density is between about 0.87 g / cm ³ and about 0.95 g / cm ³ . For example, the melting points of such polymers are in the range of about 110 ° C to about 130 ° C when the density ranges from 0.875 g / cm ³ to about 0.945 g / cm ³ . In some embodiments, the melting points of such polymers are in the range of about 115 ° C to about 125 ° C when the density ranges from 0.87 g / cm ³ to about 0.945 g / cm ³ .
[052] In another aspect, ethylene / aolefin interpolymers comprise, in polymerized form, ethylene and one or more α-olefins and are characterized by an AT, in ° C, defined as the temperature for the maximum differential scanning calorimetry peak (DSC) minus the temperature for the maximum fractionation peak by crystallization analysis (CRYSTAF) and a heat of fusion, Ah in J / g, and Ah and At satisfy the following relationships: Δτ> -0.1299 (ΔΗ) + 62.81, and preferably Δτ> -0, 1299 (Δη) + 64.38, and more preferably Δτ> -0, 1299 (Δη) + 65.95, for Δη up to 130 J / g. In addition, Δτ is greater than or equal to 48 ° C for Δη greater
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20/161 than 130 J / g. The CRYSTAF peak is determined using at least 5 percent of the cumulative polymer (that is, the peak must represent at least 5 percent of the cumulative polymer), and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature will be 30 ° C, and ÁH is the numerical value of the heat of fusion in J / g. More preferably, the maximum CRYSTAF peak contains at least 10 percent of the cumulative polymer. Figure 2 shows plotted data for inventive polymers as well as for comparative examples. Peak temperatures and peak areas are calculated using the computerized design program provided by the instrument manufacturer. The diagonal line shown for the random comparative polymers of ethylene / octene corresponds to the equation: AT = -0, 1299 (ÁH) + 62.81.
[053] In another aspect, the ethylene / aolefin interpolymers have a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using temperature gradient elution fractionation (TREF), distinguished by the fact that the said fraction has a greater comonomer molar content, preferably at least 5 percent greater, more preferably at least 10 percent greater, than that of a fraction of comparable random ethylene eluting eluting between the same temperatures, with said comparable random ethylene interpolymer having the same comonomers and has a melting index, density, and molar comonomer content (based on the entire polymer) within the 10 percent range of that of the ethylene / a-olefin multiblock interpolymer. Preferably, M _w / M _n of the comparable interpolymer is also within the limits of 10
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21/161 percent of that of the block interpolymer and / or the comparable interpolymer has a total comonomer content within the limits of 10 percent by weight of that of the block interpolymer.
[054] In yet another aspect, ethylene / a-olefin interpolymers are characterized by a percentage elastic recovery, R _e , in deformation of 300 percent, and 1 cycle, measured with a film molded by compression of the interpolymer in multiblocks ethylene / a-olefin, and have a density, d, in grams per cubic centimeter, with the numerical values of Re ed satisfying the following relationship when the ethylene / a-olefin interpolymer is substantially free of a crosslinked phase: R _and > 1481 1629 (d); and preferably R _e > 1491 - 1629 (d); and more preferably R _e > 1501 - 1629 (d); and even more preferably R _e > 1511 - 1629 (d).
[055] Figure 3 shows the effect of density on elastic recovery in non-oriented films made with certain inventive interpolymers and traditional random copolymers. For the same density, the inventive interpolymers have substantially greater elastic recoveries.
[056] In some embodiments, ethylene / a-olefin interpolymers have a tensile strength above 10 MPa, preferably a tensile strength greater than or equal to 11 MPa, more preferably a tensile strength greater than or equal to 13 MPa and / or an elongation at break of at least 600 percent, more preferably at least 700 percent, most preferably at least 800 percent, and most preferably at least 900 percent in one
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22/161 piston separation rate of 11 cm / min.
[057] In other embodiments, ethylene / a-olefin interpolymers have (1) a storage modulus ratio, G '(25 ° C) / G' (100 ° C) from 1 to 50, preferably from 1 to 50 20, more preferably from 1 to 10; and / or (2) a compression strain at 70 ° C less than 80 percent, preferably less than 70 percent, especially less than 60 percent, less than 50 percent, or less than 40 percent to a strain by 0 percent compression.
[058] In still other embodiments, ethylene / a-olefin interpolymers have a compression strain at 70 ° C less than 80 percent, less than 70 percent, less than 60 percent, or less than 50 percent. Preferably, the compression deformation at 70 ° C of the interpolymers is less
that 4 0 percent, less than 30 percent percent, smaller what 20 per percent and can decrease up to about 0 Percent. [059] In some incorporations , the interpolymers in ethylene / a-olefin have a heat of Fusion smaller what 85 J / g and / or resistance to adhesion of smaller pellets or equal to 4800 Pa (100 lb / ft ² ), preferably smaller or like s 2400 Pa (50 pound / foot ² ), and as low how much 0 Pan (0
pound / foot ² ).
[060] In other embodiments, the ethylene / a-olefin interpolymers comprise, in polymerized form, at least 50 molar percent of ethylene and have a compression strain at 70 ° C less than 80 percent, preferably less than 70 percent one percent or less than 60 percent, most preferably less than 40 to 50 percent and decrease to close to 0 percent.
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23/161 [061] In some incorporations, multi-block copolymers have a PDI adapting to a Schultz-Flory distribution instead of a Poisson distribution. Copolymers are further characterized by having both a polydispersed distribution of blocks and a polydispersed distribution of block sizes and having a very likely distribution of block lengths. Preferred multiblock copolymers are those containing 4 or more blocks or segments including terminal blocks. More preferably, the copolymers include at least 5, 10 or 20 blocks or segments including end blocks.
[062] Comonomer content can be measured using any appropriate technique, with techniques based on nuclear magnetic resonance (NMR) spectroscopy being preferred. In addition, for polymers or polymer mixtures having relatively wide TREF curves, first the polymer is desirably fractionated using TREF into fractions each having an eluted temperature range less than or equal to 10 ° C. That is, each eluted fraction has a collection temperature window less than or equal to 10 ° C. Using this technique, said block interpolymers have at least one such fraction having a higher comonomer molar content than that of a corresponding fraction of the comparable interpolymer.
[063] In another aspect, the inventive polymer is an olefinic interpolymer, preferably comprising ethylene and one or more copolymerizable comonomers in polymerized form, characterized by multiple blocks or segments (i.e. at least two blocks) of two or more polymeric monomer units differing chemical or physical properties (block interpolymer), most preferably
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24/161 a copolymer in multiblocks, said block interpolymer having a peak (but not exactly a molecular fraction) that elutes between 40 ° C and 130 ° C (but without collecting and / or isolating individual fractions), characterized by the fact that said peak, having a comonomer content estimated by spectroscopy in the infrared region when expanded using full width / semi-maximum area calculation (FWHM), having a larger molar content of comonomer, preferably at least 5 percent greater, more preferably at least 10 percent greater than that of a comparable random ethylene peak interpolymer, at the same elution temperature and expanded using the full maximum semi-area / width (FWHM) calculation, with the comparable ethylene random interpolymer having the same comonomers and has a melting index, density, and molar content of comonomer (based on the entire polymer) within 10 percent of those of the interpol block number and / or comparable interpolymer has a total comonomer content within the limits of 10 weight percent of that of the block interpolymer. The complete calculation of maximum semi-area / width (FWHM) is based on the ratio of the methyl / methylene response area (CH3 / CH2) of the infrared ATREF detector, with the maximum peak (the maximum height) being identified. from a baseline, and then, the FWHM area is determined. For a distribution measured using an ATREF peak, the FWHM area is defined as the area under the curve between T1 and T2, where T1 and T2 are determined points, to the left and right of the ATREF peak, dividing the peak height by two, and then drawing a horizontal line to the baseline, which intersects the left and right portions of the ATREF curve. A calibration curve is produced for
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25/161 comonomer content using random ethylene / a-olefin copolymers, plotting NMR comonomer content against FWHD area ratio of the ATREF peak. For this infrared method, the calibration curve for the same type of comonomer of interest is generated. The ATREF peak comonomer content of the inventive polymer can be determined by referring to this calibration curve using its FWHM methyl / methylene area (CH3 / CH2) ratio of the TREF peak.
[064] Comonomer content can be measured using any appropriate technique, with techniques based on nuclear magnetic resonance (NMR) spectroscopy being preferred. Using this technique, said block interpolymer has a molar content of comonomer greater than that of a corresponding comparable interpolymer.
[065] Preferably, for ethylene and 1-octene interpolymers, the block interpolymer has a comonomer content of the TREF fraction eluting between 40 and 130 ° C greater than or equal to the amount (-0,2013) T + 20.07 , more preferably greater than or equal to the quantity (-0,2013) T + 21.07, where T is the numerical value of the maximum elution temperature of the fraction of TREF being compared, measured in ° C.
[066] Figure 4 shows graphically an incorporation of the interpolymers in ethylene and 1-octene blocks where a graph of the comonomer content against TREF elution temperature for various comparable ethylene / 1octene interpolymers (random copolymers) is fitted to a line representing (-0,2013) T + 20.07 (continuous line). The line for the equation (-0,2013) T + 21.07 is represented by a dotted line. Also represented are the contents of
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26/161 comonomer for interpolymer fractions in ethylene / 1-octene blocks. All fractions of the block interpolymer have a significantly higher 1-octene content than any line at equivalent elution temperatures. This result is characteristic of olefinic block copolymer and is believed to be due to the presence of differentiated blocks within the polymer chains, both crystalline and amorphous in nature.
[067] Figure 5 shows graphically the TREF curve and comonomer contents of polymeric fractions for Example 5 and Comparative Example F to be discussed below. The peak is fractionated eluting from 40 ° C to 130 ° C, preferably from 60 ° C to 95 ° C for both polymers in 5 ° C increments. The actual data for three of the fractions in Example 5 are represented by triangles. The skilled person can understand that an appropriate calibration curve can be constructed for interpolymers with different comonomer content adjusted to the ATREF temperature values. Preferably, such a calibration curve is obtained using comparative interpolymers of the same monomers, preferably random copolymers prepared using metallocene or other homogeneous catalytic composition. Block olefinic copolymers are characterized by a molar content of comonomer greater than the determined value of the calibration curve at the same elution temperature as ATREF, preferably at least 5 percent higher, more preferably at least 10 percent higher.
[068] In addition to the aspects and properties described above, the inventive polymers can be characterized by one or more additional characteristics. In one respect, the
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27/161 inventive polymer is an olefinic interpolymer preferably comprising ethylene and one or more copolimerizable comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), very preferably a copolymer in multiblocks, said block interpolymer having a molecular fraction that elutes between 40 ° C and 130 ° C, when fractioned using TREF increments, characterized by the fact that said fraction has a higher molar content of comonomer, preferably by at least 5 percent higher, preferably at least 10, 15, 20 or 25 percent higher, than that of a fraction of comparable ethylene random interpolymer eluting between the same temperatures, said said comparable ethylene interpolymer comprising the same comonomers , preferably it is from the same comonomers, and a melting index, density, and molar content of comonomer (based on the whole polymer) within the 10 percent limits of those of the block interpolymer. Preferably, the Mw / Mn of the comparable interpolymer is also within the limits of 10 percent that of the block interpolymer and / or the comparable interpolymer has a total comonomer content within the limits of 10 percent by weight of that of the block interpolymer.
[069] Preferably, the above interpolymers are interpolymers of ethylene and at least one α-olefin, especially those interpolymers having a whole polymer density of about 0.855 to about 0.935 g / cm3, and more especially for polymers having more than about of 1
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28/161 mole percent comonomer, the block interpolymer can have a comonomer content of the TREF fraction eluting between 40 and 130 ° C greater than or equal to the amount (-0.1356) T + 13.89, more preferably greater or equal to the quantity (-0.1356) T + 14.93, and most preferably greater than or equal to the quantity (0.2013) T + 21.07, where T is the numerical value of the maximum elution temperature of the TREF fraction being compared, measured in ° C.
[070] In yet another aspect, the inventive polymer is an olefinic interpolymer comprising, preferably, ethylene and one or more copolymerizable comonomers in polymerized form characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (interpolymer in blocks), most preferably a multi-block copolymer, said block interpolymer having a molecular fraction that elutes between 40 ° C and 130 ° C, when fractioned using TREF increments, characterized by the fact that every fraction having a comonomer content of hair minus about 6 mole percent, have a melting point greater than about 100 ° C. For those fractions having a comonomer content of about 3 molar percent to about 6 molar percent, every fraction has a DSC melting point greater than or equal to about 110 ° C. More preferably, said polymeric fractions having at least 1 molar percent of comonomer, have a melting point by DSC that corresponds to the equation: T _m > (5.5926) (molar percentage of comonomer in the fraction) +135.90.
[071] In another aspect, the inventive polymer is an olefinic interpolymer, preferably comprising ethylene and one or more copolimerizable comonomers in form
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Polymerized 29/161 characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), most preferably a multi-block copolymer, said block interpolymer having a molecular fraction that elutes between 40 ° C and 130 ° C, when fractioned using increments
in TREF, characterized by the fact that all f feed that It has an elution temperature by ATREF bigger or equal about in 76 ° C, have a melting enthalpy (heat fusion) measure per DSC corresponding to the equation: Heat fusion (J / g) < (3, 1718) (ATREF elution temperature in ° C) -136.58.
[072] The inventive block interpolymers have a molecular fraction that elutes between 40 ° C and 130 ° C, when fractioned using TREF increments, characterized by the fact that any fraction that has an ATREF elution temperature between 40 ° C and less that at about 76 ° C, having a melting enthalpy (heat of melting) measured by DSC corresponding to the equation: Melting heat (J / g) <(1.1312) (elution temperature ATREF in ° C) +22, 97.
[073] ATREF peak comonomer composition measurement by infrared detector [074] The TREF peak comonomer composition can be measured using an IR4 infrared detector obtainable from Polymer Char, Valencia, Spain (http: //www.polymerchar. with/).
[075] The “composition mode of the detector is equipped with a measurement sensor (CH2) and composition sensor (CH3) that fix infrared narrow band filters in the region of 2800-3000 cm ^-1 . The measurement sensor detects the methylene (CH ₂ ) carbons in the polymer (which relate directly to the
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30/161 concentration of polymer in solution) while the composition sensor detects the methyl groups (CH ₃ ) of the polymer. The mathematical ratio of the composition signal (CH ₃ ) divided by the measurement signal (CH2) is sensitive to the comonomer content of the polymer measured in solution and its response is calibrated with known standards of ethylene / alpha-olefin copolymer.
[076] The detector when used with an ATREF instrument provides both a concentration signal response (CH2) and a composition response signal (CH3) of the polymer eluted during the TREF process. A specific polymer calibration can be created by measuring the area ratio from CH3 to CH2 for polymers with known comonomer content (preferably measured by NMR). The comonomer content of an ATREF peak of a polymer can be estimated by applying the reference calibration of the area ratio to the individual CH3 and CH2 response (ie, CH3 / CH2 area ratio against comonomer content).
[077] The peak area can be calculated using a full width / maximum semi-area (FWHM) calculation after applying the baselines to integrate the individual signal responses from the TREF chromatogram. The calculation of the total width area / maximum semi-area is based on the area response ratio of methyl to methylene [CH3 / CH2] of the infrared detector of ATREF, with the largest peak (the highest) being identified from baseline, and then the FWHM area is determined. For a distribution measured using an ATREF peak, the FWHM area is defined as the area under the curve between T1 and T2, where T1 and T2 are determined points, to the left and right of the ATREF peak, dividing the peak height by two, and then drawing a horizontal line to the line
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31/161 base, which intersects the left and right portions of the ATREF curve.
[078] The application of spectroscopy in the infrared region to measure the comonomer content of polymers in this ATREF infrared method is, in principle, similar to that of GPC / FTIR systems described in the following references: Markovich, Ronald P .; Hazlitt, Lonnie G .; Smith, Linley, Development of gel-permeation chromatography-Fourier transform infrared spectroscopy for characterization of ethylene-based polyolefin copolymers, Polymeric Materials Science and Engineering (1991), 65, 98100; and Deslauriers, P. J .; Rohlfing, D.C .; Shieh, E.T., Quantifying short chain branching microstructures in ethylene-1-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR), Polymer (2002), 43, 59-170.
[079] In other embodiments, the ethylene / a-olefin interpolymer is characterized by an average block index, ABI, ranging from greater than zero to about 1.0 and a molecular weight distribution, M _w / M _n , greater than about 1.3. The average block index, ABI, is the weight average of the block index (BI) of each of the polymeric fractions obtained in preparative TREF of 20 ° C and 110 ° C, with an increase of 5 ° C:
ABI = S (wiBIi) where BIi is the block index of the i-th fraction of the inventive ethylene / a-olefin interpolymer obtained in preparative TREF, and wi is the weight percentage of the i-th fraction.
For each polymeric fraction, BI is defined using one of the following two equations (both giving the same BI value):
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32/161
1 / Τχ - 1 / Τχο LnPx - LnPxo
BI = _____________ or BI = ________________
1 / T _A - 1 / T _A B LnP _A - LnP _M where T _x is the elution temperature of ATREF of the i-th fraction (expressed, preferably, in Kelvin), P _x is the molar fraction of ethylene of i- th fraction, which can be measured by NMR or IR as described above. PAB is the molar fraction of ethylene in the entire ethylene / a-olefin interpolymer (before fractionation), which can also be measured by NMR or IR. The TA and PA values are, respectively, the ATREF elution temperature and the molar fraction of ethylene for pure hard segments (which refer to the crystalline segments of the interpolymer). As a first order approximation, the T _A and P _A values are adjusted for those of high density polyethylene homopolymer, if the actual values for the hard segments are not available. For calculations performed here, T _A is 372K, P _A is 1.
[080] T _AB is the ATREF temperature for a random copolymer of the same composition and having a molar ethylene fraction of PAB. TAB can be calculated from the following equation:
Ln Pab = α / TAB + β where a and β are two constants that can be determined by calibration using a number of known random ethylene copolymers. It should be noted that α and β can vary from instrument to instrument. In addition, it would be necessary to create your own calibration curve with the polymeric composition of interest and also in a range of similar molecular weights of the fractions. There is a slight molecular weight effect. If the calibration curve is obtained from similar molecular weight ranges, such an effect would be
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33/161 essentially negligible. In some embodiments, random ethylene copolymers satisfy the following relationship:
Ln P = -237.83 / T _aTref + 0.639
TXO is the ATREF temperature for a random copolymer of the same composition and having a molar ethylene fraction of PX. T _xo can be calculated from Ln P _X = a / T _XO + β. On the other hand, PXO is the molar fraction of ethylene for a random copolymer of the same composition and having an ATREF temperature of T _x , which can be calculated from Ln P _XO = α / Τ _χ + β.
[081] Once the block index (BI) is obtained for each fraction of preparative TREF, one can calculate the weight average block index, ABI, for the entire polymer. In some embodiments, ABI is greater than zero, but less than about 0.3 or about 0.1 to about 0.3. In other incorporations, ABI is greater than 0.3 and up to about 1.0. Preferably, ABI should be in the range of about 0.4 to about 0.7, about 0.5 to about 0.7, or about 0.6 to about 0.9. In some incorporations, ABI is in the range of about 0.3 to about 0.9, about 0.3 to about 0.8, or about 0.3 to about 0.7, about from 0.3 to about 0.6, from about 0.3 to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABI is in the range of about 0.4 to about 1.0, about 0.5 to about 1.0, or about 0.6 to about 1.0, about from 0.7 to about 1.0, from about 0.8 to about 1.0, or from about 0.9 to about 1.0.
[082] Another characteristic of the inventive ethylene / αolefin interpolymer is that it comprises at least a polymeric fraction that can be obtained by preparative TREF, being
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34/161 that the fraction has a block index greater than about 0.1 and up to about 1.0 and a molecular weight distribution, M _w / M _n , greater than about 1.3. In some incorporations, the polymeric fraction has a block index greater than about 0.6 and up to about 1.0, greater than about 0.7 and up to about 1.0, greater than about 0.8 and up to about 1.0, or greater than about 0.9 and up to about 1.0. In other embodiments, the polymeric fraction has a block index greater than about 0.1 and up to about 1.0, greater than about 0.2 and up to about 1.0, greater than about 0.3 and up to about 1.0, greater than about 0.4 and up to about 1.0, or greater than about 0.5 and up to about 1.0. In other incorporations, the polymeric fraction
has a block index greater than about 0.1 and even about 0.5, higher what about 0, 2 and up fence in 0.5, greater than about 0, 3 and until about in 0.5, or bigger what fence of 0.4 and until about in 0.5. Already in others incorporations, the fraction polymeric has an index in blocks bigger what fence of 0.2 and
up to about 0.9, greater than about 0.3 and up to about 0.8, greater than about 0.4 and up to about 0.7, or greater than about 0.5 and up to about 0 , 6.
[083] For copolymers of ethylene and an α-olefin, the inventive polymers preferably have (1) PDI of at least 1.3, more preferably at least 1.5, at least 1.7, or at least minus 2.0, and most preferably from at least 2.6 to a maximum of 5.0, more preferably up to a maximum of 3.5, and especially up to a maximum of 2.7; (2) a heat of fusion less than or equal to 80 J / g;
(3) an ethylene content of at least 50 weight percent; (4) a glass transition temperature, Tg, less than -25 ° C, more preferably less than -30 ° C; and / or (5) one and
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35/161 only one T _m .
[084] Additionally, the inventive polymers may have, alone or in combination with any other properties disclosed herein, a storage module, G ', such that log (G') is greater than or equal to 400 kPa, preferably greater than or equal to 1.0 MPa, at a temperature of 100 ° C. In addition, the inventive polymers have a relatively horizontal storage module as a function of the temperature in the range 0 to 100 ° C (illustrated in Figure 6) that is characteristic of block copolymers, and until now unknown to an olefinic copolymer, especially for an ethylene copolymer and one or more C _3-8 aliphatic α-olefins. (In this context, the term relatively horizontal means that log G '(in Pascal) decreases less than an order of magnitude between 50 and 100 ° C, preferably between 0 and 100 ° C).
[085] Polymers can also be characterized by a depth of penetration by thermomechanical analysis of 1 mm at a temperature of at least 90 ° C as well as a flexural modulus of 20 MPa (3 kpsi) to 90 MPa (13 kpsi). Alternatively, the inventive interpolymers can have a penetration depth by thermomechanical analysis of 1 mm at a temperature of at least 104 ° C as well as a flexural modulus of 20 MPa (3 kpsi). They can be characterized by having an abrasion resistance (or loss of volume) of less than 90 mm ³ . Figure 7 shows TMA (1mm) against flexural modulus for the inventive polymers, when compared with other known polymers. The inventive polymers have a balance of flexibility / thermal resistance significantly better than that of other polymers.
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36/161 [086] Additionally, ethylene / aolefin interpolymers can have a melting index, I ₂ , of 0.01 to 2000 g / 10 minutes, preferably 0.01 to 1000 g / 10 minutes, more preferably of 0.01 to 500 g / 10 minutes, and especially from 0.01 to 100 g / 10 minutes. In certain embodiments, ethylene / a-olefin interpolymers have a melting index, I2, of 0.01 to 10 g / 10 minutes, 0.5 to 50 g / 10 minutes, of 1 to 30 g / 10 minutes , from 1 to 6 g / 10 minutes or from 0.3 to 10 g / 10 minutes. In certain embodiments, the melt index for ethylene / a-olefin polymers is 1 g / 10 minutes, 3 g / 10 minutes or 5 g / 10 minutes.
[087] Polymers can have molecular weights, M _w , from 1,000 g / mol to 5,000,000 g / mol, preferably from 1000 g / mol to 1,000,000 g / mol, more preferably from 10,000 g / mol to 500,000 g / mol, and especially from 10,000 g / mol to 300,000 g / mol. The density of the inventive polymers can be from 0.80 g / cm ³ to 0.99 g / cm ³ and preferably for polymers containing ethylene, from 0.85 g / cm ³ to 0.97 g / cm ³ . In certain embodiments, the density of ethylene / aolefin polymers ranges from 0.860 g / cm ³ to 0.925 g / cm ³ or from 0.867 g / cm ³ to 0.910 g / cm ³ .
[088] The polymer manufacturing process was disclosed in the following patent applications: U.S. provisional patent application No. 60 / 553,906, filed on March 17, 2004; provisional U.S. patent application No. 60 / 662,937, filed March 17, 2005; provisional U.S. patent application No. 60 / 662,939, filed March 17, 2005; provisional U.S. patent application No. 60/5662938, filed March 17, 2005; provisional U.S. patent application No. 61 / 024,674, filed on
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January 37/161, 2008; PCT application No. PCT / US2005 / 008916, filed on March 17, 2005; PCT application No. PCT / US2005 / 008915, filed on March 17, 2005; and PCT application No. PCT / US2005 / 008917, filed on March 17, 2005. For example, such a method comprises contacting ethylene and optionally one or more addition-curing monomers other than ethylene under addition-curing conditions with a catalytic composition comprising the reaction mixture or product resulting from combining: (A) a first olefinic polymerization catalyst having a high comonomer incorporation index, (B) a second olefinic polymerization catalyst having a comonomer incorporation index of less than 90 percent preferably less than 50 percent, most preferably less than 5 percent of the comonomer incorporation index of catalyst (A) _r and (C) a chain exchange agent.
[089] Representative catalysts and chain exchange agents are as follows.
[090] Catalyst (Al) is dimethyl [N- (2 _r 6-di (1-methyl ethyl) phenyl) starch) (2-isopropyl phenyl) (0C-naphthalen-2-diyl (6pyridin-2-diyl) methane )] hafnium, prepared in accordance with the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429.024, deposited on May 2, 2003, and WO 04/24740.
(H ₃ C) ₂ HC _c 'h ₃ ch ₃
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38/161 [091] The catalyst (Α2) is dimethyl [N- (2,6-di (1-methyl ethyl) phenyl) starch) (2-methylphenyl) (1,2-phenylene- (6-pyridin-2diyl ) methane)] hafnium, prepared in accordance with the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429,024, deposited on May 2, 2003, and WO 04/24740.
[092] The catalyst (A3) is dibenzyl bis [N, Ν '- (2,4,6tri (methylphenyl) starch) ethylenediamine] hafnium.
[093]
(dibenzo-1H-pyrrol-l-yl) -5- (methyl) phenyl) -2-phenoxy methyl) cyclohexane-1,2-diyl zirconium (IV), prepared substantially in accordance with US-A teachings
2004/0010103.
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[094] The catalyst (Bl) is dibenzyl 1,2-bis- (3 _r 5 ditherciobutyl phenylene) (1- (N- (1-methyl ethyl) imino) methyl) (2C (CH ₃ ) 3
oxoyl) zirconium.
[095] Catalyst (B2) is dibenzyl 1,2-bis- (3,5diterciobutyl phenylene) (1- (N- (2-methylcyclohexyl) imino) methyl) (2-oxoyl) zirconium.
[096] The catalyst (Cl) is dimethyl (terciobutyl starch) dimethyl (3-N-pyrrolyl-1,2,3,3a, 7a-r | -inden-lil) titanium silane prepared substantially according to the techniques of the USP patent 6,268,444:
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40/161
C (CH ₃ ) 3 [097] The catalyst (C2) is dimethyl (terciobutyl starch) di (4-methylphenyl) (2-methyl-1, 2,3,3a, Va-ηinden-1-yl) titanium prepared substantially according to the teachings of US-A-2003/004286:
[098] The catalyst (C3) is dimethyl (terciobutyl starch) di (4-methylphenyl) (2-methyl-1, 2,3,3a, 8a-T | -sindacen-1-yl) silane titanium prepared substantially according to the teachings of US-A-2003/004286:
[099] The catalyst (Dl) is bis (dimethyl-disiloxane) (inden-1-yl) zirconium dichloride obtainable from Sigma-Aldrich:
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[100] Exchange agents. The exchange agents employed include diethyl zinc, diisobutyl zinc, di (nhexyl) zinc, triethyl aluminum, trioctyl aluminum, triethyl gallium, bis (dimethyl (terciobutyl) siloxane) isobutyl aluminum, bis (di (trimethyl silyl) amide isobutyl aluminum, di (pyridine-2-methoxide) n-octyl aluminum, bis (n-octadecyl) isobutyl aluminum, bis (di (n-pentyl) amide) isobutyl aluminum, n-octyl aluminum bis (2,6diterciobutyloxide), di (ethyl ) amide) of n-octyl aluminum, bis (terciobutyl dimethyl siloxide) of ethyl aluminum, di (bis (trimethyl silyl) amide) ethyl aluminum, bis (2,3,6,7-dibenzo-l-aza-cycloheptanoamide ) of ethyl aluminum, bis (2,3,6,7-dibenzo-l-aza-cycloheptane amide) of n-octyl aluminum, bis (dimethyl (terciobutyl) siloxide) of noctil aluminum, (2,6-diphenyl -phenoxy) of ethyl zinc, and (terciobutoxide) of ethyl zinc.
[101] Preferably, the foregoing process may take the form of a continuous solution process to form block copolymers, especially multi-block copolymers, preferably multi-block linear copolymers of two or more monomers, more especially ethylene and a cycloolefin or olefin of 03-20 ^ θ very especially ethylene and oc-olefin of 0 ₄ _ ₂ ολ using
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42/161 multiple catalysts that are incapable of interconversion. That is, the catalysts are chemically distinct. Under continuous solution polymerization conditions, the process is ideally suited for polymerization of monomer mixtures in high monomer conversions. In these polymerization conditions, the exchange of the chain exchange agent by the catalyst becomes advantageous compared to the chain growth, and copolymers are formed in multi-blocks, especially copolymers in linear multi-blocks with high efficiency.
[102] The inventive interpolymers can be distinguished from conventional random copolymers, physical mixtures of polymers, and block copolymers prepared via sequential addition of monomers, fluxionary catalysts, and live cationic or anionic polymerization techniques. In particular, compared to a random copolymer of the same monomers and monomer content in module or equivalent crystallinity, the inventive interpolymers have better (higher) thermal resistance, measured by melting point, higher penetration temperature by TMA, higher tensile strength in elevated temperature, and / or greater torsion storage module and elevated temperature determined by dynamic-mechanical analysis. Compared to a random copolymer containing the same monomers and the same monomer content, the inventive interpolymers have less compression deformation, particularly at elevated temperatures, less stress relaxation, greater creep resistance, greater breaking strength, greater adhesion resistance, faster disposal due to higher crystallization temperature (solidification), better recovery
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43/161 (particularly at high temperatures), better abrasion resistance, greater retraction force, and better load and oil acceptance.
[103] The inventive interpolymers also exhibit a unique relationship of crystallization and branching distribution. That is, the inventive interpolymers have a relatively large difference between the maximum peak temperature measured using CRYSTAF and DSC as a function of melting heat, especially when compared to random copolymers containing the same monomers and the same level of monomers or physical mixtures polymers, such as a mixture of a high density polymer and a lower density copolymer, in equivalent overall density. It is believed that this unique characteristic of the inventive interpolymers is due to the unique distribution of the comonomer in blocks within the polymeric main chain. In particular, inventive interpolymers may comprise alternating blocks of different comonomer content (including blocks of homopolymers). The inventive interpolymers may also comprise a number and / or block size distribution of polymeric blocks of different density or comonomer content, which is a Schultz-Flory type of distribution. In addition, the inventive interpolymers also have a single maximum melting point and crystallization temperature profile that is substantially independent of polymer density, modulus and morphology. In a preferred embodiment, the microcrystalline order of the polymers demonstrates characteristic spherulites and lamellae that are distinguishable from block or random copolymers, even at PDI values that are less than 1.7, or even less than 1.5, decreasing even less than
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1.3.
[104] In addition, inventive interpolymers can be prepared using techniques to influence the degree or level of blockiness. That is, the amount of comonomer and length of each block or segment of polymer can be changed by controlling the ratio and type of catalysts and exchange agent as well as the polymerization temperature, and other polymerization variables. A surprising advantage of this phenomenon is the discovery that when the degree of blocking increases, the optical properties, resistance to breakage, and high temperature recovery properties of the resulting polymer improve. In particular, opacity decreases while clarity, resistance to breakage, and high temperature recovery properties increase when the average number of blocks in the polymer increases. By selecting combinations of catalysts and exchange agents having the desired chain transfer capacity (high exchange rates with low levels of chain termination) other forms of polymer termination will be effectively eliminated. Consequently, little or no elimination of β hydride in the polymerization of ethylene / a-olefin comonomer mixtures according to embodiments of the invention, and the resulting crystalline blocks are very, or substantially completely linear with little or no long chain branching. .
[105] Polymers with very crystalline chain ends can be selectively prepared according to embodiments of the invention. In elastomer applications, reducing the relative amount of polymer that ends with an amorphous block reduces the dilution effect
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45/161 intermolecular in the crystalline regions. This result can be obtained by choosing chain exchange agents and catalysts having an appropriate response to hydrogen or other chain terminating agents. Specifically, if the catalyst that produces very crystalline polymer is more susceptible to chain termination (such as by the use of hydrogen) than the catalyst responsible for producing the less crystalline polymeric segment (such as through greater comonomer incorporation, region-error, or formation of atactic polymer), then the very crystalline polymeric segments will preferably populate the end portions of the polymer. Not only are the resulting terminal groups crystalline, but in response to termination, the very crystalline polymer-forming catalytic site is once again available to restart polymer formation. The polymer initially formed is, therefore, another very crystalline polymeric segment. Consequently, both ends of the resulting multi-block copolymer are preferably very crystalline.
[106] The ethylene / a-olefin interpolymers used in the embodiments of the invention are preferably ethylene interpolymers with at least one C3C ₂₀ α-olefin. Copolymers of ethylene and C3-C ₂₀ α-olefin are especially preferred. The interpolymers can further comprise C ₄ -C ₁₈ diolefin and / or alkenyl benzene. Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or unconjugated dienes, polyenes, alkenyl benzenes, etc. Examples of such comonomers include C3-C20 aolefins such as propylene, isobutylene, 1-butene,
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1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Especially preferred are 1-butene and 1-octene. Other suitable monomers include styrene, styrenes substituted by halogen or alkyl, vinyl benzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics (for example, cyclopentene, cyclohexene and cyclooctene).
[107] Although ethylene / a-olefin interpolymers are preferred polymers, other ethylene / olefin polymers can also be used. When used herein, the term olefins refers to a family of compounds based on unsaturated hydrocarbons with at least one carbon-carbon double bond. Depending on the selection of catalysts, any olefin can be used in embodiments of the invention. Preferably, the appropriate olefins are C ₃ -C ₂₀ aromatic and aliphatic compounds containing vinyl unsaturation, as well as cyclic compounds such as cyclobutene, cyclopentene, di-cyclopentadiene, and norbornene, including, but not limited to, substituted norbornene at positions 5 and 6 with C ₁ -C ₂₀ hydrocarbyl or cyclohydrocarbyl groups. Mixtures of such olefins as well as mixtures of such olefins with C4C40 diolefin compounds are also included.
[108] Examples of olefinic monomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1 -tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6dimethyl-1-heptene, 4-vinyl-cycle -hexene, vinyl-cyclohexane, norbornadiene, ethylidene norbornene, cyclopentene,
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47/161 hexene, di-cyclopentadiene, cyclooctene, C ₄ -C ₄ o dienes, including, but not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5- hexadiene, 1,7-octadiene, 1,9-decadiene, other C ₄ -C ₄₀ α-olefins, and the like. In certain embodiments, α-olefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or a combination thereof. While potentially any hydrocarbon containing a vinyl group can be used in embodiments of the invention, practical issues such as monomer availability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer can become more problematic when molecular weight becomes too high.
[109] The polymerization processes described herein are well suited for the production of olefinic polymers comprising aromatic monovinylidene monomers including styrene, o-methyl-styrene, p-methyl-styrene, terciobutyl-styrene, and the like. In particular, interpolymers comprising ethylene and styrene, can be prepared following the teachings here. Optionally, copolymers comprising ethylene, styrene and a C ₃ -C ₂₀ α-olefin can be prepared, optionally comprising a C4-C20 diene, having improved properties.
[110] Suitable unconjugated diene monomers may include cyclic, branched or normal chain hydrocarbon dienes having 6 to 15 carbon atoms. Examples of suitable unconjugated dienes include, but are not limited to, normal chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene, 1,7octadiene, 1,9-decadiene, acyclic chain dienes
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48/161 branched, such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6octadiene, 3,7-dimethyl-1,7-octadiene and mixtures of dihydromyricene and dihydro isomers -okinene, single ring alicyclic dienes, such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,5-cyclododecadiene, and bridged and alicyclic fused multi-ring dienes , such as tetrahydroindene, methyl tetrahydroindene, di-cyclopentadiene, bicyclo- (2,2,1) -hepta2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene2-norbornene, 5- (4-cyclopentyl) -2-norbornene, 5-cyclohexylidene- 2-norbornene, 5-vinyl-2-norbornene, and norbornadiene. Of the dienes typically used to prepare EPDMs, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene ( MNB), and dicyclopentadiene (DCPD). Especially preferred dienes are: 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).
[111] A class of desirable polymers, which can be used according to embodiments of the invention includes ethylene elastomeric interpolymers, a C ₃ C ₂₀ α-olefin, especially propylene, and optionally, one or more diene monomers. The preferred α-olefins for use in this embodiment of the present invention are designated by
formula CH ₂ = CHR *, where R * is one linear alkyl group or branched from 1 to 12 atoms in carbon. Examples of α- olefins appropriate include,but they are not limited The, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-
methyl-1-pentene, and 1-octene. An α-olefin particularly
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Preferred 49/161 is propylene. Propylene-based polymers are generally referred to in the art as EP or EPDM polymers. Suitable dienes used in the preparation of such polymers, especially polymers of the EPDM type in multiblocks include conjugated or unconjugated, cyclic or polycyclic, normal or branched chain dienes comprising from 4 to 20 carbon atoms. Preferred dienes include 1,4 pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferred diene is 5-ethylidene2-norbornene.
[112] Since polymers containing diene comprise alternating blocks or segments containing greater or lesser amounts of diene (including none) and α-olefin (including none), the amount of diene and α-olefin can be reduced without loss of subsequent polymeric properties . That is, as the diene and α-olefin monomers preferentially incorporate into one type of polymer block rather than uniformly or randomly throughout the polymer, they are used more efficiently and subsequently, the crosslinking density can be better controlled of the polymer. Such cross-linkable elastomers and cured products have advantageous properties, including a higher limit of tensile strength and better elastic recovery.
[113] In some embodiments, the inventive interpolymers prepared with two catalysts incorporating different amounts of comonomer have a block weight ratio thus formed of 95: 5 to 5:95. Desirably, elastomeric polymers have an ethylene content of 20 to 90 percent, a diene content of 0.1 to 1.0 percent, and a
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50/161 10 to 80 percent α-olefin content, based on the total polymer weight. Preferably still, multiblock elastomeric polymers have an ethylene content of 60 to 90 percent, a diene content of 0.1 to 10 percent, and an α-olefin content of 10 to 40 percent, based on weight total polymer. Preferred polymers are high molecular weight polymers, having a weight average molecular weight (M _w ) of 10,000 to about 2,500,000, preferably from 20,000 to 500,000, more preferably from 20,000 to 350,000, and a polydispersity less than 3.5 , more preferably less than 3.0, and a Mooney viscosity (ML (1 + 4) 125 ° C) of 1 to 250. More preferably, such polymers have an ethylene content of 65 to 75 percent, a content of diene 0 to 6 percent, and α-olefin content from 20 to 35 percent.
[114] Ethylene / α-olefin interpolymers can be functionalized by incorporating at least one functional group in their polymeric structure. Exemplary functional groups may include, for example, ethylenically unsaturated mono and difunctional carboxylic acids, mono and ethylenically unsaturated difunctional carboxylic acids, salts thereof and esters thereof. Such functional groups can be grafted into an ethylene / α-olefin interpolymer, or they can be copolymerized with ethylene and an optional additional comonomer to form an ethylene interpolymer, the functional comonomer and optionally other comonomers. Means for grafting functional groups into polyethylene are described, for example, in U.S. Patent Nos. 4,762,890, 4,927,888, and 4,950,541. A particularly useful functional group is malic anhydride.
[115] The quantity of the functional group present in the
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51/161 functional interpolymer may vary. The functional group can typically be present in a functionalized copolymer-type interpolymer in an amount of at least about 1.0 weight percent, preferably at least about 5 weight percent, and more preferably at least about 7 weight percent percent by weight. The functional group will typically be present in a copolymer-type functionalized interpolymer in an amount less than about 40 weight percent, preferably less than about 30 weight percent, and more preferably less than about 25 weight percent. Test methods [116] In the following examples, the following analytical techniques are used:
GPC method for samples 1-4 and AC [117] An automatic liquid handling robot equipped with a set of needles heated to 160 ° C is used to add sufficient 1,2,4-trichlorobenzene stabilized with 300 ppm Ionol for each sample of dry polymer to give a final concentration of 30 mg / mL. A small glass stirring rod is placed in each tube and the samples are heated at 160 ° C for 2 hours in a heated orbital shaker rotating at 250 rpm. The concentrated polymeric solution is then diluted to 1 mg / mL using the automatic liquid handling robot and the set of needles heated to 160 ° C.
[118] A Symyx Rapid GPC system is used to determine the molecular weight data for each sample. A set of Gilson 350 pumps, at a flow rate of 2.0 mL / min, is used to pump purging helium in 1,2-dichlorobenzene stabilized with 300 ppm Ionol as the mobile phase through three 300 mm x 7 columns 5 mm PI gel of 10
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52/161 micrometers (end) mixed B, placed in series and heated to 160 ° C. A Polymer Labs ELS 1000 detector is used with the evaporator set at 250 ° C, the nebulizer set at 165 ° C, and the nitrogen flow rate adjusted to 1.8 SLM at a pressure of 400-600 kPa (60- 80 psi) of N ₂ . The polymeric samples are heated to 160 ° C and each sample is injected into a 250 llL loop using the liquid handling robot and a heated needle. The serial analysis of the polymeric samples uses two linked loops and overlapping injections are used. Sample data is collected and analyzed using the Symyx Epoch ^TM software. The peaks are integrated manually and the reported molecular weight information is incorrect against a standard polystyrene calibration curve.
CRYSTAF standard method [119] Branch distributions are determined by analytical crystallization fractionation (CRYSTAF) using a commercially obtainable CRYSTAF 200 unit from PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160 ° C (0.66 mg / mL) for 1 hour and stabilized at 95 ° C for 45 minutes. Sampling temperatures range from 95 to 30 ° C at a cooling rate of 0.2 ° C / min. An infrared detector is used to measure the concentrations of polymeric solution. The cumulative soluble concentration is measured when the polymer crystallizes while the temperature decreases. The analytical derivative of the cumulative profile reflects the short chain branch distribution of the polymer.
[120] The CRYSTAF peak area and temperature are identified by the peak analysis module included in the CRYSTAF software (version 2001.b, PolymerChar, Valencia,
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Spain). The CRYSTAF peak discovery routine identifies the peak temperature as a maximum on the dW / dT curve and the area between the widest positive inflections on either side of the peak identified on the derived curve. To calculate the CRYSTAF curve, the processing parameters
favorite are with a temperature limit 70 ° C and with parameters in smoothing in curves above the limit of temperature in 0.1 and below of limit temperature of 0.3.
Standard DSC method (excluding samples 1-4 and A-C) [121] The results of differential scanning calorimetry (DSC) are determined using a DSC TAI model Q1000 equipped with an RSC cooling accessory and an automatic sample collector. A flow of nitrogen purge gas of 50 mL / min is used. The sample is pressed into a thin film and melted in the press at about 175 ° C and then cooled in air at room temperature (25 ° C). Then, 3-10 mg of material is cut into a 6 mm diameter disc, weighed exactly, placed in a light aluminum pan (ca 50 mg), and then closed, set in place. The thermal behavior of the
sample is under study with the profile in temperature Following. Heats up quickly the sample The 180 ° C and remains isothermally for 3 minutes to end to remove any
previous thermal history. Then, the sample is cooled to 40 ° C at a cooling rate of 10 ° C / min and kept at -40 ° C for 3 minutes. The sample is then heated to 150 ° C at a heating rate of 10 ° C / min. The cooling and second heating curves are recorded.
[122] DSC melting peak is measured as the maximum thermal flow rate (W / g) with respect to the linear baseline drawn between -30 ° C and the melting end. Heat is measured
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54/161 melting as the area under the melting curve between -30 ° C and the melting end using a linear baseline.
GPC method (excluding samples 1-4 and A-C) [123] The gel permeation chromatographic system consists of the Polymer Laboratories instrument model PL-210 or the Polymer Laboratories instrument model PL-220. The column and carousel compartments are operated at 140 ° C. Three 10 micron Mixed-B columns from Polymer Laboratories are used. The solvent is 1,2,4-trichlorobenzene. The samples are prepared in a concentration of 0.1 gram of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). The samples are prepared by gently shaking for 2 hours at 160 ° C. The injection volume used is 100 microliters and the flow rate is 1.0 mL / minute.
[124] The GPC column set calibration was performed with 21 polystyrene standards of narrow molecular weight distribution with molecular weights ranging from 580 to 8,400,000, arranged in 6 cocktail mixes with at least a dozen separation between molecular weights individual. The standards are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights greater than or equal to 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80 ° C with gentle agitation for 30 minutes. Mixtures of narrow patterns are used first and in descending order from the highest molecular weight component to minimize degradation. The peak molecular weights of polystyrene standard are converted to weights
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55/161 molecular polyethylene using the following equation (described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): ^M polyethylene ^{0.431 (M} polystyrene) · [125] Calculations of equivalent molecular weight of polyethylene are performed using the Viscotek software from TriSEC version 3.0.
Compression strain [126] Compression strain is measured according to ASTM D 395. The sample is prepared by stacking round discs 25.4 mm in diameter with thicknesses of 3.2 mm, 2.0 mm, and 0 , 25 mm until a total thickness of 12.7 mm is reached. The discs are cut from 12.7 cm x 12.7 cm compression-molded plates molded with a thermal press under the following conditions: zero pressure for 3 min at 190 ° C, followed by 86 MPa for 2 min at 190 ° C, followed by internal cooling of the press with cold running water at 86 MPa.
Density [127] Samples are prepared for density measurement according to ASTM D 1928. Measurements are made within 1 hour of sample pressing using ASTM D 792, Method B.
Flexion / elasticity module / Storage module [128] The samples are molded by compression using ASTM D 1928. The flexion module and the 2 percent elasticity module are measured according to ASTM D-790. The storage module is measured according to ASTM D 5026-01 or equivalent technique.
Optical properties [129] 0.4 mm thick films are shaped by
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56/161 compression using a thermal press (Carver Model # 40954PR1001R). The pellets are placed between poly (tetrafluoroethylene) sheets, heated to 190 ° C and 380 kPa (55 psi) for 3 minutes, followed by 1.3 MPa for 3 minutes, and then 2.6 MPa for 3 minutes. Then, the films are cooled in the press, with cold running water at 1.3 MPa for 1 minute. Compression-molded films are used for optical measurements, behavior related to traction, recovery, and stress relaxation.
[130] Lightness is measured using a BYK Gardner dry mist intensity meter specified in ASTM D 1746.
[131] The 45 ° brightness is measured using a 45 ° BYK Gardner micro brightness meter specified in ASTM D-2457.
[132] Internal opacity is measured using a BYK Gardner dry mist intensity meter based on ASTM D 1003, procedure A. Mineral oil is applied to the film surface to remove surface scratches.
Mechanical properties - Tensile, hysteresis, and rupture [133] The stress-strain behavior in uniaxial stress is measured using ASTM D 1708 micro-tensile samples. The samples are stretched with an Instron at 500% min ^-1 at 21 ° Ç. The tensile strength and elongation at break module are reported from an average of 5 samples.
[134] 100% and 300% hysteresis is determined from cyclic loading for 100% and 300% stresses using micro-tensile samples of ASTM D 1708 with an Instron ^TM instrument. The sample is loaded and unloaded at 267% min ^-1 for 3 cycles at 21 ° C. Cyclic experiments at 300% and 80 ° C are performed using an environmental chamber. In the experiment
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80 ° C, the sample is allowed to thermal equilibrate for 45 minutes at the test temperature before performing the test. In the 300% cyclic experiment at 21 ° C, the retraction stress is recorded on request for 150% of the first cycle discharged using the request in which the load returned to the baseline. The recovery percentage is defined as:
£ f ^- £ _s % recovery = ________ x 100 £ f where e _f is the request considered for cyclic loading ee _s where the load returns to the baseline during the first unloaded cycle.
[135] Stress relaxation at 50% load and 37 ° C for 12 hours is measured using an Instron ^TM instrument equipped with an environmental chamber. The gauge geometry was 76 mm x 25 mm x 0.4 mm. After equilibrating at 37 ° C for 45 minutes in the environmental chamber, the sample was stretched 50% at 333% min ^-1 . Voltage was recorded as a function of time for 12 hours. The percentage of effort relaxation after 12 hours was calculated using the formula:
^L 0 ^{- L} 12% effort relaxation = _________ x 100
L0 where L ₀ is the load at 50% demand at time 0 and L ₁₂ is the load at 50% demand after 12 hours.
[136] Notch tensile rupture experiments were performed on samples having a density of 0.88 g / cm ³ or less using an Instron ^TM instrument. The geometry consists of a 76 mm x 13 mm x 0.4 mm gauge section with a 2 mm gauge cut in the sample at half the length of the specimen. The sample is stretched at 508 mm min ^-1 at 21 ° C until it breaks. The burst energy is calculated
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58/161 as the area under the stress-elongation curve until deformation at maximum load. An average of at least 3 specimens is reported.
TMA [137] Thermomechanical analysis (penetration temperature) is performed on compression molded discs 30 mm in diameter x 3.3 mm thick, formed at 180 ° C and molding pressure of 10 MPa for 5 minutes and then tempered in air. The instrument used is a TMA 7 brand obtainable from Perkin-Elmer. In the test, a probe with a 1.5 mm radius tip (P / N N519-0416) is applied to the surface of the sample disc with a force of 1 N. From 25 ° C, the temperature is increased by 5 ° C / min. The probe penetration distance is measured as a function of temperature. The experiment ends when the probe has penetrated 1 mm in the sample.
DMA [138] Dynamic mechanical analysis (DMA) is measured on compression-shaped discs formed in a thermal press at 180 ° C and a pressure of 10 MPa for 5 minutes and then cooled in the press at 90 ° C / min. The test is performed using an ARES controlled strain rheometer (TA Instruments) equipped with a fixed double cantilever accessory for torsion testing.
[139] A 1.5 mm plate is pressed and cut into a 32x12 mm bar. The sample is fixed at both ends between the fixed accessories separated by 10 mm (clamp separation LA) and subjected to successive temperature steps from -100 ° C to 200 ° C (5 ° C per step). At each temperature the torsion module G 'is measured at an angular frequency of 10 rad / s, the amplitude of deformation being kept between 0.1 percent and 4 percent to ensure
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59/161 that the torque is sufficient and the measurement remains in the linear regime.
[140] An initial static force of 10 g (self-tension mode) is maintained to prevent loosening when thermal expansion occurs. As a consequence, the staple separation AL increases with temperature, particularly above the melting point or the softening point of the polymer sample. The test stops at the maximum temperature or when the gap between the fixed accessories reaches 65 mm.
Melting index [141] The melting index, or I2, is measured according to ASTM D 1238, condition 190 ° C / 2.16 kg. The melting index, or I10, is also measured according to ASTM D 1238, condition 190 ° C / 10 kg.
ATREF [142] Fractional analysis by elution with analytical temperature gradient (ATREF) is performed according to the method described in U.S. Patent No. 4,798,081 and in Wilde, L .; Ryle, T.R .; Knobeloch, D. C .; Peat, I.R., “Determination of Branching Distributions in Polyethilene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455 (1982). The composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel filler), slowly reducing the temperature to 20 ° C at a cooling rate of 0.1 ° C / min. The column is equipped with an infrared detector. An ATREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the elution solvent (trichlorobenzene) from 20 to 120 ° C at a rate of 1.5 ° C / min.
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¹³ C NMR analysis [143] Samples are prepared by adding approximately 3 g of a 50/50 mixture of tetrachloroethane-d ² / orthodichlorobenzene to 0.4 g of sample in a 10 mm NMR tube. The samples are dissolved and homogenized by heating the tube and its contents to 150 ° C. data is collected using a 400 MHz JEOL Eclipse ^TM spectrometer or a 400 MHz Varian Unity Plus ^TM spectrometer, corresponding to a resonance frequency of ¹³ C of 100.5 MHz. Data is acquired using 4000 transients per data file with a 6-second pulse repeat delay. To achieve minimum signal-to-noise for quantitative analysis, multiple data files are added together. The spectral width is 25,000 Hz with a minimum data point file size of 32K. Samples are analyzed at 130 ° C on a 10 mm wide band probe. Comonomer incorporation is determined using Randall's triad method (Randall, JC, JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989)).
TREF polymer fractionation [144] Large scale TREF fractionation is performed by dissolving 15-20 g of polymer in 2 liters of 1,2,4 trichlorobenzene (TCB), stirring for 4 hours at 160 ° C. The polymer solution is forced by 100 kPa (15 psig) of nitrogen onto a 7.6 cm x 12 cm steel column packed with a 60:40 (v / v) mixture of 425- technical quality spherical glass beads 600 pm (available from Potters Industries, HC 30 Box 20, Brownwood, TX, 76801) and stainless steel, 0.7 mm diameter cut wire projectile (available from Pellets, Inc. 63 Industrial Drive, North
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Tonawanda, NY, 14120). The column is immersed in a thermally controlled oil jacket, initially set at 160 ° C. First, the column is ballistically cooled to 125 ° C, then slowly cooled to 20 ° C at 0.04 ° C / minute and maintained for one hour. New TCB is introduced at about 65 ml / min while lowering the temperature to 0.167 ° C / minute.
[145] Eluent portions of approximately 2000 mL of the preparative TREF column are collected in a 16 station heated fraction collector. The polymer is concentrated in each fraction using a rotary evaporator until about 50 to 100 ml of the polymeric solution remain. The concentrated solutions are allowed to rest overnight before adding excess methanol, filtering and rinsing (approximately 300500 mL of methanol including the final rinse). The filtration step is performed in a 3 position vacuum assisted filtration station using 5.0 gm poly (tetrafluoroethylene) coated filter paper (obtainable from Osmonics Inc., Cat # Z50WP04750). The filtered fractions are dried overnight in a vacuum oven at 60 ° C and weighed on an analytical balance before further testing.
Melt strength [146] Melt strength (MS) is measured using a capillary rheometer prepared with a diameter of 2.1 mm, a 20: 1 matrix with an entry angle of approximately 45 degrees. After equilibrating the samples at 190 ° C for 10 minutes, the piston is moved at a speed of 2.54 cm / minute. The standard test temperature is 190 ° C. The sample is stretched uniaxially by a set of acceleration clamps located 100 mm below the matrix with an acceleration of 2.4 mm / s ² . The required pulling force is recorded as a
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62/161 function of the stretching speed of the traction cylinders. The maximum tensile strength achieved during the test is defined as the tensile strength. In the case of polymer fusion exhibiting tensile resonance, the tensile strength before the beginning of the tensile resonance was considered as tensile strength. The tensile strength is recorded in centiNewton (cN).
Catalysts [147] If used, the expression “overnight” refers to a time interval of approximately 16-18 hours; the term room temperature refers to a temperature of 20-25 ° C; and the term mixture of alkanes refers to a mixture of C _6-9 aliphatic hydrocarbons obtained commercially under the trade name ISOPAR E, from ExxonMobil Chemical Company. In case the name of a compound does not agree with its structural representation, the structural representation will prevail. The synthesis of all complexes and the preparation of all screening experiments were carried out in a dry nitrogen atmosphere using dry box techniques. All solvents used were HLPC grade and were dried before using them.
[148] MMAO refers to modified methyl aluminoxane, a methyl aluminoxane modified with triisobutyl aluminum commercially obtainable from Akzo-Noble Corporation.
[149] The preparation of the catalyst (B1) is carried out as follows.
a) Preparation of (1-methyl ethyl) (2-hydroxy-3,5di (terciobutyl) phenyl) methyl imine
3,5-di (terciobutyl) salicylic aldehyde (3.00 g) is added to
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63/161 mL of isopropylamine. The solution quickly turns bright yellow. After stirring for 3 hours at room temperature, the volatiles are removed in vacuo to produce a bright yellow crystalline solid (97 percent yield).
b) Preparation of dibenzyl 1,2-bis- (3,5-di (terciobutyl phenylene) (1-N- (1-methyl ethyl) imino) methyl) (2-oxoyl) zirconium [150] solution of (1-methyl ethyl) (2-hydroxy-3,5-di (terciobutyl) phenyl) imine (605 mg, 2.2 mmol) in 5 ml of toluene in a solution of Zr (CH ₂ Ph) 4 (500 mg, 1.1 mmol) in 50 ml of toluene. The resulting dark yellow solution is stirred for 30 min. The solvent is removed under reduced pressure to obtain the desired product as a reddish brown solid.
[151] Catalyst preparation (B2) is carried out as follows.
a) Preparation of (1- (2-methyl cyclohexyl) ethyl) (2oxoyl-3,5-di (terciobutyl) phenyl) imine [152] 2-Methyl cyclohexylamine (8.44 mL, 64 , 0 mmol) in methanol (90 mL), and di (terciobutyl) salicylic aldehyde (10.00 g, 42.67 mmol) is added. The reaction mixture is stirred for three hours and then cooled to -25 ° C for 12 hours. The resulting yellow solid precipitate is collected by filtration and washed with cold methanol (2 x 15 ml), and then dried under reduced pressure. The product is 11.17 g of a yellow solid. The ¹ H NMR is consistent with the desired product as a mixture of isomers.
b) Preparation of dibenzyl bis- (1- (2-methyl cyclohexyl) ethyl) (2-oxoyl-3,5-di (terciobutyl) phenyl) imino) zirconium [153] A solution of (1 -methyl
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64/161 cyclohexyl) ethyl) (2-oxoyl-3,5-di (terciobutyl) phenyl) imine (7.63 g, 23.2 mmol) in 200 ml of toluene in a solution of Zr (CH ₂ Ph) ₄ (5.28 g, 11.6 mmol) in 600 mL of toluene. The resulting dark yellow solution is stirred for 1 hour at 25 ° C. The solution is further diluted with 680 ml of toluene to give a solution having a concentration of 0.00783M.
[154] Co-catalyst 1. A mixture of methyldi salts (C14-18 alkyl) tetrakis borate ammonium (pentafluorfenyl) (hereinafter armenium borate), prepared by reaction with a long chain trialkylamine (ARMEEN ^TM M2HT, obtainable from Akzo-Nobel, Inc.), HCl and Li [B (C6H5) 4], substantially as disclosed in USP 5,919,983, Ex. 2.
[155] Co-catalyst 2. A mixture of (C14-18 alkyl) dimethyl ammonium salts of bis (tris (pentafluor phenyl) alumino) -2-undecyl-imidazolid, prepared according to USP 6,395,671, Ex. 16.
[156] Exchange agents. The exchange agents employed include diethyl zinc (TEN, SA1), diisobutyl zinc (SA2), di (n-hexyl) zinc (SA3), triethyl aluminum (TEA, SA4), trioctyl aluminum (SA5), triethyl gallium (SA6) , aluminum bis (dimethyl (terciobutyl) siloxane) isobutyl (SA7), aluminum bis (di (trimethyl silyl) amide (SA8), aluminum di (pyridine-2-methoxide) n-octyl (SA9), isobutyl bis (noctadecyl) aluminum (SA10), bis (di (npentyl) amide) isobutyl aluminum (SA11), bis (2,6di (terciobutyl) phenoxide) n-octyl aluminum (SA12), di (ethyl (1naphthyl) amide) n-octyl aluminum ( SA13), bis (terciobutyldimethyl siloxide) ethyl aluminum (SA14), di (bis (trimethylsilyl) amide) ethyl aluminum (SA15), bis (2,3,6,7-dibenzo-1-azacycloheptanamide) ethyl aluminum ( SA16), bis (2,3,6,7-dibenzo
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1-aza-cycloheptanamide) n-octyl aluminum (SA17), bis (dimethyl (terciobutyl) siloxide n-octyl aluminum (SA18), (2,6-diphenyl-phenoxide) ethyl zinc (SA19), and (terciobutoxide) ethyl zinc (SA20).
Examples 1-4, Comparative Examples A * -C * [157] General conditions of high operational productivity parallel polymerization [158] Polymerizations are carried out using a high operational productivity parallel polymerization reactor (PRR) obtainable from Symyx Technologies, Inc operated substantially in accordance with US Patent Nos. 6,248,540, 6,030,917, 6,362,309, 6,306,658, and 6,316,663. Copolymerizations of ethylene at 130 ° C and 1.4 MPa (200 psi) are performed with ethylene when ordered using 1.2 equivalents of co-catalyst 1 based on the total catalyst used (1.1 equivalents when MMAO is present) . A series of polymerizations are carried out in a parallel pressure reactor (PPR) containing 48 individual reactor cells in a 6 x 8 arrangement which are prepared with a heavy glass tube. The working volume in each reactor is 6000 μL. The temperature and pressure of each cell is controlled with agitation provided by stirring paddles. The gaseous monomer and the quench gas are pumped directly into the PPR unit and controlled by automatic valves. Liquid reagents are added robotically to each reactor cell using syringes and the reservoir solvent is a mixture of alkanes. The order of addition is: alkane mixture solvent (4 mL), ethylene, 1-octene comonomer (1 mL), co-catalyst 1 co-catalyst mixture 1 / MMAO, exchange agent, and catalyst or mixture of catalysts. When using a mixture of co
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66/161 catalyst 1 and MMAO or a mixture of two catalysts, the reagents are premixed in a small fraction just before addition to the reactor. When a reagent is omitted in an experiment, the above order of addition in the plus is maintained. Polymerizations are carried out for approximately 1-2 minutes, until the predetermined ethylene consumption is reached. After quenching with CO, the reactors are cooled and the glass tubes are discharged. The tubes are transferred to a vacuum centrifugation / drying unit, and dried for 12 hours at 60 ° C. The tubes containing dry polymer are weighed and the difference between this weight and the tare weight gives net weight of polymer. The results are contained in Table 1. In Table 1 and elsewhere in this patent application, comparative compounds are indicated by an asterisk (*).
[159] Examples 1-4 show the synthesis of linear block copolymers by the present invention evidenced by the formation of an essentially monomodal, very narrow MWD copolymer when TEN is present and a wide molecular weight distribution product, bimodal (a mixture polymers produced separately) in the absence of TEN. Due to the fact that Catalyst (A1) is known to incorporate more octene than Catalyst (B1), the different blocks or segments of the copolymers resulting from the invention are distinguishable based on branching or density.
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Table 1
Ex. Cat. (A1)(gmol) Cat. (B1)(gmol) Co-cat.(gmol) MMAO(gmol) AgentExchange(gmol) Product(g) Mn Mw / Mn hexyl ¹ THE* 0.06 - 0.066 0.3 - 0.1363 300502 3.32 - B* - 0, 1 0.10 0.5 - 0.1581 36957 1.22 2.5 Ç* 0.06 0, 1 0. 176 0.8 - 0.2038 45526 5.30 ² 5.5 1 0.06 0, 1 0, 192 - TEN (8.0) 0.1974 28715 1, 19 4.8 2 0.06 0, 1 0, 192 - TEN (80.0) 0.1468 2161 1, 12 14.4 3 0.06 0, 1 0, 192 - TEA (8.0) 0.208 22675 1.71 4.6 4 0.06 0, 1 0, 192 - TEA (80.0) 0.1879 3338 1.54 9, 4
67/161 ¹ C ₆ or higher chain content per 1000 carbons.
Bimodal molecular weight distribution.
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68/161 [160] It can be seen that the polymers produced according to the invention have a relatively narrow polydispersion (Mw / Mn) and a larger block copolymer content (trimer, tetramer, or greater) than the polymers prepared in the absence of the exchange agent.
[161] Additional characterizing data for the polymers in Table 1 are determined by reference to the figures. More specifically, the DSC and ATREF results show the following:
[162] The DSC curve for the polymer of Example 1 shows a melting point (Tm) of 115.7 ° C with a melting heat of 158.1 J / g. The corresponding CRYSTAF curve shows the maximum peak at 34.5 ° C with a peak area of 52.9 percent. The difference between Tm by DSC and TCRYSTAF is 81.2 ° C.
[163] The DSC curve for the polymer of Example 2 shows a peak with a melting point (Tm) of 109.7 ° C with a melting heat of 214.0 J / g. The corresponding CRYSTAF curve shows the maximum peak at 46.2 ° C with a peak area of 57.0 percent. The difference between Tm by DSC and TCRYSTAF is 63.5 ° C.
[164] The DSC curve for the polymer of Example 3 shows a peak with a melting point (Tm) of 120.7 ° C with a melting heat of 160.1 J / g. The corresponding CRYSTAF curve shows the maximum peak at 66.1 ° C with a peak area of 71.8 percent. The difference between Tm by DSC and TCRYSTAF is 54.6 ° C.
[165] The DSC curve for the polymer of Example 4 shows a peak with a melting point (Tm) of 104.5 ° C with a melting heat of 170.7 J / g. The corresponding CRYSTAF curve shows the maximum peak at 30 ° C with a peak area of 18.2 percent. The difference between Tm by DSC and TCRYSTAF is 74.5 ° C.
[166] The DSC curve for Comparative Example A * shows
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69/161 a melting point (Tm) of 90.0 ° C with a melting heat of 86.7 J / g. The corresponding CRYSTAF curve shows the maximum peak at 48.5 ° C with a peak area of 29.4 percent. Both of these values are consistent with a low density resin. The difference between Tm by DSC and TCRYSTAF is 41.8 ° C.
[167] The DSC curve for Comparative Example B * shows a melting point (Tm) of 129.8 ° C with a melting heat of 237.0 J / g. The corresponding CRYSTAF curve shows the maximum peak at 82.4 ° C with a peak area of 83.7 percent. Both of these values are consistent with a high density resin. The difference between Tm by DSC and TCRYSTAF is 47.4 ° C.
[168] The DSC curve for Comparative Example C * shows a melting point (Tm) of 125.3 ° C with a melting heat of 143.0 J / g. The corresponding CRYSTAF curve shows the maximum peak at 81.8 ° C with a peak area of 34.7 percent as well as a smaller crystalline peak at 52.4 ° C. The separation between the two peaks is consistent with the presence of a very crystalline polymer and a low crystalline polymer. The difference between Tm by DSC and T _CRYSTAF is 43.5 ° C.
[169] Examples 5-19, Comparative Examples D * -F *, continuous polymerization in solution, Catalyst A1 / B2 + TEN [170] Continuous solution polymerizations are carried out in a computer controlled autoclave reactor and equipped with an internal stirrer. Purified alkane mixture solvent (ISOPAR ™ E obtainable from ExxonMobil Chemical Company), ethylene at 1.22 kg / h (2.70 lb / h), 1-octene, and hydrogen (where used) are supplied to a reactor of 3.8 L equipped with a jacket for temperature control and a thermocouple
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70/161 internal. The solvent load to the reactor is measured by a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and the pressure to the reactor. At the pump discharge, a side stream is used to provide jet streams for the catalyst and co-catalyst 1 injection lines and for the reactor agitator. These flows are measured by Micro-Motion mass flow meters and controlled by control valves or by manually adjusting needle valves. The remaining solvent is combined with 1-octene, ethylene, and hydrogen (where used) and fed to the reactor. A mass flow controller is used to release hydrogen to the reactor when necessary. The temperature of the monomer / solvent solution is controlled by using a heat exchanger before entering the reactor. This current enters the bottom of the reactor. The catalyst component solutions are dosed using mass pumps and flow meters and are combined with the catalyst jet solvent and introduced into the bottom of the reactor. The reactor operates full of liquid at 3.45 MPa (500 psig) with vigorous agitation. The product is removed through exit lines at the top of the reactor. All of the reactor's output lines are steam traversed and isolated. The polymerization is interrupted by adding a small amount of water to the outlet line together with stabilizers or other additives and passing the mixture through a static mixer. The product stream is then heated by passing it through a heat exchanger before devolatilization. The polymeric product is recovered by extrusion using a devolatilization extruder and water-cooled pelletizer. The results and process details are contained in the
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Table 2. Table 3 provides the selected polymer properties.
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Table 2. Process details for preparing exemplary polymers
Ex. CsH16 kg / h Solv. kg / h h ₂ sccm ¹ T° C Cat A1 ² ppm FlowCatA1 kg / h Cat B2 ³ ppm FlowCat B2 kg / h Conc.TEN% Flow TEN kg / h Conc. cocat ppm Flow cocat kg / h [C2H4] / [TEN] ⁴ Poly rate.kg / h Conv.% Solids% Ef. ⁷ D * 1.63 12, 7 29, 90 120 142.2 0.14 - - 0, 19 0.32 820 0.17 536 1.81 88.8 11.2 95.2 AND* 1.63 9, 5 5.00 120 - - 109 0.10 0, 19 0.32 1743 0.40 485 1.47 89, 9 11.3 126.8 F * 1.63 11, 3 251, 6 120 71.7 0.06 30, 8 0, 06 - - 1743 0.11 - 1.55 88.5 10.3 257.7 5 1.63 11, 3 - 120 71.7 0.14 30, 8 0.13 0.17 0.43 1743 0.26 419 1.64 89, 6 11.1 118.3 6 1.63 11, 3 4.92 120 71.7 0.10 30, 4 0, 08 0.17 0.32 1743 0.18 570 1.65 89.3 11.1 172.7 7 1.63 11, 3 21, 70 120 71.7 0.07 30, 8 0, 06 0.17 0.25 1743 0.13 718 1.60 89.2 10.6 244.1 8 1.63 11, 3 36, 90 120 71.7 0.06 30, 8 0, 06 0.17 0.10 1743 0.12 1778 1.62 90.0 10.8 261.1 9 1.63 11, 3 78, 43 120 71.7 0.06 30, 8 0, 06 0.17 0.04 1743 0.12 4596 1.63 90.2 10.8 267.9 10 1.63 11, 3 0, 00 123 71.1 0.12 30.3 0.14 0.34 0, 19 1743 0.08 415 1.67 90.31 11.1 131.1 11 1.63 11, 3 0, 00 120 71.1 0.16 30.3 0.17 0.80 0.15 1743 0.10 249 1.68 89, 56 11.1 100.6 12 1.63 11, 3 0, 00 121 71.1 0.15 30.3 0.07 0.80 0, 09 1743 0.07 396 1.70 90, 02 11.3 137.0 13 1.63 11, 3 0, 00 122 71.1 0.12 30.3 0, 06 0.80 0.05 1743 0.05 653 1.69 89, 64 11.2 161, 9 14 1.63 11, 3 0, 00 120 71.1 0.05 30.3 0.29 0.80 0.10 1743 0.10 395 1.41 89, 42 9.3 114.1 15 2.45 11, 3 0, 00 120 71.1 0.14 30.3 0.17 0.80 0.14 1743 0.09 282 1.80 89, 33 11.3 121.3 16 2.45 11, 3 0, 00 122 71.1 0.10 30.3 0.13 0.80 0.07 1743 0.07 485 1.78 90, 11 11.2 159.7 17 2.45 11, 3 0, 00 121 71.1 0.10 30.3 0.14 0.80 0, 08 1743 0.07 506 1.75 89, 08 11.0 155.6 18 0.69 11, 3 0, 00 121 71.1 0.10 30.3 0.22 0.80 0.11 1743 0.10 331 1.25 89, 93 8.8 90.2 19 0.32 11, 3 0, 00 122 71.1 0.06 30.3 0.22 0.80 0, 09 1743 0.08 367 1, 16 90, 74 8.4 106.0
72/161 * Comparative Example, not an example of the invention.
¹ cm3 standard / min ² Dimethyl [N- (2,6-di (1-methyl ethyl) phenyl) starch) (2-isopropyl phenyl) (a-naphthalen-2-diyl (6-pyridin-2diyl) methane) hafnium
3Dibenzyl bis- (1- (2-methyl cyclohexyl) ethyl) (2-oxoyl-3,5-di (terciobutyl) phenyl) imino) zirconium
4 Molar ratio in reactor ⁵ Polymer production rate ⁶ Percentage of ethylene conversion in reactor ⁷ Efficiency, kg of polymer / g of M where g of M = g of HF + g of Zr
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Table 3. Properties of exemplary polymers.
Ex. Density (g / cm ³ ) I2 I10 I10 / I2 Mw (g / mol) Mn (g / mol) Mw / Mn Fusion heat (J / g) Tm (° C) Tc (° C) ^T CRYSTAF (° C) Tm- ^T CRYSTAF (° C) Peak areaCRYSTAF (%) D * 0.8627 1.5 10.0 6, 5 110,000 55,800 2.0 32 37 45 30 7 99 AND* 0.9378 7.0 39, 0 5, 6 65,000 33,300 2.0 183 124 113 79 45 95 F * 0.8895 0, 9 12.5 13.4 137,300 9,980 13.58 90 125 111 78 47 20 5 0.8786 1.5 9, 8 6, 7 104,600 53,200 2.0 55 120 101 48 42 60 6 0.8785 1, 1 7.5 6, 5 109,600 53,300 2.1 55 115 94 44 71 63 7 0.8825 1.0 7.2 7, 1 118,500 53,100 2.2 69 121 103 49 72 29 8 0.8828 0, 9 6, 8 7.7 129,000 40,100 3.2 68 124 106 80 43 13 9 0.8836 1, 1 9, 7 9, 1 129,600 28,700 4.5 74 125 109 81 44 16 10 0.8784 1.2 7.5 6, 5 113,100 58,200 1, 9 54 116 92 41 75 52 11 0.8818 9, 1 59, 2 6, 5 66,200 36,500 1.8 63 114 93 40 74 25 12 0.8700 2.1 13.2 6, 4 101,500 55,100 1.8 40 113 80 30 83 91 13 0.8718 0.7 4.4 6, 5 132,100 63,600 2.1 42 114 80 30 81 8 14 0.9116 2.6 15, 6 6, 0 81,900 43,600 1, 9 123 121 106 73 48 92 15 0.8719 6, 0 41, 6 6, 9 79,900 40,100 2.0 33 114 91 32 82 10 16 0.8758 0.5 3.4 7, 1 148,500 74,900 2.0 43 117 96 48 69 65 17 0.8757 1.7 11.3 6, 8 107,500 54,000 2.0 43 116 96 43 73 57 18 0.9192 4, 1 24.9 6, 1 72,000 37,900 1, 9 136 120 106 70 50 94 19 0.9344 3.4 20.3 6, 0 76,800 39,400 1, 9 169 125 112 80 45 88
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74/161 [171] The resulting polymers are tested by DSC and ATREF as with the previous examples. The results are as follows:
[172] The DSC curve for the polymer of Example 5 shows a peak with a melting point (T _m ) of 119.6 ° C with a melting heat of 60.0 J / g. The corresponding CRYSTAF curve shows the maximum peak at 47.6 ° C with a peak area of 59.5 percent. The delta between the DSC Tm and the TCRYSTAF is 72.0 ° C.
[173] The DSC curve for the polymer of Example 6 shows a peak with a melting point (Tm) of 115.2 ° C with a melting heat of 60.4 J / g. The corresponding CRYSTAF curve shows the maximum peak at 44.2 ° C with a peak area of 62.7 percent. The delta between the DSC Tm and the TCRYSTAF is 71.0 ° C.
[174] The DSC curve for the polymer of Example 7 shows a peak with a melting point (Tm) of 121.3 ° C with a melting heat of 69.1 J / g. The corresponding CRYSTAF curve shows the maximum peak at 49.2 ° C with a peak area of 29.4 percent. The delta between the DSC Tm and the TCRYSTAF is 72.1 ° C.
[17 5] The DSC curve for the polymer of Example 8 shows a peak with a melting point (Tm) of 123.5 ° C with a melting heat of 67.9 J / g. The corresponding CRYSTAF curve shows the maximum peak at 80.1 ° C with a peak area of 12.7 percent. The delta between the DSC Tm and the TCRYSTAF is 43.4 ° C.
[17 6] The DSC curve for the polymer of Example 9 shows a peak with a melting point (Tm) of 124.6 ° C with a melting heat of 73.5 J / g. The corresponding CRYSTAF curve shows the maximum peak at 80.8 ° C with a peak area of 16.0 percent. The delta between the DSC Tm and the TCRYSTAF is 43.8 ° C.
[177] The DSC curve for the polymer of Example 10 shows a peak with a melting point (Tm) of 115.6 ° C with a heat of
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75/161 melting of 60.7 J / g. The corresponding CRYSTAF curve shows the maximum peak at 40.9 ° C with a peak area of 52.4 percent. The delta between the DSC T _m and the _CRYSTAF T is 7 4.7 ° C.
[178] The DSC curve for the polymer of Example 11 shows a peak with a melting point (T _m ) of 113.6 ° C with a melting heat of 70.4 J / g. The corresponding CRYSTAF curve shows the maximum peak at 39.6 ° C with a peak area of 25.2 percent. The delta between the DSC Tm and the TCRYSTAF is 74.1 ° C.
[179] The DSC curve for the polymer of Example 12 shows a peak with a melting point (Tm) of 113.2 ° C with a melting heat of 48.9 J / g. The corresponding CRYSTAF curve shows the maximum peak greater than or equal to 30 ° C (TCRYSTAF for additional calculation purposes is therefore adjusted to 30 ° C). The delta between
the Tm of DSC ^{and T} CRYSTAF ^is of 83 , 2 ° C. [180] THE curve of DSC for the polymer of Example 13 shows a peak with a dot in Fusion (Tm) of 114.4 ° C with a heat of
melting of 49.4 J / g. The corresponding CRYSTAF curve shows the maximum peak at 33.8 ° C with a peak area of 7.7 percent. The delta between the DSC Tm and the TCRYSTAF is 84.4 ° C.
[181] The DSC curve for the polymer of Example 14 shows a peak with a melting point (Tm) of 120.8 ° C with a melting heat of 127.9 J / g. The corresponding CRYSTAF curve shows the maximum peak at 72.9 ° C with a peak area of 92.2 percent. The delta between the DSC Tm and the TCRYSTAF is 47.9 ° C.
[182] The DSC curve for the polymer of Example 15 shows a peak with a melting point (Tm) of 114.3 ° C with a melting heat of 36.2 J / g. The corresponding CRYSTAF curve shows the maximum peak at 32.3 ° C with a peak area of 9.8 percent. The delta between the DSC Tm and the TCRYSTAF is 82.0 ° C.
[183] The DSC curve for the polymer of Example 16 shows
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76/161 a peak with a melting point (T _m ) of 116.6 ° C with a melting heat of 44.9 J / g. The corresponding CRYSTAF curve shows the maximum peak at 48.0 ° C with a peak area of 65.0 percent. The delta between the DSC Tm and the TCRYSTAF is 68.6 ° C.
[184] The DSC curve for the polymer of Example 17 shows a peak with a melting point (Tm) of 116.0 ° C with a melting heat of 47.0 J / g. The corresponding CRYSTAF curve shows the maximum peak at 43.1 ° C with a peak area of 56.8 percent. The delta between T _m of DSC and T _CRYSTAF is 72.9 ° C.
[185] The DSC curve for the polymer of Example 18 shows a peak with a melting point (Tm) of 120.5 ° C with a melting heat of 141.8 J / g. The corresponding CRYSTAF curve shows the maximum peak at 70.0 ° C with a peak area of 94.0 percent. The delta between the DSC Tm and the TCRYSTAF is 50.5 ° C.
[186] The DSC curve for the polymer of Example 19 shows a peak with a melting point (Tm) of 124.8 ° C with a melting heat of 174.8 J / g. The corresponding CRYSTAF curve shows the maximum peak at 79.9 ° C with a peak area of 87.9 percent. The delta between DSC Tm and TCRYSTAF is 45.0 ° C.
[187] The DSC curve for the polymer of Comparative Example D * shows a peak with a melting point (Tm) of 37.3 ° C with a melting heat of 31.6 J / g. The corresponding CRYSTAF curve shows the peak greater than or equal to 30 ° C. Both values are consistent with a low density resin. The delta between the DSC Tm and the TCRYSTAF is 7.3 ° C.
[188] The curve of DSC to polymer of Example Comparat ive E * shows a peak common Score in Fusion (Tm) in 124.0 ° C with a heat fusion 179.3 J / g. The curve in CRYSTAF corresponding show the peak maximum to 7 9.3 ° C with an area peak 94, 6 by cent. Both the values are
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77/161 consistent with a high density resin. The delta between the DSC Tm and the Tcrystaf is 4 4, 6 ° C.
[189] The DSC curve for the polymer of Comparative Example F * shows a peak with a melting point (T _m ) of 124.8 ° C with a melting heat of 90.4 J / g. The corresponding CRYSTAF curve shows the maximum peak at 77.6 ° C with a peak area of 19.5 percent. The separation between the two peaks is consistent with the presence of a very crystalline polymer as well as a low crystalline polymer. The delta between the DSC Tm and the _CRYSTAF T is 47.2 ° C.
Physical property tests [190] Polymer samples are evaluated for physical properties such as high temperature resistance properties, evidenced by TMA temperature test, resistance to pellet agglomeration, high temperature recovery, high temperature compression deformation and ratio of storage modules, G '(25 ° C) / G' (100 ° C). Various commercially available polymers are included in the tests: Comparative Example G * is a substantially linear ethylene / 1-octene copolymer (AFFINITY®, obtainable from The Dow Chemical Company); Comparative Example H * is a substantially linear, elastomeric ethylene / 1-octene copolymer (AFFINITY® EG8100, obtainable from The Dow Chemical Company); Comparative Example I * is a substantially linear ethylene / 1-octene copolymer (AFFINITY® PL1840, obtainable from The Dow Chemical Company); Comparative Example J * is a copolymer in hydrogenated styrene / butadiene / styrene triblocks (KRATON ™ G1652, obtainable from KRATON Polymers); Comparative Example K * is a thermoplastic vulcanized product (TPV, a polyolefin mixture containing
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78/161 crosslinked elastomer dispersed in it). Table 4 shows the results.
Table 4. Mechanical properties at high temperature
Ex. TMApenetration of 1 mm(° C) Resistance to adhesion of kPa pellets G '(25 ° C) /G '(100 ° C) Deformation recovery of 300% (80 ° C) (%) Compression deformation (%) D * 51 - 9 Failed - AND* 130 - 18 - - F * 70 6, 8 9 Failed 100 5 104 0 6 81 49 6 110 - 5 - 52 7 113 - 4 84 43 8 111 - 4 Failed 41 9 97 - 4 - 66 10 108 - 5 81 55 11 100 - 8 - 68 12 88 - 8 - 79 13 95 - 6 84 71 14 125 - 7 - - 15 96 - 5 - 58 16 113 - 4 - 42 17 108 0 4 82 47 18 125 - 10 - - 19 133 - 9 - - G * 75 22.2 89 Failed 100 H* 70 10, 2 29 Failed 100 I * 111 - 11 - - J * 107 - 5 Failed 100 K * 152 - 3 - 40
[191] In Table 4, Comparative Example F * (which is a physical mixture of the two polymers resulting from simultaneous polymerisations using catalysts A1 and B1) has a penetration temperature of 1 mm of about 70 ° C, whereas Examples 5-9 have a penetration temperature of 1 mm greater than or equal to 100 ° C. In addition, all Examples 10-19 have a penetration temperature of 1 mm greater than 85 ° C, with most having a TMA temperature of 1
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79/161 mm greater than 90 ° C or even greater than 100 ° C. This shows that the new polymers have better dimensional stability at higher temperatures compared to a physical mixture. Comparative Example J * (a commercial SEBS) has a good 1 mm TMA temperature of about 107 ° C, but it has a lower compression strain (high temperature of 70 ° C) of about 100 percent and it also failed recovery (sample broke) during a 300 percent high temperature (80 ° C) deformation recovery. Consequently, the exemplified polymers have a unique combination of properties not available even in some commercially available high-performance thermoplastic elastomers.
[192] Similarly, Table 4 shows a low (good) ratio of storage modules, G '(25 ° C) / G' (100 ° C) of 6 or less for the inventive polymers, while a physical mixture ( Comparative Example F *) has a storage module ratio of 9 and a random ethylene / octene copolymer (Comparative Example G *) of similar density has a storage module ratio in an order of magnitude greater (89). It is desirable that the storage modulus ratio of a polymer is as close to 1 as possible. Such polymers will not be relatively affected by temperature, and manufactured articles produced from such polymers can be usefully employed over a wide temperature range. This low modulus ratio and temperature independence feature is particularly useful in elastomer applications such as pressure sensitive adhesive formulations.
[193] The data in Table 4 also shows that the
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80/161 polymers of the invention have improved pellet adhesion resistance. In particular, Example 5 has a pellet adhesion resistance of 0 MPa, meaning that it flows freely under the conditions tested, compared to Comparative Examples F * and G * which shows considerable adherence. Adhesion resistance is important since a bulk polymer load having high adhesion resistances can result in product agglomeration or adhesion during transport or storage, resulting in lower handling properties.
[194] High temperature (70 ° C) compression strain is generally good for inventive polymers, generally meaning less than about 80 percent, preferably less than about 70 percent and especially less than about 60 percent . In contrast, Comparative Examples F *, G *, H * and J * all have a compression strain at 70 ° C of 100 percent (the maximum possible value, indicating no recovery). Good compression deformation at high temperature (low numerical values) is especially necessary in applications such as gaskets, window profiles, circular gaskets, and the like.
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Table 5. Mechanical properties at room temperature.
Ex. Bending module(MPa) Traction module (MPa) Tensile strength limit (MPa) ¹ Elongation until break ¹ (%) Tensile strength limit (MPa) ¹ Elongation until break ¹ (%) Abrasion: loss of volume (mm ³ ) Notched tensile strength (mJ) 100% deformation recovery at 21 ° C (%) 100% deformation recovery at 21 ° C (%) Retractable stress at 150% deformation(kPa) Compression strain at 21 ° C (%) Stress relaxation at 50% strain ² D * 12 5 - - 10 1074 - - 91 83 760 - - AND* 895 589 - - 31 1029 - - - - - - - F * 57 46 - - 12 824 93 339 78 65 400 42 - 5 30 24 14 951 16 1116 48 - 87 74 790 14 33 6 33 29 - - 14 938 - - - 75 861 13 - 7 44 37 15 846 14 854 39 - 82 73 810 20 - 8 41 35 13 785 14 810 45 461 82 74 760 22 - 9 43 38 - - 12 823 - - - - - 25 - 10 23 23 - - 14 902 - - 86 75 860 12 - 11 30 26 - - 16 1090 - 976 89 66 510 14 30 12 20 17 12 961 13 931 - 1247 91 75 700 17 - 13 16 14 - - 13 814 - 691 91 - - 21 - 14 212 160 - - 29 857 - - - - - - - 15 18 14 12 1127 10 1573 - 2074 89 83 770 14 - 16 23 20 - - 12 968 - - 88 83 1040 13 - 17 20 18 - - 13 1252 - 1274 13 83 920 4 - 18 323 239 - - 30 808 - - - - - - - 19 706 483 - - 36 871 - - - - - - - G * 15 15 - - 17 1000 - 746 86 53 110 27 50 H* 16 15 - - 15 829 - 569 87 60 380 23 - I * 210 147 - - 29 697 - - - - - - - J * - - - - 32 609 - - 93 96 1900 25 - K * - - - - - - - - - - - 30 -
81/161 ¹ Tested at 51 cm / minute.
2Measured at 38 ° C for 12 hours.
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82/161 [195] Table 5 shows results of mechanical properties of the new polymers as well as of several comparative polymers at room temperature. It can be seen that the inventive polymers have very good abrasion resistance when tested according to ISO 4649, generally showing a loss of volume less than about 90 mm, ₃ preferably less than about 80 mm, and especially less than about 50 mm ³ . In this test, larger numbers indicate greater volume loss and consequently less resistance to abrasion.
[196] The tensile strength as measured by notch tensile strength of the inventive polymers is generally greater than or equal to 1000 mJ, as shown in Table 5. The tensile strength for the inventive polymers can be as high as 3000 mJ, or even, as high as 5000 mJ. The breaking strength of comparative polymers generally does not exceed 750 mJ.
[197] Table 5 also shows that the polymers of the invention have better shrinkage stress at 150% strain (demonstrated by higher shrinkage stress values) than some of the comparative samples. Comparative Examples F *, G * and H * have 150% strain values less than or equal to 400 kPa, while the inventive polymers have 150% strain values of 500 kPa (Example 11) up to as high as 1100 kPa (Example 17). Polymers having 150% higher strain values would be very useful in elastic applications, such as cloths and elastic fibers, especially non-woven cloths. Other applications include applications in diapers, hygiene, and costume waistband
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83/161 doctors, such as straps and elastic bands.
[198] Table 5 also shows that stress relaxation (at 50 percent strain) also improves (less) for inventive polymers when compared to, for example, Comparative Example G *. Lower stress relaxation means that the polymer retains its strength better in applications such as diapers and other clothing where retention of elastic properties for long periods at body temperatures is desired.
Optical tests
Table 6. Optical properties of polymers
Example Internal opacity (%) Clarity (%) Brightness at 45 °(%) F * 84 22 49 G * 5 73 56 5 13 72 60 6 33 69 53 7 28 57 59 8 20 65 62 9 61 38 49 10 15 73 67 11 13 69 67 12 8 75 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 17 29 73 66 18 61 22 60 19 74 11 52 G * 5 73 56 H* 12 76 59 I * 20 75 59
[199] The optical properties reported in Table 6 are based on compression-molded films substantially devoid of orientation. The optical properties of polymers can vary over wide ranges, due to the
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84/161 variation in crystallite size, resulting from variation in the amount of chain exchange agent used in the polymerization.
Extractions of copolymers in multiblocks [200] Extraction studies of the polymers of Examples 5, 7 and Comparative Example E * are carried out. In the experiments, the polymer sample is weighed in a glass frit extraction thimble and fitted in a Kumagawa type extractor. The sample extractor is purged with nitrogen and a 500 ml round bottom flask is loaded with 350 ml of diethyl ether. Then the balloon fits in the extractor. The ether is heated with stirring. Note the time when the ether begins to condense in the thimble, and the extraction continues in nitrogen for 24 hours. At this point, heating is stopped and the solution is allowed to cool. Any remaining ether in the extractor is returned to the flask. The ether in the flask is evaporated in a vacuum and at room temperature, and the resulting solids are purged dry with nitrogen. Any residue is transferred to a heavy bottle using successive washes of hexane. The combined hexane washes are then evaporated with another nitrogen purge, and the residue is vacuum dried overnight at 40 ° C. Any ether remaining in the extractor is purged dry with nitrogen.
[201] A second clean round-bottom flask is loaded with 350 mL of hexane and then connected to the extractor. The hexane is heated to reflux with stirring and maintained at reflux for 24 hours after condensation of the hexane in the thimble is noted. Heating is then interrupted and the flask is cooled. Any hexane remaining in the extractor is transferred back to the flask. The vacuum is removed and at room temperature the
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85/161 hexane, and any residue remaining in the flask is transferred to a heavy bottle using successive washes of hexane. The hexane in the flask is evaporated by nitrogen purging, and the residue is vacuum dried overnight at 40 ° C.
[202] The remainder of the polymer sample in the thimble after extractions is transferred from the thimble to the heavy bottle and is vacuum dried overnight at 40 ° C. Table 7 contains the results.
Table 7
Sample Weight(g) Soluble ether(g) Soluble ether (%) Molar% ¹ of C ₈ Soluble hexane(g) Soluble hexane (%) Molar% ¹ of C ₈ Molar% ¹ of residual C ₈ Length.F * 1.097 0.063 5.69 12.2 0.245 22.35 13, 6 6, 5 Ex. 5 1.006 0.041 4.08 - 0.040 3.98 14.2 11, 6 Ex.7 1,092 0.017 1.59 13, 3 0.012 1.10 11.7 9, 9
¹ Determined by NMR of ¹³ C.
Additional examples of 19A-F polymers, continuous polymerization in solution, catalyst A1 / B2 + TEN
For Examples 19A-I [203] Continuous solution polymerizations are carried out in a reactor with good computer controlled mixing. Purified alkane mixture solvent (ISOPAR ™ E obtainable from ExxonMobil Chemical Company), ethylene, 1-octene, and hydrogen (where used) are combined and fed into a 27-gallon reactor. The loads to the reactor are measured by mass flow controllers. The temperature of the feed stream is controlled using a glycol-cooled heat exchanger before entering the reactor. Catalytic component solutions are dosed using pumps and mass flow meters. The reactor operates full of liquid at a pressure of approximately 550 psig. After leaving the reactor, water and additive are injected into the polymeric solution. The water hydrolyzes the
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86/161 catalysts, and termination of polymerization reactions. The post-reactor solution is then heated in preparation for two-stage devolatilization. The unreacted solvent and monomers are removed during the devolatilization process. The molten polymer is pumped to cut pellets underwater.
For Example 19J [204] Polymerizations in continuous solution are carried out in a computer controlled autoclave reactor equipped with an internal stirrer. Purified alkane mixture solvent (ISOPAR ™ E obtainable from ExxonMobil Chemical Company), ethylene at 1.22 kg / h (2.70 lb / h), 1-octene, and hydrogen (where used) are supplied to a reactor 3.8 L with a jacket for temperature control and an internal thermocouple. The solvent fed to the reactor is measured by a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and the reactor pressure. When discharging the pump, a side current is allowed to provide discharge flows to the catalyst and co-catalyst injection lines and the reactor agitator. These flows are measured by Micro-Motion mass flow meters and controlled by control valves or by manually adjusting needle valves. The remaining solvent is combined with 1-octene, ethylene and hydrogen (when used) and fed into the reactor. A mass flow controller is used to release hydrogen to the reactor when necessary. The temperature of the monomer / solvent solution is controlled by using a heat exchanger before entering the reactor. This current enters the bottom of the reactor. The reactor operates full of liquid at 3.45 MPa (500 psig) with
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87/161 vigorous agitation. The product is removed through exit lines at the top of the reactor. All reactor output lines are drawn with steam and isolated. The polymerization is stopped by adding a small amount of water to the outlet line together with any stabilizers or other additives and passing the mixture through a static mixer. Then, the product stream is heated by passing it through a heat exchanger before devolatilization. The polymer product is recovered by extrusion using a devolatilization extruder and water-cooled pelletizer.
[205] Table 8 shows the details of the process and results. The polymer properties selected are provided in Table 9A-C.
[206] In Table 9B, Inventive Examples 19F and 19G show low immediate strain around 65-70% strain after 500% elongation.
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Table 8. Polymerization conditions for 19A-J polymers
Ex. C2H4 lb / h ⁸ C8H16 lb / h ⁸ Solv. lb / h ⁸ H2 scc m ¹ T° C Conc. Cat A1 ² ppm FlowCat A1 lb / h Conc. Cat B2 ³ ppm Flow Cat B2 lb / h ⁸ Conc.TEN% weight Flow TEN lb / h ⁸ Conc. cocat1 ppm Cocat flow 1 lb / h ⁸ Conc. cocat2 ppm Cocat flow 2 lb / h ⁸ Zn ⁴ in polim ppm Polimy rate ⁵ lb / h Conv ⁶ % weight Polim%Weight Eff ⁷ 19A 55.29 32, 03 323.03 101 120 600 0.25 200 0.42 3.0 0.70 4500 0.65 525 0.33 248 83, 94 88.0 17.28 297 19B 53, 95 28, 96 325.3 577 120 600 0.25 200 0.55 3.0 0.24 4500 0.63 525 0.11 90 80, 72 88.1 17.2 295 19C 55.53 30, 97 324.37 550 120 600 0.216 200 0.609 3.0 0.69 4500 0.61 525 0.33 246 84, 13 88.9 17.16 293 19D 54.83 30, 58 326, 33 60 120 600 0.22 200 0.63 3.0 1.39 4500 0.66 525 0.66 491 82, 56 88.1 17.07 280 19E 54.95 31, 73 326, 75 251 120 600 0.21 200 0.61 3.0 1.04 4500 0.64 525 0.49 368 84, 11 88.4 17.43 288 19F 50.43 34, 80 330.33 124 120 600 0.20 200 0.60 3.0 0.74 4500 0.52 525 0.35 257 85, 31 87.5 17.09 319 19G 50.25 33, 08 325.61 188 120 600 0, 19 200 0.59 3.0 0.54 4500 0.51 525 0.16 194 83, 72 87.5 17.34 333 19H 50.15 34, 87 318.17 58 120 600 0.21 200 0.66 3.0 0.70 4500 0.52 525 0.70 259 83, 21 88.0 17.46 312 19I 55.02 34, 02 323.59 53 120 600 0.44 200 0.74 3.0 1.72 4500 0.70 525 1.65 600 86, 66 88.0 17, 6 275 19J 7.46 9, 04 50, 6 47 120 150 0.22 76.7 0.36 0.5 0.19 - - - - - - - - -
¹ cm ³ / min standard
2Dimethyl [N-2,6-di (1-methyl ethyl) phenyl) starch (α-naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium ³ Dimethyl bis- (1- (2-methyl cyclohexyl) ethyl) (2-oxoyl-3,5-di (terciobutyl) phenyl) imino) zirconium 4ppm in final product calculated by mass balance. ⁵ Polymer production rate. ⁶ percentage by weight of ethylene conversion in the reactor 7Efficiency, kg of polymer / g of M where M = g of Hf + g of Z.
⁸ 1 lb / h = 0.45 kg / h
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Table 9A. Physical properties of polymers
Ex. Density (g / cm ³ ) ¹ I2 I10 I10 / I2 Mw g / mol Min g / mol Mw / Mn Fusion heat (J / g) Tm(° C) Tc(° C) CRISTAF ^T = (° c) ^T m- ^T CRYSTAF (° C) Peak areaCRYSTAF(%Weight) 19A 0.8781 0, 9 6, 4 6, 9 123700 61000 2.0 56 119 97 46 73 40 19B 0.8749 0, 9 7.3 7.8 133000 44300 3.0 52 122 100 30 92 76 19C 0.8753 5, 6 38.5 6, 9 81700 37300 2.2 46 122 100 30 92 8 19D 0.8770 4.7 31.5 6, 7 80700 39700 2.0 52 119 97 48 72 5 19E 0.8750 4.9 33.5 6, 8 81800 41700 2.0 49 121 97 36 84 12 19F 0.8652 1, 1 7.5 6, 8 124900 60700 2.1 27 119 88 30 89 89 19G 0.8649 0, 9 6, 4 7, 1 135000 64800 2.1 26 120 92 30 90 90 19H 0.8654 1.0 7.0 7, 1 131600 66900 2.0 26 118 88 - - - 19I 0.8774 11.2 75.2 6, 7 66400 33700 2.0 49 119 99 40 79 13 19J 0.8995 5, 6 39, 4 7.0 75500 29900 2.5 101 122 106 - - -
89/161 g / cm3 = 1 g / cm3
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Table 9B. Physical properties of compression-molded film polymer.
Ex. Density (g / cm ³ ) Melting index (g / 10 min) Immediate deformation after 100% deformation (%) Immediate deformation after deformation of 300% (%) Immediate deformation after deformation of 500% (%) Recovery after 100% (%) Recovery after 300% (%) Recovery after 500% (%) 19A 0.878 0, 9 15 63 131 85 79 74 19B 0.877 0.88 14 49 97 86 84 81 19F 0.865 1 - - 70 - 87 86 19G 0.865 0, 9 - - 66 - - 87 19H 0.865 0.92 - 39 - - 87 -
Table 9c. Average block index for exemplary polymers ¹
Example Zn / C2 ^{1 2} Medium BI Polymer F 0 0 Polymer 8 0.56 0.59 Polymer 19A 1.3 0.62 Polymer 5 2.4 0.52 Polymer 19B 0.56 0.54 Polymer 19H 3, 15 0.59
90/161 ¹ Additional information regarding the calculation of block indices for various polymers is disclosed in US Patent Application Publication No. 2006-0199930, entitled “Ethylene / a — Olefin Block Interpolymers, filed on March 15, 2006, on behalf of Colin LP Shan, Lonnie Hazlitt, et al., and transferred to Dow Global Technologies Inc.
² Zn / C2 * 1000 = (Zn feed flow * Zn concentration / 1000000 / Mw Zn) / (Total ethylene feed flow * (1 ^the fractionated ethylene conversion rate / Mw ethylene) * 1000) .
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Please note that Zn in Zn / C ₂ * 1000 refers to the amount of zinc in diethyl zinc (“TEN”) used in the polymerization process, and C ₂ refers to the amount of ethylene used in the polymerization process.
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Modified impact compositions [208] The interpolymer in ethylene / a-olefin multiblocks and the amount used as an impact modifier will vary depending, among other variables, on the polymer to be modified for impact, the application, and the desired properties. It has been found that if improved low temperature impact is desired then an ethylene / α-olefin multiblock interpolymer prepared using relatively more chain exchange agent may be more useful. While any amount of exchange agent can be useful, it is often preferable to prepare the interpolymer using from about 50 to about 300 ppm chain exchange agent. While not wishing to be linked to any particular theory, it is believed that this often results in an advantageous multi-core / film morphology as described, for example, in PCT application No. PCT / US2005 / 008917, filed on March 17, 2005, which claims priority for provisional US patent application No. 60 / 553,906, filed on March 17, 2004.
[209] It has also been found that to a certain extent the toughness efficiency (the expected amount of improvement from a minimum amount of impact modifier) is improved when the interpolymer density in ethylene / a-olefin multiblocks decreases. For this reason it is often desirable to employ an interpolymer with a density of about 0.85 to about 0.93 g / cm ³ .
[210] The amount of interpolymer used in ethylene / a-olefin multiblocks will vary depending, among other variables, on the polymer to be modified for impact, the application, and the desired properties. Typically,
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93/161 an impact modifying amount is employed to maintain or increase the resistance to Izod impact at 20 ° C by at least about 5%, preferably by at least about 10%, more preferably by at least about 15% compared to a similar composition without the interpolymer in ethylene / a-olefin multiblocks. If low temperature impact properties are desired then sufficient amount can be employed to maintain or increase the Izod notch impact strength at -20 ° C by at least about 5%, preferably by at least about 10%, more preferably at least about 15% with respect to a similar composition without the interpolymer in ethylene / α-olefin multiblocks. This amount can be the same or different from the amount used to maintain or increase the resistance to Izod impact at notch at 20 ° C.
[211] The amounts of ingredients used will differ depending on, among other things, the application and the desired properties. Often, the weight ratio of multiblock copolymer to polyolefin can be from about 49:51 to about 5:95, more preferably from 35:65 to about 10:90. Preferably, it is preferable to employ at least about 1, preferably at least about 5, more preferably at least about 10, even more preferably at least about 20 weight percent of the interpolymer in ethylene / α-olefin multiblocks or mixture as an impact modifier. Similarly, it is desirable to employ no more than about 50, preferably no more than about 35, more preferably no more than about 25 weight percent of the multi-block interpolymer of
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94/161 ethylene / a-olefin or mixture as an impact modifier.
[212] In some embodiments, the amount of the interpolymer in ethylene / a-olefin multiblocks is about
of 10 per percent in weight a fence 40 percent by weight, in fence in 15 by percent in Weight about 35 percent in Weight, in fence in 20 per percent in weight at about 30 per
weight percent based on the total weight of the impact modified composition.
Polymeric compositions that can be modified for impact [213] Virtually any thermoplastic polymer composition can be advantageously modified for impact by adding one or more interpolymers in ethylene / a-olefin multiblocks discussed above. Such polymeric compositions comprise thermoplastic polyurethanes (for example, PELLATANE ™ and ISOPLAST ™ produced by The Dow Chemical Company), poly (vinyl chlorides) (PVCs), styrenics, hydrogenated styrenics, polynorbornene, polyethylene-co-norbornene, poly (4- methyl-pentene) including poly (4-methyl-pentene) pre-grafted with one or more functional monomers for compatibility, polyolefins (including, for example, ethylene / carbon monoxide (ECO) copolymers or linear alternating ECO copolymers such as those disclosed by US serial No. 08 / 009,198, filed on January 22, 1993 (now abandoned) under the names of John G. Hefner and Brian WS Kolthammer, entitled Improved Catalysts For The Preparation of Linear Carbon Monoxide / Alpha Olefin Copolymers for the preparation of linear carbon monoxide / alpha-olefin copolymers), and polymers of
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95/161 ethylene / propylene / carbon monoxide (EPCO)), various engineering thermoplastics (eg, polycarbonate, thermoplastic polyester, polyamides (eg, nylon), polyacetals, or polysulfones), and mixtures thereof. Generally, the polyolefinic polymers that can be most frequently used are polyethylene (for example, high density polyethylene, such as that produced by semi-fluid (sludge) or gas phase polymerization processes) or polypropylene or propylene-based polymers.
[214] The properties of the high density polyethylene (HDPE) useful in the present invention may vary depending on the desired application. Typically, useful HDPE has a density greater than 0.94 g / cm3. Preferably, the density is greater than 0.95 g / cm3, but less than about 0.97 g / cm3. HDPE can be produced by any process including Cr or Ziegler-Natta catalyst processes. The molecular weight of HDPE for use in the present invention varies depending on the application, but can be conveniently indicated using a melt flow measurement, according to ASTM D-1238-03, condition 190 ° C / 2.16 kg and condition 190 ° C / 5.0 kg, which are known as I2 and I5, respectively. The melt flow determinations can also be performed even at higher weights, such as according to ASTM D-1238, condition 190 ° C / 10.0 kg and condition 190 ° C / 21.6 kg, which are known as I10 and I21, respectively. The melt flow rate for propylene-based polymers is used and it is inversely proportional to the molecular weight of the polymer. The melt flow rate is tested according to ASTM D 1238, condition 230 ° C / 2.16 kg (formerly, condition L).
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Therefore, the higher the molecular weight, the lower the melt flow rate, although the relationship is not linear. The lower limit for melt index (I2) for HDPE useful here varies widely depending on the application, for example, blow molding or injection molding, etc., but is generally at least about 0.1 gram / 10 minutes ( g / 10 min), preferably about 0.5 g / 10 min, especially about 1 g / 10 min, to an upper limit of about 80 g / 10 min, preferably about 25 g / 10 min , and especially about 20 g / 10 min. The molecular weight of HDPE for use in the present invention, especially in pipe applications, varies depending on the application and can also be indicated using a melt flow measurement according to ASTM D-1238, condition 190 ° C / 5 kg (also known as I5). The lower limit for the melt index (I5) for HDPE useful here is generally about 0.1 g / 10 min, preferably about 0.2 g / 10 min, at an upper limit for the melt index of about 0.6 g / 10 min. The molecular weight distribution (Mw / Mn) of the selected HDPE can be wide or narrow, for example, Mw / Mn from about 2 to as high as about 40.
[215] In general, polypropylene is in the isotactic form of homopolymer polypropylene, although other forms of polypropylene (for example, syndiotactic or atactic) may also be used. Copolymers for polypropylene impact (for example, those in which a secondary copolymerization step is used reacting ethylene with propylene) and random copolymers (also modified in the reactor and usually containing 1.5-7% ethylene copolymerized with propylene), however , can also be used in
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97/161 TPO formulations disclosed herein. A full discussion of various polypropylene polymers is contained in Modern Plastics Encyclopedia / 89, published in mid-October 1988, volume 65, number 11, pages 86-92. The molecular weight and hence the melt flow rate of the polypropylene for use in the present invention varies depending on the application. The melt flow rate for the polypropylene useful here is generally from about 0.1 g / 10 min to about 100 g / 10 min, preferably from about 0.5 g / 10 min to about 80 g / 10 min, and especially from about 4 g / 10 min to about 70 g / 10 min. The propylene polymer can be a propylene homopolymer, or it can be a random copolymer or even an impact copolymer (which already contains a rubber phase). Examples of such propylene polymers include VISTAMAX (produced by ExxonMobil), VERSIFY and INSPIRE (produced by The Dow Chemical Company), and PROFAX (produced by Lyondell).
Methods for preparing mixing compositions [216] The mixing compositions of the present invention are prepared by any convenient method, including dry mixing of the individual components and subsequently mixing by melting, either directly in the extruder used to manufacture the finished article (for example, the automotive part), or by pre-mixing by melting in a separate extruder (for example, a Banbury mixer). Typically, mixtures are prepared by mixing or kneading the respective components at a temperature around or above the melting point temperature of one or both components. For most multi-block copolymers, this temperature can be above 130 ° C,
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98/161 very generally above 145 ° C, and most preferably above 150 ° C. Typical polymer mixing or kneading equipment can be used which is capable of reaching the desired temperatures and plasticizing the mixture by melting. These include mills, kneaders, extruders (both single spindle and twin spindle), Banbury mixers, and the like. The sequence and method of mixing may depend on the final composition. A combination of Banbury batch mixers and continuous mixers can also be employed, such as a Banbury mixer followed by a mill mixer followed by an extruder.
Molding operations [217] There are many types of molding operations that can be used to form parts or manufactured articles useful from TPO formulations disclosed herein, including various injection molding processes (for example, the one described in Modern Plastics Encyclopedia / 89, published in mid-October 1988, Volume 65, Number 11, pp. 264-268, “Introduction to Injection Molding (“ Introduction to Injection Molding) and pp. 270-271, “Injection Molding Thermoplastics (“ Injection molding thermoplastics), and blow molding processes (for example, the one described in Modern Plastics Encyclopedia / 89, published in mid-October 1988, Volume 65, Number 11, pp. 217-218, “Extrusion-Blow Molding (“blow molding / extrusion), profile extrusion, sheet extrusion, and thermoforming. Some of the manufactured items include fuel tanks, external furniture, tubes, automotive container applications, automotive shocks, instruments, grilles and wheel covers, as well as other household and personal items,
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99/161 including, for example, freezer container. Of course, a person skilled in the art can also combine polymers to advantageously use refractive index to improve or maintain clarity of end-use articles, such as freezer containers.
Additives [218] Additives such as antioxidants (eg, hindered phenolics (eg, IRGANOX ™ 1010), phosphites (eg, IRGAFOS ™ 168)), adhesion additives (eg, PIB) can also be included in TPO formulations ), non-stick additives, pigments, fillers (eg talc, diatomaceous earth, nanocharges, metal particles, glass particles or fibers, carbon black, other reinforcing fibers, etc.), and the like, to the extent that they do not interfere with the improved formulation properties discovered by applicants.
[219] Optionally, the impact modified compositions disclosed herein may comprise independently or may be substantially free of at least one additive. Some non-limiting examples of suitable additives include slip agents, non-stick agents, adhesion additives, plasticizers, oils, waxes, antioxidants, UV stabilizers, dyes or pigments, fillers, flow aids, coupling agents, crosslinking agents, surfactants, solvents, lubricants, antifogging agents, nucleating agents, flame retardants, antistatic agents and combinations thereof. The total amount of the additives can vary from about more than 0 to about 50% by weight, from about 0.001% by weight to about 40% by weight, from about 0.01% by weight to
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about 30% by weight, fence in 0, 1% by weight at about 20% in Weight, in fence of 0.5 % by weight The about 10% in Weight, or in fence in 1% in weight a fence in 5% in weight of weight total gives
composition modified for impact. Some polymer additives have been described in Zweifel Hans et al., "Plastics Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition (2001). In some embodiments, the impact modified compositions disclosed herein do not comprise an additive such as those disclosed herein. In some embodiments, the impact modified compositions disclosed herein optionally comprise a sliding agent. Sliding is the translation movement of film surfaces on top of each other or of film surfaces on other substrates. Sliding performance of films can be measured by ASTM D 1894, “Static and Kinetic Coefficients of Friction of Plastics Films and Sheeting (“ Static and kinetic friction coefficients of sheet and plastic film). In general, the slip agent can transfer slip properties by modifying the surface properties of articles such as films, and reduce friction between layers of films and between films and other surfaces with which they come into contact.
[220] Any slip agent known to a person of ordinary skill in the art can be added to at least one outer layer of the manufactured articles disclosed herein. Non-limiting examples of glidants include primary amides, having from about 12 to about 40 carbon atoms (for example, erucamide, oleamide, stearamide and beenamide); secondary amides having
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101/161 of about 18 to about 80 carbon atoms (for example, stearyl erucamide, beenyl erucamide, methyl erucamide and ethyl erucamide); secondary bis-amides having from about 18 to about 80 carbon atoms (for example, ethylene-bisstearamide and ethylene-bis-oleamide); and combinations thereof.
[221] Optionally, the impact modified compositions disclosed herein may comprise a non-stick agent. The non-stick agent can be used to prevent undesirable adhesion between the touch surfaces of the manufactured articles disclosed herein, particularly in heat and moderate pressure during storage, manufacture or use. Any nonstick agent known to a person of ordinary skill in the art can be added to the impact modified compositions disclosed herein. Non-limiting examples of non-stick agents include minerals (feet, clays, chalk, and calcium carbonate), synthetic silica gel (eg, SYLOBLOC ^® by Grace Davison, Columbia, MD), natural silica (eg, SUPER FLOSS® from Celite Corporation, Santa Barbara, CA), talc (for example, OPTIBLOC ^® of Luzenac, Centennial, CO), zeolites (for example, SIPERNAT ^® of Degussa, Parsippany, NJ), aluminum silicates (for example, SILTON ^® of Mizusawa Industrial Chemicals, Tokyo, Japan), limestone (for example, CARBOREX ^® by Omya, Atlanta, GA), spherical polymer particles (for example, EPOSTAR ^® , poly (methyl methacrylate) particles from Nippon Shokubai, Tokyo, Japan and TOSPEARL ^® , silicone particles from GE Silicones, Wilton, CT), waxes, amides (erucamide, oleamide, stearamide, beenamide, ethylene-bis-stearamide, ethylene-bis-oleamide, stearyl erucamide and other agents
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102/161 slip), molecular sieves, and combinations thereof. Mineral particles can decrease adherence by creating a gap between articles, although organic non-stick agents can migrate to the surface to limit surface adhesion. When used, the amount of the nonstick agent in the impact modified compositions disclosed herein can be from about more than 0 to about 3% by weight, from about 0.0001 to about 2% by weight, from about 0.001 to about 0.5% by weight of the total weight of the impact-modified composition. Some release agents have been described in Zweifel Hans et al., "Plastics Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 7, pages 585-600 (2001). Optionally, the impact modified compositions disclosed herein can comprise a plasticizer. In general, a plasticizer is a chemical that can increase flexibility and decrease the glass transition temperature of polymers. Any plasticizer known to a person of ordinary skill in the art can be added to the impact modified compositions disclosed herein. Non-limiting examples of suitable plasticizers include mineral oils, abietates, adipates, alkyl sulfonates, azelates, benzoates, chlorinated paraffins, citrates, epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils, isobutyrates, oleates, pentaerythritol derivatives, phosphates, phthalates, esters, polybutenes, ricinoleates, sebacates, sulfonamides, tri- and pyromelitates, biphenyl derivatives, stearates, difuran diesters, fluorine-containing plasticizers, hydroxy benzoic acid esters, isocyanate adducts, aromatic compounds
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103/161 of multiple rings, derived from natural products, nitriles, siloxane-based plasticizers, tar-based products, thioethers and combinations thereof. Where used, the amount of plasticizer in the impact modified compositions disclosed herein can be from more than 0 to about 15% by weight, from about 0.5% by weight to about 10% by weight, or from about 1 % by weight to about 5% by weight of the total weight of the impact modified composition. Some plasticizers have been described in Gerge Wypych, “Handbook of Plasticizers, ChemTec Publishing, Toronto-Scarborough, Ontario (2004).
[222] In some embodiments, the impact modified compositions disclosed herein optionally comprise an antioxidant that can prevent the oxidation of polymeric components and organic additives in the impact modified composition. Any antioxidant known to a person of ordinary skill in the art can be added to the impact modified compositions disclosed herein. Non-limiting examples of appropriate antioxidants include hindered or aromatic amines such as alkyl diphenylamines, phenyl-a-naphthylamine, alkyl or aralkyl-substituted phenyl-α-naphthylamine, alkylated p-phenylene diamines, tetramethyl diamino diphenylamine and the like; phenols such as 2,6-ditherciobutyl-4-methyl phenol, 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-ditherciobutyl-4'hydroxybenzyl) benzene, tetrakis [(methylene (3 , 5diterciobutyl-4-hydroxy hydrokinamate)] methane (eg, IRGANOX ™ 1010, from Ciba Geigy, New York); acryloyl modified phenols; 3,5-ditherciobutyl-4-hydroxy octadecyl cinnamate (eg, IRGANOX ™ 1076 , commercially available from Ciba Geigy), phosphites and phosphonites;
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104/161 hydroxylamines; benzofuranone derivatives; and combinations thereof. Where used, the amount of antioxidant in the impact modified compositions disclosed herein can be from more than 0 to about 5% by weight, from about 0.0001% by weight to about 2.5% by weight, from about 0.001% by weight to about 1%, or from about 0.001% by weight to about 0.5% by weight of the total weight of the impact modified composition. Some antioxidants have been described in Zweifel Hans et al., "Plastics Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 1, pages 1-140 (2001).
[223] In other embodiments, the impact modified compositions disclosed herein optionally comprise a UV stabilizer that can prevent or reduce the degradation of the impact modified composition by UV radiation. Any UV stabilizer known to a person of ordinary skill in the art can be added to the impact modified compositions disclosed herein. Non-limiting examples of suitable UV stabilizers include benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidines, carbon black, hindered amines, nickel extinguishers, phenolic antioxidants, metal salts, zinc compounds and combinations thereof. Where used, the amount of UV stabilizer in the impact modified compositions disclosed herein can be from more than 0 to about 5% by weight, from about 0.01% by weight to about 3% by weight, from about 0.1% by weight to about 2%, or from about 0.1% by weight to about 1% by weight of the total weight of the impact modified composition. Some UV stabilizers have been described in Zweifel Hans et al.,
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Plastics Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 2, pages 141-426 (2001).
[224] In additional embodiments, the impact modified compositions disclosed herein optionally comprise a dye or pigment that can change the look of the modified compositions for impact on human eyes. Any dye or pigment known to a person of ordinary skill in the art can be added to the impact modified compositions disclosed herein. Non-limiting examples of suitable dyes or pigments include inorganic pigments such as metal oxides such as iron oxide, zinc oxide, and titanium oxide, mixed metal oxides, carbon black, organic pigments such as anthraquinones, anthraxes, azo and monoazo compounds, arylamides, benzimidazolones, BONA lacquers, diketopyrrole-pyrroles, isoindolinones, metal complexes, monoazo salts, naphthols, b-naphthols, naphthol AS, naphthol lacquers, perylenes, perinones, phthalocyanines, pyranthrones, quinacridones, quinacridones, quinacridones and quinacridones themselves. Where used, the amount of dye or pigment in the impact modified compositions disclosed herein can be from about more than 0 to about 10% by weight, from about 0.1% by weight to about 5% by weight, or from about 0.25% by weight to about 2% by weight of the total weight of the impact modified composition. Some colorants have been described in Zweifel Hans et al., Plastics Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, chapter 15, pages 813-882 (2001).
[225] Optionally, compositions modified for
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106/161 impacts disclosed herein may comprise a load that can be used to adjust, among others, volume, weight, costs and / or technical performance. Any charge known to a person of ordinary skill in the art can be added to the impact modified compositions disclosed herein. Non-limiting examples of suitable fillers include talc, calcium carbonate, chalk, calcium sulphate, clay, kaolin, silica, glass, fumed colloidal silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina such as trihydrated alumina, glass microspheres, thermoplastic microspheres, barite, sawdust, glass fibers, carbon fibers, carbon black, marble powder, cement powder, magnesium oxide, magnesium hydroxide, oxide antimony, zinc oxide, barium sulfate, titanium dioxide and combinations thereof. In some embodiments, the filler is barium sulfate, talc, calcium carbonate, silica, glass, fiberglass, alumina, titanium dioxide, or a mixture thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, fiberglass or a mixture of them. Where used, the amount of filler in the impact modified compositions disclosed herein can be from about more than 0 to about 50% by weight, from about 0.01% by weight to about 40% by weight, from about 0.1% by weight to about 30% by weight, from about 0.5% by weight to about 20% by weight, or from about 1% by weight to about 10% by weight of the total weight of the composition modified for impact. Some fillers have been disclosed in US Patent No. 6,103,803 and Zweifel Hans et al., "Plastics Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 17, pages 901-948 (2001).
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107/161 [226] Optionally, the impact modified compositions disclosed herein may comprise a lubricant. In general, the lubricant can be used, among others, to modify the rheology of the molten oriented film, to improve the surface finish of molded articles, and / or to facilitate the dispersion of fillers or pigments. Any lubricant known to a person of ordinary skill in the art can be added to the impact modified compositions disclosed herein. Non-limiting examples of suitable lubricants include fatty alcohols and their esters of dicarboxylic acids, fatty acid esters of short chain alcohols, fatty acids, fatty acid amides, metal soaps, oligomeric fatty acid esters, fatty acid esters of chain alcohols long, lignite waxes, polyethylene waxes, polypropylene waxes, synthetic and natural paraffin waxes, fluorinated polymers and combinations thereof. Where used, the amount of lubricant in compositions modified for
impact disclosed here may be fence in more that 0 to about 5% in weight of about 0.1% by weight about 4% in weight, or in about 0.1% by weight at fence in 3% in weight of total weight gives modified composition for impact. Some
Suitable lubricants have been disclosed in Zweifel Hans et al., Plastics Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 5, pages 511-552 (2001). Optionally, the impact modified compositions disclosed herein can comprise an antistatic agent. In general, the antistatic agent can increase the conductivity of the manufactured articles disclosed here and prevent the accumulation of static charge. Any
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108/161 antistatic agent known to a person of ordinary skill in the art can be added to the compositions modified for impact disclosed herein. Non-limiting examples of suitable antistatic agents include fillers (for example, carbon black, metallic particles and other conductive particles), fatty acid esters (for example, glycerol monostearate), ethoxylated alkylamines, diethanolamides, ethoxylated alcohols, alkyl sulfonates, phosphates alkyl, quaternary ammonium salts, alkyl betaines and combinations thereof. Where used, the amount of the antistatic agent in the impact modified compositions disclosed herein can be from about more than 0 to about 5% by weight, from about 0.01% by weight to about 3% by weight, or about 0.1% by weight to about 2% by weight of the total weight of the impact modified composition. Some suitable antistatic agents have been disclosed in Zweifel Hans et al., Plastics Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 10, pages 627-646 (2001).
[227] In additional embodiments, the impact modified compositions disclosed herein optionally comprise a crosslinking agent that can be used to increase the crosslink density of the impact modified composition. Any crosslinking agent known to a person of ordinary skill in the art can be added to the impact modified compositions disclosed herein. Non-limiting examples of suitable cross-linking agents include organic peroxides (for example, alkyl peroxides, aryl peroxides, peroxyesters, peroxy carbonates, diacyl peroxides,
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109/161 peroxykets, and cyclic peroxides) and silanes (e.g., vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxy ethoxy) silane, vinyl triacetoxy silane, vinyl methyl dimethoxysilane, and 3-methacryloyloxy propyl trimethoxysilane). Where used, the amount of the crosslinking agent in the impact modified compositions disclosed herein can be from about more than 0 to about 20% by weight, from about 0.1% by weight to about 15% by weight, or from about 1% by weight to about 10% by weight of the total weight of the impact modified composition. Some suitable cross-linking agents have been disclosed in Zweifel Hans et al., Plastics Additives Handbook, Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 14, pages 725-812 (2001).
[228] In certain embodiments, the impact modified compositions disclosed herein optionally comprise a wax, such as a petroleum wax, low molecular weight polypropylene or polyethylene, synthetic wax, polyolefin wax, beeswax, vegetable wax, soy wax, palm wax, candle wax or an ethylene / a-olefin interpolymer having a melting point greater than 25 ° C. In certain embodiments, the wax is a low molecular weight polypropylene or polyethylene having a numerical average molecular weight of about 400 to about 6,000 g / mol. The wax can be present in the range of about 0% by weight to about 50% by weight or from about 1% by weight to about 40% by weight of the total weight of the impact modified composition.
Improved impact strength [229] The compositions of the present invention have strength
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110/161 to improved impact. Impact strength can be measured using, for example, the Izod notch impact test. The notched Izod impact is a single point test that measures a material's resistance to the impact of an oscillating pendulum. Izod impact is defined as the kinetic energy needed to start the fracture and continue the fracture until the specimen breaks. Izod specimens are notched to prevent specimen deformation in response to impact. The test is performed according to ASTM D56. Typically, the compositions of this invention maintain or increase the resistance to Izod notch impact at 20 ° C by at least about 5%, preferably by at least about 10%, more preferably by at least about 15% with respect to a similar composition without ethylene / a-olefin interpolymer. In addition, often, compositions of this invention maintain or increase the resistance to Izod notch impact at 20 ° C by at least about 5%, preferably by at least about 10%, more preferably by at least about 15% with respect to to a similar composition devoid of ethylene / α-olefin interpolymer. These new impact compositions also have an improved ductile-brittle transition temperature i.e. the transition from ductile to brittle failure occurs at lower temperatures, typically at least 5 ° C, preferably 10 ° C, and more preferably at least 15 ° C less than that of the polymer that was modified for impact, and less than that of a composition modified for impact using a random copolymer of ethylene / a-olefin (of density and melt index approximately equal to that of multiblocks) as the impact modifier.
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Comparative Examples and Examples of the present invention Mixture preparation [230] A series of mixtures of high density polyethylene (Component 1) + impact modification polymer (Component 2) was prepared by melting various concentrations of the two components. Before processing the mixtures, an antioxidant powder package is added to a physical mixture of the two components in a sealed bag. The package consists of 200 ppm of IRGANOX 1010 and 400 ppm of IRGAFOS 168. The physical mixture is turned over to disperse the antioxidant throughout the resin sample. Each physical mixture is purged with nitrogen to help remove any residual oxygen from the bag.
[231] The combination of polymeric physical mixture + additive package is processed in a Haake system supplied with an 18 mm Leistritz extruder with two spindles (L / D = 30), a two spindle drill feeder K2VT20 equipped with powder spindles long-pitch, two chilled water bath temper tanks, and a 4-blade PELL-2 blade chipper from Berlyn. A water circulator is attached to the extruder feed throat jacket and the temperature is adjusted to 20 ° C in order to prevent the polymer from melting and forming voids in the feed throat. The extruder temperature zones are set to 150, 180, 200, 215, and 215 ° C. The extruder die is set at 215 ° C. Before extrusion, a cap provided with a nitrogen line is placed on top of the feed funnel. Seal the transition area from the feeder discharge to the feed throat cone of the extruder with heavy aluminum foil. The extruder is preheated, calibrated and operated empty with
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112/161 nitrogen flowing throughout the system to purge it of oxygen.
[232] The physical polymer / antioxidant mixture is placed in the extruder feed hopper with the cap supplied with nitrogen in place. The physical mixture is fed into the extruder, melted and extruded. The extrudate passes through two quick-cooling tanks to solidify the melt in a polymer row. The row passes through a pneumatic knife to remove water, and subsequently cut it into pellets with the Berlyn row cutter. The pellets are collected from the discharge chute in a labeled bag.
Test methods [233] Density of resin is measured by the Archimedes displacement method, according to ASTM D792-03, Method B, in isopropanol. The specimens were measured within 1 hour of molding, after conditioning in the isopropanol bath at 23 ° C for eight minutes, to achieve thermal equilibrium before measurement. The specimens were molded by compression according to ASTM D-4703-00, Annex A, with an initial warm-up period of five minutes, at about 190 ° C, and a cooling rate of 15 ° C / min by Procedure C. The specimen was cooled to 45 ° C in the press, with continuous cooling until cold to the touch.
Melt flow rate by extrusion plastomer [234] Melt flow rate measurements by extrusion plastomer melt flow rate for ethylene-based polymers according to ASTM D-1238-03, Condition 190 ° C / 2.16 kg, and Condition 190 ° C / 5 kg, which are known, respectively, as I ₂ and I ₅ . The rate
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113/161 melt flow is inversely proportional to the molecular weight of the polymer. Consequently, the higher the molecular weight, the lower the melt flow rate, although the relationship is not linear. The melt flow rate determinations can also be performed with even higher weights, such as according to ASTM D-1238, Condition 190 ° C / 10.0 kg and Condition 190 ° C / 21.6 kg, which are known , respectively, as I10 and I21. The melt flow rate ratio (FRR) is the melt flow rate ratio (I21) to melt flow rate (I2) unless otherwise specified. For example, in some cases FRR can be expressed as I ₂₁ / I ₅ , especially for higher molecular weight polymers.
Differential Scanning Calorimetry (DSC) [235] All results reported here were generated via TA Instruments DSC Model Q1000 DSC equipped with an RCS cooling accessory (refrigerated cooling system) and an automatic sample collector. A nitrogen purge gas flow of 50 mL / min was used throughout. The sample was pressed into a thin film using a 175 ° C press and a maximum pressure of 10.3 MPa (1500 psi) for about 15 seconds, then cooled with air to room temperature under atmospheric pressure. Then, about 3 to 10 mg of material was cut into a 6 mm diameter disk using a paper hole punch, weighed accurately to the nearest 0.001 mg, placed in a light aluminum pan (ca 50 mg) and then closed crimped . The thermal behavior of the sample was investigated with the following temperature profile: The sample was quickly heated to 180 ° C and this temperature was maintained for 3 minutes in order to remove
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114/161 any previous thermal history. Then, the sample was cooled to -40 ° C at a cooling rate of 10 ° C / min and then kept at -40 ° C for 3 minutes. Then, the sample was heated to 150 ° C at a heating rate of 10 ° C / min. Cooling and second heating were recorded.
Gel Permeation Chromatography (GPC) [236] The following procedure was used to determine the molecular architecture of the various polymeric compositions. The chromatographic system consisted of a 150 ° C Waters high temperature gel permeation chromatograph (Millford, MA) equipped with a Precision Detectors Model 2040 2-angle laser light scattering detector (Amherst, MA). For calculation purposes, the 15 ° angle of the light scattering detector was used. Data collection was performed using Viscotek's TriSEC software version 3 and a Viscotek 4-channel DM400 data manager. The system was equipped with a solvent degassing device in the Polymer Laboratories line.
[237] The carousel compartment was operated at 140 ° C and the column compartment was operated at 150 ° C. Four SHODEX HT 806M columns of 300 mm and 13 pm and a SHODEX HT 803M column of 150 mm and 12 pm were used. The solvent used was 1,2,4trichlorobenzene. The samples were prepared in a concentration of 0.1 g of polymer in 50 ml of solvent. The chromatographic solvent and the sample preparation solvent contained 200 pg / g of butylated hydroxytoluene (BHT). Both solvent sources were sprayed with nitrogen. The polyethylene samples were stirred slightly for 4 hours at 160 ° C. The injection volume used was 200 pL and the flow rate was 0.67 mL / min.
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115/161 [238] The GPC column set calibration was performed with 21 polystyrene standards of narrow molecular weight distribution, with molecular weights ranging from 580 to 8,400,000 g / mol, arranged in 6 cocktail mixes with at least a dozen separation between individual molecular weights. The standards were purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards were prepared in 0.025 g in 50 mL of solvent for molecular weights greater than or equal to 1,000,000, and 0.05 g in 50 mL of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80 ° C with slight agitation for 30 minutes. Mixtures of narrow patterns were used first, and in decreasing order from the highest molecular weight component, to minimize degradation. The peak molecular weights of polystyrene pattern are converted to molecular weights of polyethylene using equation 8 (described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):
^M polyethylene ^{A x (M} polystyrene) ⁽¹⁾ where M is the molecular weight, A has a value of 0.41 and B is equal to 1.0.
[239] The systematic approach for determining multi-detector displacements was made in a manner consistent with that published by Balke, Mourey, et al. (Mourey & Balk, Chromatography Polym. Chapter 12, (1992) and Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chapter 13, (1992)), optimizing Dow 1683 wide polystyrene triple detector log results for the narrow pattern column calibration results of the narrow polystyrene pattern calibration curve. The
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116/161 molecular weight data for determining detector volume displacement are obtained in a manner consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P ., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injected concentration used to determine the molecular weight is obtained from the mass detector area and the mass detector constant derivative of a linear polyethylene homopolymer of molecular weight 115,000 g / mol that was measured in reference to the 1475 homopolymer standard polyethylene from NIST. The chromatographic concentrations were assumed to be low enough to eliminate the treatment of the 2nd viral coefficient effects (concentration effects on molecular weight).
[240] Molecular weight calculations were performed using internal software. The calculations of the numerical average molecular weight, the average molecular weight and the average molecular weight z, were performed according to the following equations, assuming that the refractometer signal is directly proportional to the weight fraction. The refractometer signal taken from the baseline can be replaced directly by a weight fraction in the equations below. Note that the molecular weight can be from the conventional calibration curve or the absolute molecular weight of the light scattering ratio for refractometer. An improved estimate of average molecular weight z, refractometer signal taken from baseline can be replaced by the product of average molecular weight and weight fraction in equation (2) below:
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[241] When used here, the term bimodal means that the MED on a GPC curve exhibits two component polymers and one component polymer can still exist as a hump, bump or tail in relation to the MWD of the other component polymer. A bimodal MWD can be divided into two components: LMW component and HMW component. After unfolding, the peak width at half its maximum height (WAHM) and the average molecular weight (M _w ) of each component can be obtained. Then, the degree of separation (DOS) between the two components can be calculated by equation 3:
_{DOS =} lQg (^^) - log (^ 5 wahm ^h + wahm ^l (3) in which M _W ^H and M _W ^L are the respective weight average molecular weights of the HMW component and the LMW component; and WAHM ^h and WAHM ^l are the respective peak widths at half their maximum height of the unfolded molecular weight distribution curve for the HMW component and for the LMW component. 0 DOS for the new composition is greater than or equal to 0.01. In some embodiments, DOS is greater than about 0.05, 0.1, 0.5, or 0.8. Preferably, DOS for bimodal components is at least about 1 or May. For example, DOS is at least about 1.2, 1.5, 1.7, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0. In some embodiments, DOS is between about between 5.0 and about 100, between about 100 and 500, or between about 500 and 1000. It should be noted that DOS can
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118/161 be any number in the ranges above. In other incorporations, DOS exceeds 1,000.
ATREF [242] In some embodiments, the bimodality of the distributions is characterized by the weight fraction of the maximum peak temperature in temperature gradient elution fractionation data (typically abbreviated by TREF) as described, for example, in Wild et al ., Journal of Polymer Science, Poly. Phys. Ed., Volume 20, p. 441 (1982); U.S. Patent No. 4,798,081 (Hazlitt et al.); or in U.S. Patent No. 5,089,321 (Chum et al.). The weight fraction corresponding to the maximum temperature peak is referred to as the high density fraction, since it contains little or no short chain branches. The remaining fraction is therefore referred to as the short chain branch fraction (SCB), since it represents the fraction that contains virtually all short chain branches inherent in the polymer. This fraction is also known as the low density fraction.
[243] In the analytical fractionation analysis by temperature gradient elution (described in US Patent No. 4,798,081 and abbreviated as ATREF), the composition to be analyzed is dissolved in an appropriate heated solvent (for example, 1.2, 4-trichlorobenzene), and allowed to crystallize in a column containing an inert support (for example, stainless steel granule), slowly reducing the temperature of the column. The column is equipped with both an infrared detector and a differential viscosimetric (DV) detector. An ATREF-DV chromatogram curve is then generated by eluting the crystallized polymer sample from the column,
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119/161 slowly increasing the temperature of the eluting solvent (1,2,4-trichlorobenzene). The ATREF-DV method is further described in WO 99/14271. WO 99/14271 also describes an unfolding technique for multi-component polymeric mix compositions. Often, the ATREF curve is also called short-chain branch distribution (SCBD), since it indicates how evenly the comonomer (eg hexene) is distributed throughout the sample in the sense that when the temperature of elution decreases, comonomer content increases. The refractive index detector provides short-chain distribution information and the differential viscometer detector provides an estimate of the average viscosimetric molecular weight. A discussion of the precedent can be found in LG Hazlitt, J. Appl. Polym. Sci .: Appl. Poly. Symp., 45, 25-37 (1990). Swelling (swelling) [244] Resin swelling was measured using the Dow Lab swelling method, which consists of measuring the time required by a row of extruded polymer to cover a predetermined distance of 230 mm. For the measurement, a Gottfert 2003 reograph was used, with a 12 mm cylinder and equipped with a L / D 10 capillary matrix. The measurement was performed at 190 ° C, in two fixed shear rates, 300 s ^-1 and 1,000 s ^-1 , respectively. The more the resin swells (swells), the more slowly the free end of the row will move and the more time it will take to travel the distance of 230 mm. The swelling (swelling) is reported as values t300 and t1000 (s).
Rheology [245] For the measurement of rheology the sample was shaped by
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120/161 compression on a disc. The disks were prepared by pressing the samples onto 1.8 mm (0.071) thick plates and were subsequently cut into 25.4 mm (1 inch) disks. The compression molding procedure was as follows: 185 ° C (365 ° F) for 5 min at 689 kPa (100 psi); 185 ° C (365 ° F) for 3 min at 10.3 MPa (1500 psi); cooling to room temperature (about 23 ° C) at a rate of 15 ° C (27 ° F) / min.
[246] The rheology of the resin was measured on an ARES I rheometer (Advanced Rheometric Expansion System). ARES is a controlled strain rheometer. A rotary actuator (servomotor) applies shear strain in the form of strain to a sample. In response, the sample generates torque, which is measured by the transducer. Deformation and torque are used to calculate dynamic-mechanical properties such as modulus and viscosity. The viscoelastic properties of the sample in the melt were measured using a parallel plate arrangement, at constant temperature (190 ° C) and deformation (5%), and as a function of variable frequency (0.01 to 500 s ^-1 ). Storage modulus (G '), loss modulus (G), delta tg, and complex viscosity (eta *) of the resin were determined using the Orchestrator software (version 6.5.8) from Rheometrics.
[247] Low shear rheological characterization was performed on a SR5000 Rheometrics instrument in tension-controlled mode, using a 25 mm parallel plate fixture. This type of geometry was preferred over cone and plate because it requires minimal compression flow during sample loading, thus reducing residual stresses.
Flexural modulus and elastic modulus properties [248] The resin stiffness was characterized by measuring the
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121/161 flexural modulus in 5% strain and elasticity modulus in 1% and 2% strain, and test speed of 13 mm / min (0.5 inch / min) by ASTM D 790-99, Method B. The specimens were molded by compression according to ASTM D-4703-00 Annex 1 with an initial heating period of 5 min at about 190 ° C and a cooling rate of 15 ° C / min by the Procedure B The specimen was cooled to 45 ° C in the press with continuous cooling until cold to the touch.
Tensile properties [249] Tensile and break tensile strength was measured according to ASTM D-638-03. Both measurements were carried out at 23 ° C on rigid specimens of type IV that were molded by compression by ASTM D 4703-00 Annex A-1 with an initial heating period of 5 min at about 190 ° C and a rate cooling temperature of 15 ° C / min by Procedure C. The specimen was cooled to 45 ° C in the press with continuous cooling until cold to the touch.
Crack resistance by environmental stress (ESCR) [250] Crack resistance by environmental stress under ASTM D 1693-01, Method B. The specimens were molded according to ASTM D 470300 Appendix A with an initial warm-up period of 5 min at about 190 ° C and a cooling rate of 15 ° C / min per Procedure C. The specimen was cooled to 45 ° C in the press with continuous cooling until cold to the Touch.
[251] In this test, the susceptibility of a resin to mechanical failure by cracking is measured in conditions of constant deformation, and in the presence of a crack accelerating agent such as soaps, wetting agents, etc. At
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122/161 measurements were performed on specimens incised in a 100% by volume aqueous solution of IGEPAL CO-630 (vendor Rhone-Poulec, NJ), maintained at 50 ° C. Ten specimens were evaluated by measure. The ESCR value of the resin is reported as F50, the 50% failure time calculated from the probability graph.
Impact resistance [252] Izod impact resistance (foot / pound / inch) for compression molded plates notched at 23 ° C and -40 ° C was determined according to ASTM D 256-03, Method A using a device of Izod Olsen Tinius manual impact with a 200 inch-pound capacity pendulum.
[253] Izod compression-molded plates were prepared by ASTM D 4703-00 Annex A with an initial heating period of 5 min at about 190 ° C and a cooling rate of 15 ° C / min by Procedure C. The specimen was cooled to about 45 ° C in the press with continuous cooling until “cold to the touch.
HDPE impact property modification [254] Table 10 shows mixtures of high density polyethylene (HDPE) modified for impact.
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Table 10. Mixing components
Material description Source Density (g / cm ³ ) Melting index I2.16 (dg / min) Flow rate I21.6 (dg / min) DMDA 6230 of UNIVAL * High density polyethylene Commercial polymer from The DowChemical company (TDCC) 0.949 0, 3 25 UNIVAL DMDH 6400 * High density polyethylene Commercial polymer from The DowChemical company (TDCC) 0.961 0, 8 57 Example A Impact modification multi-block polymer TDCC 0.930 0, 5Example B Impact modification multi-block polymer TDCC 0.909 0, 5Example C Impact modification polymer TDCC 0.922 0, 5 - Example D Impact modification polymer TDCC 0.913 0, 5 - IRGANOX1010 Polymer stabilization additive Ciba - - - IRGAFOS168 Polymer stabilization additive Ciba - - -
Polymerization conditions [256] The polymerization process conditions used to produce the inventive and comparative samples are described below.
Example A: Polymer production conditions [257] Polymerizations in continuous solution are carried out in a computer controlled autoclave reactor equipped with
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124/161 internal stirrer. Purified alkane mixture solvent (ISOPAR ™ E obtainable from ExxonMobil Chemical Company), ethylene at 1.22 kg / h (2.70 lb / h), 1-octene, and hydrogen (where used) are supplied to a reactor 3.8 L equipped with a jacket for temperature control and an internal thermocouple. The solvent supply to the reactor is measured by a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and the pressure to the reactor. At the pump discharge, a side stream is used to provide jet streams for the catalyst and co-catalyst 1 injection lines and for the reactor agitator. These flows are measured by Micro-Motion mass flow meters and controlled by control valves or by manually adjusting needle valves. The remaining solvent is combined with 1-octene, ethylene, and hydrogen (where used) and fed to the reactor. A mass flow controller is used to release hydrogen to the reactor when necessary. The temperature of the monomer / solvent solution is controlled by using a heat exchanger before entering the reactor. This current enters the bottom of the reactor. The catalyst component solutions are dosed using mass pumps and flow meters and are combined with the catalyst jet solvent and introduced into the bottom of the reactor. The reactor operates full of liquid at 3.45 MPa (500 psig) with vigorous agitation. The product is removed through exit lines at the top of the reactor. All of the reactor's output lines are steam traversed and isolated. Polymerization is stopped by adding a small amount of water to the outlet line together with stabilizers or other additives and passing the mixture through a mixer
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125/161 static. The product stream is then heated by passing it through a heat exchanger before devolatilization. The polymeric product is recovered by extrusion using a devolatilization extruder and water-cooled pelletizer. The results and process details are contained below in Table 11.
Example B. Conditions for the production of polymer in multiblocks.
[258] Continuous solution polymerizations are performed in a well-mixed reactor controlled by computer and equipped with an internal stirrer. Purified alkane mixture solvent (ISOPAR ™ E obtainable from ExxonMobil Chemical Company), 2.7 kg / h ethylene (5.96 lb / h), 1-octene, and hydrogen (where used) are supplied to a 5.0 L equipped with a jacket for temperature control and an internal thermocouple. The solvent load to the reactor is measured by a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and the pressure to the reactor. At the pump discharge, a side stream is used to provide jet streams for the catalyst and co-catalyst 1 injection lines and for the reactor agitator. These flows are measured by Micro-Motion mass flow meters and controlled by control valves or by manually adjusting needle valves. The remaining solvent is combined with 1-octene, ethylene, and hydrogen (where used) and fed to the reactor. A mass flow controller is used to release hydrogen to the reactor when necessary. The temperature of the monomer / solvent solution is controlled by using a heat exchanger before entering the reactor. This current enters the bottom of the reactor. Catalyst component solutions are dosed using
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reactor. The reactor operates liquid filled at 2.8 MPa (406 psig)
with vigorous agitation. The product is removed through exit lines at the top of the reactor. All of the reactor's output lines are steam traversed and isolated. Polymerization is stopped by adding a small amount of water
on the outlet line together with stabilizers or others additives and passing the mixture through a mixer static. The product stream is then heated passing it through heat exchangers, and passes for two
devolatilizers in series before being cooled with water.
The results and process details are contained in the Table below.
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Table 11. Conditions of production of polymer sample in multiblocks.
Process conditions Units Ex. A Ex. B C2H4 kg / h (lb / h) 1.85 (4.08) 2.75 C8H16 kg / h (lb / h) 0.43 (0.95) 1.65 Solvent kg / h (lb / h) 15, 87 (34, 99) 23 H2 sccm ^{1 2 *} 11, 4 2 T ° C 135, 1 125 Concentration of ₂ catalyst A1 ppm 95, 2 115, 9 Catalyst flowTO 1 kg / h (lb / h) 0.075 (0.165) 0.245 B23 catalyst concentration ppm 41, 8 59, 2 Catalyst flowB2 kg / h (lb / h) 0.145 (0.319) 0.21 TEN concentration ppm 4055 5000 TEN flow kg / h (lb / h) 0. 149 (0. 328) 0.272 Concentration of cocatalyst ppm 1215.5 1665.6 Cocatalyst flow kg / h (lb / h) 0.122 (0.248) 0.16 Zn ⁴ in the polymer ppm 347, 1 802.6 Polymerization rate ⁵ kg / h (lb / h) 1,736 (3,827) 3 Conversion from C ₂ H ₄ ⁶ 0% 90 90 Solids 0% 9, 564 11,538 Efficiency ⁷ 132 73
¹ sccm = standard cm3 / min.
² Dimethyl [N- (2,6-di (1-methyl ethyl) phenyl) starch) (2-isopropyl phenyl) (α-naphthalen-2-diyl (6-pyridin-2-diyl) methane)] hafnium.
3Dimethyl bis- (1- (2-methyl cyclohexyl) ethyl) (2-oxoyl-3,5di (terciobutyl) phenylimino) zirconium.
4ppm in final product calculated by mass balance.
⁵ Polymer production rate.
⁶ Percent by weight of ethylene conversion in the reactor.
⁷ Efficiency, kg of polymer / g of M where g of M = g of Hf + g of Z.
[259] Examples C and D are prepared according to USP
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5,272,236 and USP 5,278,272, obviously adjusted for molecular weight and density.
Mixture preparation [260] A series of high density polyethylene mixtures is prepared (a) mixtures of DMDF 6230 + impact modification polymer (inventive or comparative polymer) and (b) mixtures of DMDH 6400 + modification polymer for impact (inventive or comparative polymer) by melting various concentrations of the two components (Table 12). For comparison purposes, HDPE samples are subjected to the same thermal extrusion history as samples of impact-modified HDPE mixtures. The concentration of the comparative polymer in the blend is adjusted to produce the same overall blend density as that of inventive HDPE blends.
[261] Before processing the mixtures, an antioxidant powder package is added to a physical mixture of the two components in a sealed bag. The package consists of 200 ppm of IRGANOX 1010 and 400 ppm of IRGAFOS 168. The physical mixture is turned over to disperse the antioxidant throughout the resin sample. Each physical mixture is purged with nitrogen to help remove any residual oxygen from the bag.
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Table 12. Mixture composition
Sample Impact modification pol. Concentration of DMDH 6400 in the mixture Modification polymer concentration.for impact on the mixture Calculated mixing density Units - % by weight % by weight g / cm ³ DMDA 6230 UNIVAL (HD1) none 100 0 - Inventive mix HD1A1 ₁ Example A 95 5 0.948 Inventive mix HD1A2 ₁ Example A 90 10 0.9471 Inventive mix HD1A3 ₁ Example A 80 20 0.9451 DMDH 6400 UNIVAL (HD2) none 100 0 - Inventive mix HD2A1 ₁ Example A 95 5 0.9594 Inventive mix HD2A2 ₁ Example A 90 10 0.9557 Comparative mixingHD2C1C Example C 90 10 0.9575 Inventive mix HD2A3 ₁ Example A 80 20 0.9546 Comparative mix HD2C2C Example C 84 16 0.9546 Comparative mixingHD2C3C Example C 78 22 0.9526 Inventive mix HD2B1 ₁ Example B 88 12 0.9544 Comparative mix HD2D1 _C Example D 87 13 0.9545 Inventive mix HD2B2 ₁ Example B 85 15 0.9528 Comparative mix HD2D2 _C Example D 83 17 0.9526
[263] The combination of physical polymer mixture + additive package is processed in a Haake supplied with an extruder
Leistritz 18 mm with two spindles (L / D = 30), a drill feeder with two K2VT20 spindles from K-TRON equipped with long pitch powder spindles, two bath quench tanks
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130/161 chilled water circulation, and a 4-blade PELL-2 blades from Berlyn. A water circulator is attached to the extruder feed throat jacket and the temperature is adjusted to 20 ° C in order to prevent the polymer from melting and forming voids in the feed throat. The extruder temperature zones are set to 150, 180, 200, 215, and 215 ° C. The extruder die is set at 215 ° C. Before extrusion, a cap provided with a nitrogen line is placed on top of the feed funnel. Seal the transition area from the feeder discharge to the feed throat cone of the extruder with heavy aluminum foil. The extruder is preheated, calibrated and operated empty with nitrogen flowing throughout the system to purge it of oxygen.
[264] The physical polymer / antioxidant mixture is placed in the extruder feed hopper with the cap supplied with nitrogen in place. The physical mixture is fed into the extruder, melted and extruded. The extrudate passes through two quick-cooling tanks to solidify the melt in a polymer row. The row passes through a pneumatic knife to remove water, and subsequently cut it into pellets with the Berlyn row cutter. The pellets are collected from the discharge chute in a labeled bag.
[265] It is calculated the density of mixing using the interface1 w ₁ 1-w ₁= + Pb P1 P2 where p _b is the density of the mixture, w1 is the weight fraction of
component 1 of the mixture, ρ ₁ is the density of component 1 of the mixture, and p ₂ is the density of component 2 of the mixture.
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Mixing properties of HDPE [266] Pure HDPE polymer DMDH 6400 and mixing samples are characterized by various analytical methods.
[267] Figure 8 shows overlapping DSC of HDPE DMDH 6400 and mixtures of DMDH 6400 + Example A of polymer in impact modification multi-blocks. A single peak of DSC is observed indicating the compatibility of the two components. Figure 9 shows the molecular weight distribution characterized by GPC. Figure 10 shows the comparison of melt strength.
[268] Table 13 shows the measured properties.
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Table 13. Physical properties of impact modification / HDPE polymer blend.
Sample Impact modification polymer Conc. impact modification polymer Calculated mixing density Density ^I 2.16 ^I 21.6 ^I 21.6 ^{/ I} 2.16 % by weight g / cm ³ g / cm ³ dg / min dg / minDMDA 6230 UNIVAL (HD1) none 00.9501 0.26 28.0 108 Inventive mix HD1A1 ₁ Example A 5 0.948 0.9486 0.24 26, 5 109 Inventive mix HD1A2 ₁ Example A 10 0.9471 0.9474 0.26 25.2 96 Inventive mix HD1A3 ₁ Example A 20 0.9451 0.9449 0.30 20.0 67 DMDH 6400 UNIVAL (HD2) none 0 - 0.9617 0.88 67.9 77 Inventive mix HD2A1 ₁ Example A 5 0.9594 0.9597 0.83 97.1 117 Inventive mix HD2A2 ₁ Example A 10 0.9557 0.95582 0.77 50.8 66 Comparative mix HD2C1C Example C 10 0.9575 0.9579 0.78 49, 5 63 Inventive mix HD2A3 ₁ Example A 20 0.9546 0.9545 0.71 37.9 53 Comparative mix HD2C2C Example C 16 0.9546 0.9536 0.71 40.8 57 Comparative mix HD2C3C Example C 22 0.9526 0.9521 0.73 35.7 49 Inventive mix HD2B1 ₁ Example B 12 0.9544 0.9555 0.79 48.5 61 Comparative mix HD2D1C Example D 13 0.9545 0.9546 0.74 43.8 59 Inventive mix HD2B2 ₁ Example B 15 0.9528 0.9536 0.73 45 62 Comparative mix HD2D2C Example D 17 0.9526 0.9218 0.69 40 58
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133/161 [269] Figure 11 shows the DSC comparison of the inventive sample and the comparative sample and Figure 12 shows the ATREF comparison of the inventive sample and the comparative sample. Table 14 lists the mechanical properties (stiffness / toughness) of the inventive mixture and the comparative mixture.
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Table 14. Mechanical properties of impact modification / HDPE polymer blend
Sample Modification polymer. for impact Conc. in. of mod.for impact Density Elast.de module 2% medium Medium bending module Tensile yield stress Along. for traction for break Izod impact at 23 ° C Izod impact at -20 ° C ESCR ofIGEPAL 1005, 50 ° C, F50 % by weight g / cm ³ kpsi kpsi kpsi O,% ft. lb / in ft. lb / in H (GPa) (GPa) (GPa)(N.m / m) (N.m / m)DMDA 6230 none 0 0.9501 122, 8 185, 2 2.53 1.62 111 UNIVAL HD1 (0.846) (1,276) (135) (87)Mist.inv. Ex.A 5 0.9486 123, 9 182.7 3, 18 1.97 207 HD1A1 ₁ (0.854) (1,260) (169) (105)Mist.inv. Ex.A 10 0.9474 118.7 173, 7 3.89 2.28 368 HD1A2 ₁ (0.818) (1,120) (208) (121)Mist.inv. Ex.A 20 0.9449 112, 4 162, 4 7.37 2.86 > 800 HD1A3 ₁ (0.775) (1,120) (393) (153)DMDH 6400 none 0 0.9617 178.3 244, 1 - - 2.23 2.19 17 UNIVAL HD2 (1,229) (1,683) (119) (117)Mist.inv. Ex.A 5 0.9597 168, 4 245.7 - - 3.36 2.49 24 HD2A1 ₁ (1,161) (1,694) (179) (133)Mist.inv. Ex.A 10 0.95582 163, 2 245, 1 - - 5, 17 2.77 31 HD2A2 ₁ (1,125) (1,690) (276) (148)Mist. comp. Ex.C 10 0.9579 158, 0 241, 3 - - 4, 15 2.69 27 HD2C1 _C (1,089) (1,663) (222) (144)Mist.inv. Ex.A 20 0.9545 150, 4 233, 5 4, 01 1098 11.8 5.31 38 HD2A3 ₁ (1,037) (1,610) (0.028)(631) (284)Mist. comp. Ex.C 16 0.9536 154.6 233, 6 3.82 837 5.41 3.07 51 HD2C2 _C (1,066) (1,610) (0.026)(289) (164)Mist. comp. Ex.C 22 0.9521 139, 1 206, 3 - - 6, 72 3.44 107 HD2C3 _C (0.959) (1,422) (359) (184)Mist.inv. Ex.B 12 0.9555 153, 4 234, 9 - - 10.87 2.96 26 HD2B1 ₁ (1,057) (1,620) (581) (158)Mist. comp. Ex.D 13 0.9546 150.2 228.7 - - 10.46 3.89 52
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HD2D1 _C (1,035) (1,576) (559) (208)Mist.inv. HD2B2 ₁ Ex.B 15 0.9536 146, 4(1,010) 221, 4(1,527) 3.63 (0.025) 883 13 (694) 4.18 (223) 29 Mist. comp. HD2D2 _C Ex.D 17 0.9518 145.8(1,005) 216, 8(1,495) 3.62 (0.025) 831 12.1 (646) 4.41 (236) 123
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136/161 [270] The increase in the inventive multiblock polymer concentration, Example A, from 0% by weight to 10% by weight in the HD2 mix series, is accompanied by a gradual improvement in crack resistance properties per action environmental stress and impact of the mixture (Table 14). The stiffness of the mixture, characterized by density and flexural modulus, basically does not change.
However, in increasing the polymer concentration of Example A to 20%, there is a significant improvement in the performance of Izod impact at room temperature and at low temperature of the mixture (inventive mixture HD2A31) (Table 14). The performance of the mixture (DMDH 6400 HD2 + Example A) was compared with that of the mixture (DMDH 6400 HD2 + Example C). In order to minimize the variables, a comparison is made between mixtures of similar global density and melting index. The mixtures (DMDH 6400 HD2 + Example A) show a superior balance of rigidity and impact properties when compared with the mixtures (DMDH 6400 HD2 + Example C). The tensile properties are also superior (Table 14). The second series of inventive mixtures, mixtures (DMDH 6400 HD2 + Example B), also has a good flexural modulus and impact resistance balance (Table 14). In this case, the performance is similar to that of comparative mixtures. TPO impact property modification [271] Table 15 shows the raw materials used in the preparation of the composite samples. The materials were used in the condition as received except for the ICP impact copolymer polypropylene sample. This sample was ground before use.
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Table 15: Raw materials
Material description Source ICP Impact copolymer polypropylene (MFR 35, 17% EPR) Commercial polymer from The Dow Chemical Company Example E Impact modification ethylene / octene multiblock copolymer The Dow Chemical Company Example E Impact modification ethylene / butene multi-block copolymer The Dow Chemical Company AFFINITY® Copolymer of Commercial Polymer EG 8150 ethylene / octene of The Dow (Example G) impact modification (density 0.868 / MI 0.5) Chemical Company Baby powderJETFIL 700C Compacted talc (average particle size 1.5 µm) Luzenac IRGANOXB225 IRGANOX 1010 + IRGAFOS 168 (50:50 ratio) Ciba Calcium stearate Mold release (NF grade) Witco
Polymerization conditions [273] The octene multiblock copolymer Example E was produced using the process described immediately below.
[274] Continuous solution polymerizations are carried out in a computer controlled autoclave reactor and equipped with an internal stirrer. Purified alkane mixture solvent (ISOPAR ™ E obtainable from ExxonMobil Chemical Company), ethylene at 1.22 kg / h (2.70 lb / h), 1-octene, and hydrogen (where used) are supplied to a reactor of 3.8 L equipped with a jacket for temperature control and an internal thermocouple. The solvent load to the reactor is measured by a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and the pressure to the reactor. When discharging the pump, a side chain is used to provide jet streams to the catalyst and co-catalyst injection lines and to the
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138/161 reactor. These flows are measured by Micro-Motion mass flow meters and controlled by control valves or by manually adjusting needle valves. The remaining solvent is combined with 1-octene, ethylene, and hydrogen (where used) and fed to the reactor. A mass flow controller is used to release hydrogen to the reactor when necessary. The temperature of the monomer / solvent solution is controlled by using a heat exchanger before entering the reactor. This current enters the bottom of the reactor. The catalyst component solutions are dosed using mass pumps and flow meters and are combined with the catalyst jet solvent and introduced into the bottom of the reactor. The reactor operates full of liquid at 3.45 MPa (500 psig) with vigorous agitation. The product is removed through exit lines at the top of the reactor. All of the reactor's output lines are steam traversed and isolated. The polymerization is interrupted by adding a small amount of water to the outlet line together with stabilizers or other additives and passing the mixture through a static mixer. The product stream is then heated by passing it through a heat exchanger before devolatilization. The polymeric product is recovered by extrusion using a devolatilization extruder and water-cooled pelletizer.
[275] The multi-block butene copolymer Example F was produced using the process described immediately below.
[276] Continuous solution polymerizations are carried out in a well-mixed reactor controlled by computer and equipped with an internal stirrer. Purified alkane mixture solvent (ISOPAR ™ E obtainable from ExxonMobil Chemical
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Company), ethylene at 2.7 kg / h (5.96 lb / h), 1-butene, and hydrogen (where used) are supplied to a 5.0 L reactor equipped with a jacket for temperature control and a internal thermocouple. The solvent load to the reactor is measured by a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and the pressure to the reactor. At the pump discharge, a side stream is used to provide jet streams for the catalyst and co-catalyst 1 injection lines and for the reactor agitator. These flows are measured by Micro-Motion mass flow meters and controlled by control valves or by manually adjusting needle valves. The remaining solvent is combined with butene, ethylene, and hydrogen (where used) and fed into the reactor. A mass flow controller is used to release hydrogen to the reactor when necessary. The temperature of the monomer / solvent solution is controlled by using a heat exchanger before entering the reactor. This current enters the bottom of the reactor. The catalyst component solutions are dosed using mass pumps and flow meters and are combined with the catalyst jet solvent and introduced into the bottom of the reactor. The reactor operates liquid-filled at 2.8 MPa (406 psig) with vigorous agitation. The product is removed through exit lines at the top of the reactor. All of the reactor's output lines are steam traversed and isolated. Polymerization is stopped by adding a small amount of water
on the line in output together with stabilizers or others additions and passing to mixture through on one mixer static. THE current product is So heated passing it through in changers heat, and goes by for two
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140/161 devolatilizers in series before being cooled with water. Mixing conditions [277] All samples were mixed using a 30mm W&P co-rotating twin screw extruder with ZSK30-0097 screw design. During extrusion, vacuum (0.06 MPa (18-20 inches Hg)) was used. The dropped mixed samples were fed into the extruder feed throat. Table 16 shows the mixing conditions. It was desired to feed the sample at a rate to maintain torque around 80%. The condition of the extruder has also been adjusted to eliminate line drops.
Table 16. Mixing conditions
Temp. of Zone1 (° C) Temp.of Zone2 (° C) Temp.of Zone3 (° C) Temp.of Zone4 (° C) Temp.of Zone5 (° C) Temp.melting point (° C) rpm ofspindle % intorque Matrix pressure MPa (psi) 167-190 184-206 197-213 192-207 198-223 198-222 398-411 55-03 0.62 -1.79(90-260)
[278] The samples were injection molded in a Toyo 90-ton molding machine.
[279] Mold: 1 0.318 cm (1/8) ASTM unventilated T bar and 1 10.16 x 0.318 cm (4 x 1/8) disc of unventilated ASTM in the cavity.
[280] Molding conditions:
Cylinder temperature: 204 ° C (400 ° F)
Mold temperature: 60 ° C (140 ° F)
Filling time; 1.6 seconds
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Conditioning pressure: 4.83MPa (700 psi)
Retention time: 25 seconds
Cooling time: 25 seconds
Testing methods
Izod - ASTM D256
Bending properties - ASTM D790, 2 mm / min
Tensile-related properties - ASTM D638, 50 mm / min Sample properties [281] Table 17 shows the dependence on Izod notch / temperature impact strength of the inventive mixtures samples ICP-E _I and ICP-F _I , and the comparative sample ICO-G _C and plotted on a graph shown in Figure 13.
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Table 17. Notched Izod impact test results
Component icp Ex.G Ex.AND Ex.f Jetfil Talc 700C Izod notch impact test results J / cm (pound-foot / inch) Sample #ASTM Izod at room temperature ASTM Izod in-10 ° C(14 ° F) ASTM Izod at -17.8 ° C(0 ° F) ASTM Izod at -28.9 ° C(20 ° F) ASTM Izod at -28.9 ° C (20 ° F) re-test Mix comp. ICP-G _c 63 27 - - 10 7.39 (13.84) 13, 35 10.1 1,753 1,539 Inv. ICP-E _I 63 - 27 - 10 7.38(13.83) 13, 78 12 10,288 9, 447 Inv.ICP-Fi 63 - - 27 10 6.54 (12.25) 11, 91 9, 5 6, 735 7, 561
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143/161 [282] The inventive examples show greater tenacity at low temperature than that of the comparative example.
[283] Material ductility is often measured in terms of the ductile-brittle transition temperature defined as the temperature below which a material fails in a brittle mode. For this comparison, the ductile-brittle transition temperature is defined as the temperature at which the notched Izod impact resistance reaches about 3.20 J / cm (6 pound-feet / inch). Figure 13 shows that the inventive examples (-28.9 ° C (-20F °) for ICP-F _I ; -34.4 ° C (30 ° F) for ICP-E _I ) exhibit lower ductile transition temperature fragile than that of the comparative example (-23.3 ° C (-10 ° F) for ICP-GC). Since the modulus of all three examples is similar, it follows that a smaller amount of the inventive modifier can be added to the formulation to increase its modulus or stiffness. The resulting mixture should still have a similar low temperature toughness compared to the comparative example. These data indicate that mixtures modified with the inventive polymer will have a better balance of stiffness / toughness than those modified with comparative modifiers.
Additional mixtures using OBC77 and REOC [284] The following polymers have been used in various mix compositions.
[285] The Inventive Example OBC77 is an ethylene / 1-octene block olefinic copolymer (OBC) having a composite content of 77% by weight, a composite density of 0.854 g / cm ³ , a melting point maximum per DSC of 105 ° C, a hard segment level based on a DSC measurement of
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6.8% by weight, an ATREF crystallization temperature of 73 ° C, a hard segment density of 0.915 g / cm ³ , a soft segment density of 0.851 g / cm ³ , a numerical average molecular weight of 188.254 Daltons , a weight average molecular weight of 329,600 Daltons, a melting index at 190 ° C / 2.16 kg of 1.0 dg / min and a melting index at 190 ° C / 10 kg of 37.0 dg / min.
[286] The REOC Comparative Example is a random ethylene / 1-octene copolymer (REOC) having a density of 0.87 g / cm ³ , a 1-octene content of 38% by weight, a maximum melting point of 59.7 ° C, a numerical average molecular weight of 59,000 Daltons, a weight average molecular weight of 121,300 Daltons, a melting index at 190 ° C / 2.16 kg of 1.0 dg / min and a melting index at 190 ° C / 10 kg of 7.5 dg / min. The product is commercially available from The Dow Chemical Company under the trade name ENGAGE® 8100.
[287] The above polymers were mixed melted with a polypropylene homopolymer (PPH) having a melt flow index at 230 ° C / 2.16 kg of 2.0 dg / min, and a density of 0.9 g / cm ³ . The product is commercially available from The Dow Chemical Company under the polypropylene trade name Dow H110-02N. In all mixtures, 0.2 part per 100 total polymer was added of a 1: 1 mixture of phenolic antioxidant / phosphite obtainable under the trade name IRGANOX B215 for thermal stability. This additive is designated as AO in Table I.
[288] The following mixing procedure was used. A 69 cm ³ Haake batch mixing vessel equipped with rotating blades was heated to 200 ° C for all areas. The rotor speed of the
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145/161 mixing vessel was set at 30 rpm. The PPH mixing vessel was loaded, allowed to drain for one minute, then loaded with AO and drained for two more minutes. Then, the mixing vessel was loaded either with the OBC77 Inventive Example or the REOC Comparative Example or with a 1: 1 mixture of the OBC77 Inventive Example and the REOC Comparative Example. After adding the elastomer, the mixing bowl rotor speed was increased to 60 rpm and mixing continued for another 3 minutes. Then, the mixture was removed from the mixing vessel and pressed between sheets of Mylar interspersed between metallic cursors and compressed in a Carver compression molding machine adjusted to cool to 15 ° C with a pressure of 137.8 MPa (20 kpsi) ). The cooled mixture was then molded by compression into 5 x 5 x 0.15 cm (2 inches x 2 inches x 0.06 inches) plates via compression molding for 3 minutes at 190 ° C, 13.8 MPa pressure ( 2 kpsi) for 3 minutes, 190 ° C and pressure of 137.8 MPa (20 kpsi) for 3 minutes, then cooling to 15 ° C and 137.8 MPa (20 kpsi) for 3 minutes.
[289] Mixtures prepared using this procedure described above are listed in Table 18 below.
Table 18
Blends with PP Mix 1 Mix 2 Mix 3 Ingredient Parties Parties Parties PPH 70 70 70 Inventive example OBC77 30 0 15 Comparative Example REOC 0 30 15 TO 0, 2 0, 2 0, 2
[290] Compression-molded plates were cut out so that they could have sections collected in the core. The cut plates were cold-polished before dyeing by removing
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146/161 block sections at -60 ° C to prevent greasing of the elastomer phases. The cold-polished blocks were dyed with the vapor phase of an aqueous solution of 2% ruthenium tetroxide for 3 hours at room temperature. The dyeing solution was prepared by weighing 0.2 mg of hydrated ruthenium (III) chloride (RuCl3.H2O) in a glass bottle with a screw cap and adding 10 mL of a 5% aqueous solution of sodium hypochlorite to the container, 25%. The samples were placed in the glass bottle using a glass slide having a double-sided tape. The slide was placed in the bottle to suspend the blocks about 2.54 cm (1 inch) above the dyeing solution. Sections approximately 100 nm thick were collected at room temperature using a diamond knife in a Leica EM UC6 microtome and placed in virgin 400 mesh TEM networks for observation.
[291] Bright field images were collected in a JEOL JEM 1230 operated at 100 kV acceleration voltage and collected using Gatan 791 and Gatan 794 digital cameras. The images were post-processed using Adobe Photoshop 7.0.
[292] Figures 14, 15, and 16 are electron micrographs for Mixtures 1, 2 and 3, respectively. The dark domains are ethylene / 1-octene polymers stained with RuCl3.H2O. As can be seen, the domains containing the OBC77 Inventive Example are much smaller than the REOC Comparative Example. The domain sizes of the OBC7 Inventive Example 7 range from less than 0.1 to 2 µm, while the domain sizes of the REOC Comparative Example range from about 0.2 to 5 µm. Mixture 3 contains a 1: 1 mixture of Inventive Example OBC77 and Comparative Example REOC. Note that the domain sizes for Mix 3 are well below
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147/161 of those in Mixture 2, indicating that the OBC77 Inventive Example improves the compatibility of the REOC Comparative Example with PPH.
[293] Image analysis of Mixtures 1, 2, and 3 was performed using Leica's Qwin Pro V2.4 software on 5kX TEM images. The magnification selected for image analysis depended on the number and size of particles to be analyzed. In order to allow binary image generation, manual tracing of the elastomer particles of the TEM impressions was performed using a black Sharpie marker. The traced TEM images were scanned using a Hewlett Packard Scan Jet 4c to generate digital images. The digital images were imported by Leica's Qwin Pro V2.4 program and converted into binary images by adjusting the gray level threshold to include the characteristics of interest. Once the binary images were generated, other processing tools were used to edit the images before analyzing the images. Some of these features included removing border features by accepting or deleting features, and manually cutting features that required separation. Once the particles in the images were measured, the sizing data was exported to a dispersion sheet that was used to create binary images for the rubber particles. The design data were placed in appropriate binary images and a histogram of particle lengths (maximum particle length) was generated against frequency percentage. The reported parameters were minimum, maximum and standard deviation. Table 19 below shows the results of the image analysis
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Table 19
Mix No. 1 2 3 Count (number) 718 254 576 Maximum domain size (mm) 5, 1 15, 3 2, 9 Minimum domain size (mm) 0, 3 0, 3 0, 3 Average domain size (mm) 0, 8 1, 9 0, 8 Standard deviation (mm) 0, 5 2.2 0, 4
[294] The results clearly showed that both Mixtures 1 and 2 exhibited significantly smaller mean elastomer domain size and narrower domain size distribution. The beneficial interfacial effect of Inventive Example 1 can be clearly seen as a 1: 1 mix with Comparative Example A in Mixture 3. The resulting range and average domain size are approximately identical for Mixture 1, which contains only Inventive Example 1 as the component elastomer. Procedure for preparing the OBC77 Inventive Example [295] The procedure for preparing OBC77 used in the aforementioned mixtures is as follows: For the experiments, a single autoclave reactor of continuously stirred tank of 1 gallon was used. The reactor operates full of liquid at ca. 3.72 MPa (540 psig) with process flow entering the bottom and exiting the top. The reactor is jacketed with oil to remove some of the reaction heat. The main temperature control is achieved by two heat exchangers in the solvent / ethylene addition line. ISOPAR® E, hydrogen, ethylene, and 1-octene were supplied to the reactor at controlled rates.
[296] The component catalysts were diluted in an air-free glove box. The two catalysts were fed individually at the desired ratio of different
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149/161 waiting tanks. To avoid clogging the catalyst feed line, the catalyst and cocatalyst lines were split and fed separately into the reactor. The co-catalyst was mixed with the diethyl zinc chain exchange agent before entering the reactor.
[297] The main product was collected under stable reactor conditions after several frequent product samples showed no substantial change in melt index and density. The products were stabilized with a mixture of IRGANOX® 1010, IRGANOX® 1076 and IRGAFOS® 176. The polymerization conditions and polymer properties are summarized in Table 20 below.
Table 20
Density I2 I10 / I2 Temp.(° C) Flow ofC2 (kg / h) Flow ofC8 (kg / h) H ₂ flow (sccm) 0.8540 1, 05 37, 90 120.0 0.600 5.374 0.9 Conversion of C2 (%) Conversion of C ₈ (%) % solids Polymer production rate (kg / h) Catalyst efficiency (kg of polymer / g of total metal Catalyst flow A1 (kg / h) A1 catalyst concentration (ppm) 89, 9 20,263 10.0 1.63 287 0.0343 88,099 Catalyst flow A1(kg / h) A1 catalyst concentration (ppm) A2 molar% Flow ofRIBS-2 (kg / h) Concentration of RIBS-2 (ppm) TEN flow (kg / h) TEN concentration(ppm of Zn) 0.196 9, 819 50,039 0.063 1417 0.159 348
[298] The structures of the catalysts are shown below
A1 and A2:
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t-Bu
Catalyst Al
Catalyst A2
Examples of polymers modified with maleic anhydride [299] First, interpolymer-based polymers were prepared in ethylene / octene blocks as described in PCT application No. PCT / US2005 / 08917, filed on March 17, 2005, which by in turn claims priority for provisional US patent application No. 60 / 553,906, filed on March 17, 204. Comparative base polymers are random ethylene / octene copolymers prepared using constrained geometry catalysts such as those sold under the trade name AFFINITY ® by The Dow Chemical Company. The properties of the base polymers are listed in Table 21 below.
Table 21
Polymer base Density (g / cm ³ ) melting index (I ₂ ) g / 10 min Copolymer type Block type AFFINITY®KC8852 0.875 3.0 Random AT AFFINITY®EG8200 0.87 5.0 Random AT R21 in multiblocks 0.877 4.7 Block Long R22 in multiblocks 0.877 4, 6 Block I enjoy
NA = Not applicable melting index (I ₂ ): 190 ° C / 2.16 kg.
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Continuous polymerization in solution of R21 in multiblocks and R22 in multiblocks, Catalyst A1 / B2 + TEN [300] Continuous solution polymerizations were carried out in a well-mixed computer-controlled reactor. Purified alkane mixture solvent (ISOPAR ™ E obtainable from ExxonMobil, Inc.), ethylene, 1-octene, and hydrogen (where used) were combined and fed into a 102 L reactor. Feeds to the reactor were measured by mass flow. The temperature of the feed stream was controlled by using a glycol-cooled heat exchanger before entering the reactor. Component catalyst solutions were dosed using pumps and mass flow meters. The liquid-filled reactor operated at a pressure of approximately 3.79 MPa (550 psig). After leaving the reactor, water and additive were injected into the polymeric solution. The water hydrolyzes the catalysts, and ends the polymerization reactions. The post-reactor solution was then heated in preparation for two-stage devolatilization. Unreacted monomers and solvent were removed during the devolatilization process. The polymeric melt was pumped for underwater cutting into pellets. The process conditions are summarized in Table 22 below.
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Table 22. Process conditions for R21 in multiblocks and for R22 in multiblocks
R21 in multiblocks R22 in multiblocks C ₂ H ₄ (pound / h) * 55, 53 54.83 C8H16 (pound / h) 30, 97 30, 58 Solvent (pound / h) 324.37 326, 33 H ₂ (sccm ¹ ) 550 60 T (° C) 120 120 Catalyst A1 (ppm) 600 600 Catalyst flow A1 (lb / h) 0.216 0.217 B2 ³ catalyst (ppm) 200 200 B2 catalyst flow (pound / h) 0.609 0.632 TEN concentration (% by weight) 3.0 3.0 TEN flow (pound / h) 0.69 1.39 Co-catalyst concentration 1 (ppm) 4500 4500 Co-catalyst flow 1 (lb / h) 0.61 0.66 Concentration of co-catalyst 2 (ppm) 525 525 Co-catalyst flow 2 (lb / h) 0.33 0.66 [TEN] ⁴ in polymer (ppm) 246 491 Polymerization rate ⁵ (pound / h) 84, 13 82.56 Conversion ⁶ (% by weight) 88, 9 88, 1 Polymer (% by weight) 17, 16 17.07 Efficiency ⁷ 293 280
* 1 pound / h = 0.45 kg / h.
¹ cm ³ / min standard.
² Dimethyl [N- (2,6-di (1-methyl ethyl) phenyl) starch) (2-isopropyl phenyl) (α-naphthalen-2-diyl (6-pyridin-2-diyl) methane) hafnium.
³ Dibenzyl bis- (1- (2-methyl cyclohexyl) ethyl) (2-oxoyl-3,5di (terciobutyl) phenyl) imino) zirconium.
⁴ ppm in final product calculated by mass balance.
⁵ Polymer production rate.
⁶ Percent by weight of ethylene conversion in the reactor.
7Efficiency, kg of polymer / g of M, where, g of M = g of Hf + g of Z.
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153/161 [302] Maleation / melt grafting for olefinic interpolymer in two spindle extruder [303] Resins grafted with MAH in a continuous reactive extrusion process using a two spindle extruder. The resins used in this process were: AFFINITY® KC8852, AFFINITY® EG8200, R21 in multiblocks, and R-22 in multiblocks described above. The apparatus was a 30 mm ZSK-30 extruder with a length / diameter ratio of 35.67. The prescribed temperature value in the extruder was 235 ° C. The spindle rotation rate was 300 rpm. The resin pellets were fed into the extruder at a rate of 4.5 kg / h (10 pounds / h). The initiator peroxide was 2.5bis (terciobutyl peroxy) -2,5-dimethyl hexane. A solution containing approximately 1.24% by weight of peroxide, 49.38% by weight of MAH, and 49.38% by weight of methyl ethyl ketone was fed to the extruder at a rate of approximately 6.17 g / min. This rate of addition corresponded to the addition of 4% by weight of MAH and 1000 ppm peroxide based on the resin mass. A vacuum inlet was installed at the end of the extruder to remove methyl ethyl ketone and excess un grafted MAH. The grafted resin left the extruder and was pelleted and collected.
[304] Approximately 2.5 g of each resin was dissolved in 100 ml of boiling xylene, and then precipitated by pouring the solution into five volumes of acetone. The solids were collected, dried, and titrated to determine the MAH level grafted. The EO870 resin contained 1.85% by weight of grafted MAH. The EO875 resin contained 1.85% by weight of grafted MAH. The multi-block R21 resin contained 1.80% by weight of grafted MAH. The multi-block R22 resin contained 1.49% by weight of grafted MAH. The grafted resins were
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154/161 mixed with a polyamide resin as discussed below.
Mixtures of resin grafted with MAH / polyamide
MAH grafted resins [305] Table 23 below shows the melt index data for MAH grafted resins.
Table 23. Fusion index and GPC data
Resin % by weight of grafted MAH I2, g / 10 min 1. MAH-g-AFFINITY® EG8200 * 1.85 0.0912 2. MAH-g-AFFINITY® KC8852 * 1.85 0.049 3. MAH-g-R22 in multiblocks 1.49 0.2339 4. MAH-g-R21 in multiblocks 1.80 0.1482
* Comparative resins.
I ₂ ; 190 ° C / 2.16 kg.
Mixtures: Representative procedure [306] Approximately 454 g of resin grafted with maleic anhydride (MAH-g-EO870, MAH-g875, MAH-g-R22 in multiblocks or MAH-g-R21 in multiblocks) was mixed into pellets with 1816 g of a polyamide (ULTRAMIDE® B-3, obtainable from BASF), feeding both resins in a 25 mm two-spindle Haake extruder at an instant rate of 2724 g / h. The temperature profile of the extruder was a constant of 250 ° C. The collected sample was subsequently injection molded to produce ASTM test bars for IZOD and flexural modulus testing. The mechanical test data are summarized in Table 24 below.
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Table 24. Mechanical data
Average flexural strength, psi Medium bending module, ksi Average elastic modulus @ 1% ksi Medium Izod at temp.environment @ B-3833, ft-lb / in I average zodJ / m Color of molded plates 1. MAH-gAFFINITY®EG8200 * 5873 267 266 7.391 394.6 light brown 2. MAH-gAFFINITY®KC8852 * 5799 265 265 10.08 537, 9 light brown 3. MAH-gR2 2 in multiblocks 5864 264 264 8, 624 460, 4 light brown 4. MAH-gR21 in multiblocks 5463 246 246 7.346 392.2 light brown
[307] Resins in lower viscosity multiblock resins have comparable or even better mechanical properties when compared to comparative higher viscosity resins.
[308] The resins were made into injection molded plates and tested for impact properties. The Table below shows the results.
Table 25
Resin Average flexural modulus (ksi) Impact analyzer (30 ° C) Impact analyzer (room temperature) Medium Izod impact (J / m) 1. MAH-gAFFINITY®EG8200 * 267 with standard deviation of 6 48, 62 56, 99 394.6 2. MAH-gAFFINITY®KC8852 * 265 with standard deviation of 4 58, 18 56, 64 537, 9 3. MAH-g-R22 in multiblocks 264 with 10 standard deviation 68, 17 63, 25 460, 4 4. MAH-g-R21 in multiblocks 246 with standard deviation of 9 63, 92 66, 25 392.2
Note: The inventive polymers (3 and 4) have resistance to
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156/161 significantly higher impact at low temperature against comparative samples (1 and 2). Sample # 3 has the best balance between high modulus and high impact. This improved impact is demonstrated both at low temperature and at room temperature. The test bodies were injection molded plates and the test was completed using the procedure outlined in ASTM D 3763 (Injection molded parts). The bending module according to ASTM D790 and the Izod impact according to D-256 were obtained.
Examples 20-21 and Comparative Examples L-M [309] The ethylene / α-olefin interpolymers of Examples 20 and 21 and Comparative Examples L-M were prepared in a substantially similar manner to that of Examples 19A-I and Examples R21 and R22 above.
[310] The levels of soft segments and hard segments of Examples 20-21 and Comparative Examples L-M as well as the octene contents of the soft segments of Examples 20-21 and Comparative Examples L-M are determined by NMR of
3
C according to the following steps. A solvent mixture of 5:95 (weight: weight) of para-dichlorobenzene-d ₄ (PDCB-d4) and odichloro-benzene (ODCB) containing 0.025M chromium (III) tris (acetyl acetonate), i.e. Cr ( AcAc) 3 is purged with nitrogen either by bubbling a stream of nitrogen through the sample or placing the sample in a dry box with nitrogen for each. 40 minutes to displace dissolved oxygen. Polymer samples are prepared as 6% by weight solutions by adding 0.25 g of polymer in 3.75 g of solvent, taking care to ensure a homogeneous solution. NMR data is acquired using a 400 MHz NMR spectrometer from VARIAN ™ or BRUKER ™. All measures
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157/161 are made on non-rotating samples in locked mode. Before data acquisition, samples are fitted to optimize the magnetic field. The CH2 main chain peak is used to assess the quality of the instrumental arrangement. Chemical displacements of ¹³ C NMR are reported internally to the methylene group (-CH2-) at 30.00 ppm. A range of predefined integrals is applied to general a list of integrals. The integrals for carbons in or near an octene repeating unit are combined with a library of ethylene / 1-octene copolymer spectra with different levels of octene. The combination provided the level of octene in the soft segment. The octene level for the hard segment is calculated from the soft segment. The polymer hardness (Shore A) is measured according to ASTM D1240. The modulus is measured at 100% elongation according to ASTM D638. The I2 melt index is measured according to ASTM D1238. Table 26 below shows the properties of Examples 20-21 and Comparative Examples LM.
Table 26
Ex. Sec content soft (% by weight) Sec content hard (% by weight) Octene content in sec. soft (% by weight) Shore A Mod. and m 100% (Mpa) Fusion indexI2 (dg / min) Overall density (g / cm ³ ) Ex.20 62 38 58, 2 81 3.91 0, 9 0.884 Ex.21 60 40 53, 6 84 4.62 0, 9 0.888 Ex.Comp. L 79 21 58, 4 60 1.41 1, 0 0. 872 Ex.Comp. M 82 18 51, 7 62 1, 7 1, 1 0. 872
Adherence test [311] The specific adherence test is performed on
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Examples 20-21 and LM Comparative Examples to assess their anti-compacting behavior. The adhesion test is performed according to the following procedure to measure the pellet mass strength that has consolidated at a known level of tension and temperature for a predetermined duration. A 2-inch-diameter cylinder consisting of two halves held together by a hose clamp is used. The inner surface of the cylinder is coated with calcium stearate. Excess calcium stearate powder is removed using a compressed air gun. A quantity of 60-150 g of pellets is poured into the cylinder. The side walls of the cylinder are slightly shaken during loading to set the solids. A two-inch circular sheet of TEFLON® is placed on top of the solids in the cylinder to prevent sticking to the weight load. The test loads, temperature, and test duration are adjusted to simulate relatively stringent transport and storage conditions. A weight load is placed on the sheet and the cylinder is placed in an oven at 37 ° C for a prescribed interval. A 6-pound load is used to simulate a pressure of 13167 N / m ² (275-pound-force / foot ² ). After the test interval, the load is removed and the cylinder is allowed to cool to ambient conditions for at least 12 hours. Then, the sample is removed from the cylinder. The unconstrained conventional yield strength is measured using an INSTRON® tensile testing machine in compression mode.
[312] Table 27 below shows the adherence test results for Examples 20-21 and Comparative Examples L-M.
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Table 27
Example 4 weeks, 37 ° C 8 weeks,37 ° C Average force N / m ² (lb / ft ² ) Visual observations Average force N / m ² (lb / ft ² ) Example20 0 Totally free flow 0 Example21 0 Totally free flow, no stickiness 0 Ex. 120, 6 Slightly sticky, 219.29 Comp. L (2,519) maintained form (4.58) Ex. 103.07 Slightly sticky, 241.22 Comp. M (2, 1526) maintained form (5,038)
[313] Table 27 showed that Examples 20-21 exhibited free-flowing (flowing) pellet behavior without the need for force to separate them. No partition was used.
Examples 22-23 and Comparative Examples N-O [314] Examples 22-23 and Comparative Examples N-O are prepared according to the formulations listed in Table 28 below. INNOVENE® H352-02 is a polypropylene homopolymer with melt flow 35 and high isotactic content. Examples 20-21 and Comparative Examples L-M are used as impact modifying polymers. The weight percentages of the polymers are adjusted so that
the reason volumetric in polypropylene for polymer impact modifier in each one From Examples 22-23 and Examples Comparatives AT THE stay in about 65:53. JETFILL® 700C is a talc compacted in fine particles. IRGANOX® B-225 is a mix of primary antioxidant
phenolic and phosphate secondary antioxidant (1: 1 ratio).
Examples 22-23 and Comparative Examples N-O are prepared according to the following steps. A two-wire extruder is used
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160/161 COPERION® ZSK-25 spindles with a thermoplastic olefin / talc spindle design to combine the ingredients. Polypropylene and the other mixing components are fed into the extruder using individual loss / weight feeders. The talc is fed through a side arm that is inserted into the third zone of the extruder cylinder. A vacuum of 0.061 - 0.067 MPa (18-20 inches) of mercury is used in the extruder right after mixing talc. Examples 22-23 and Comparative Examples N-O are injection molded in an ASTM family die using an 80 ton ARBURG ™ 370 injection molding machine (obtainable from Arburg Incorporation, Lossburg, Germany).
Table 28
Ingredient (% by weight) Ex. Comp.N Example22 Example23 Ex.Comp. O INNOVENE ™ H352-02 52.37 52, 18 52, 14 52.37 Comparative Example L 27, 63 0 0 0 Example 22 0 27.82 0 0 Example 23 0 0 27.86 0 ExampleComparative M 0 0 0 27, 63 JETFIIL® 700C 20 20 20 20 IRGAFOS ™ B225 0, 2 0, 2 0, 2 0, 2
Dart crash test with instruments [315] Examples 22-23 and Comparative Examples N-O are stored in the laboratory at room temperature for at least seven days before testing. The samples for each of Examples 22-23 and Comparative Examples N-O are 3 inches in diameter and 0.3175 cm (0.125 inch) thick. Ten samples of each example are tested. The dart impact test with instruments according to ASTM D3763 is performed. Table 29 below shows the dart impact results with instruments.
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Table 29
Example Total dart impact energy with instruments at -30 ° C, ft-lb Dart% dart impact with instruments at -30 ° C Ex. Comp. N 40.27 100 Example 22 41, 74 100 Example 23 42.8 100 Ex. Comp. O 39, 63 100
[316] As can be seen in Table 29, all Examples 22-23 and Comparative Examples show ductile impact behavior. In addition, Examples 22 and 23 containing Examples 20 and 21, respectively, have a desirable combination of low pellet adhesion characteristics and good impact efficiency of thermoplastic olefin.
[317] Although the invention has been described with respect to a limited number of embodiments, the specific characteristics of an embodiment should not be attributed to other embodiments of the invention. No single embodiment represents all aspects of the invention. In some embodiments, the compositions or methods may include numerous compounds or steps not mentioned here. In other embodiments, the compositions or methods do not include, or are substantially free from, any compounds or steps not listed here. From the described incorporations there are variations and modifications. Finally, any number disclosed here must be constructed to mean approximate, regardless of whether the term "about or" is used in describing the number. The appended claims are intended to cover all those modifications and variations as falling within the scope of the invention.

权利要求:
Claims (11)
[1]
1. Modified composition for impact, characterized by the fact that it comprises:
(A) a thermoplastic polymer composition; and (B) an amount of impact modification of an interpolymer in ethylene / a-olefin multiblocks comprising hard segments and soft segments, the quantity of the hard segments being 35 weight percent to 50 weight percent, with based on the total weight of the interpolymer in ethylene / a-olefin multiblocks, and the interpolymer in ethylene / a-olefin multiblocks:
(a) has an M _w / M _n of 1.7 to 3.5, at least one melting point, Tm, in ° C and density, d, in g / cm ³ , with the numerical values of T _m ed correspond to the relation:
Tm> -2002, 9 + 4538, 5 (d) - 2422.2 (d) ² ;
or (b) has an M _w / M _n of 1.7 to 3.5, and exhibits a heat of fusion, Δη in J / g, and a delta amount, ΔΤ, in ° C, defined as the temperature difference between the maximum DSC peak and the maximum CRYSTAF peak, with the numerical values of ΔΤ and Δη having the following relationships:
ΔΤ> -0, 1299 (ΔΗ) + 62.81 for Δη greater than zero and up to 130 J / g;
ΔΤ> 48 ° C for Δη greater than 130 J / g, the peak of CRYSTAF being determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature will be 30 ° C; or (c) has a percentage elastic recovery, Re, in 300 percent deformation, and 1 cycle, measured with a
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[2]
2/4 film molded by compression of the interpolymer in ethylene / a-olefin multiblocks, and has a density, d, in grams per cubic centimeter, with the numerical values of R _and ed satisfying the following relationship when the ethylene / a-olefin is free of a cross-linked phase:
R _e > 1481 - 1629 (d); or (d) it has at least one molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF, the fraction having a block index of 0.5 and up to 1; or (e) has an average block index greater than zero and up to 1.0 and a molecular weight distribution, M _w / M _n , greater than 1.3; or (f) has a storage module at 25 ° C, G '(25 ° C), and a storage module at 100 ° C, G' (100 ° C), with the ratio G '(25 ° C) ) for G '(100 ° C) is in the range of 1: 1 to 9: 1.
2. Impact-modified composition according to claim 1, characterized in that the thermoplastic polymer composition comprises one or more polymers selected from the group consisting of polyurethanes, poly (vinyl chlorides), styrenics, hydrogenated styrenics, polynorbornene, poly (ethylene-co-norbornene), poly (4-methyl-pentene) with one or more pre-grafted functional monomers, polyolefins, polycarbonates, thermoplastic polyester, polyamides, polyacetals, and polysulfones.
[3]
3. Impact-modified composition according to claim 1, characterized in that the interpolymer in ethylene / a-olefin multiblocks has an M _w / M _n of 1.7 to 3.5, at least one melting point , Tm, in ° C, and a density, d, in g / cm ³ , with the numerical values of Tm
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3/4 and d correspond to the relation:
T _m > -2002, 9 + 4538, 5 (d) - 2422.2 (d) 2.
[4]
4. Impact-modified composition according to claim 1, characterized in that the interpolymer in ethylene / a-olefin multiblocks has an M _w / M _n of 1.7 to 3.5, and exhibits a heat of fusion , Δη in J / g, and a delta quantity, ÁT, in ° C, defined as the temperature difference between the maximum DSC peak and the maximum CRYSTAF peak, with the numerical values of Δτ and Ah having the following relationships :
Δτ> -0, 1299 (ΔΗ) + 62.81 for Δη greater than zero and up to 130 J / g;
Δτ> 48 ° C for Δη greater than 130 J / g, the peak of CRYSTAF being determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature will be 30 ° C.
[5]
5. Modified composition for impact, according to claim 1, characterized by the fact that the interpolymer in ethylene / a-olefin multiblocks has a percentage elastic recovery, Re, in 300 percent deformation, and 1 cycle, measured with a compression-molded film of interpolymer in ethylene / a-olefin multiblocks, and have a density, d, in grams per cubic centimeter, with the numerical values of Re ed satisfying the following relationship when the ethylene / a-olefin interpolymer is free of a crosslinked phase: Re> 1481 - 1629 (d).
[6]
6. Impact-modified composition according to claim 1, characterized in that the interpolymer in ethylene / a-olefin multiblocks has at least one
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4/4 molecular fraction that elutes between 40 ° C and 130 ° C when fractioned using TREF, the fraction having a block index of 0.5 and up to 1.
[7]
7. Modified impact composition according to claim 1, characterized by the fact that the interpolymer in ethylene / a-olefin multiblocks has an average block index greater than zero and up to 1.0 and a molecular weight distribution, Mw / Mn, greater than 1.3.
[8]
8. Impact-modified composition according to claim 1, characterized in that the interpolymer in ethylene / a-olefin multiblocks has a storage module at 25 ° C, G '(25 ° C), and a storage module storage at 100 ° C, G '(100 ° C), with the ratio of G' (25 ° C) to G '(100 ° C) ranging from 1: 1 to 9: 1.
[9]
9. Modified composition for impact, according to claim 1, characterized by the fact that it comprises as a thermoplastic polymer composition:
(A) a propylene polymer.
[10]
10. Composition modified for impact, according to claim 9, characterized by the fact that it comprises as a thermoplastic polymer composition:
A) an isotactic propylene polymer.
[11]
11. Manufactured article, characterized by the fact that it comprises the composition modified for impact as defined by claim 1.

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KR101319124B1|2013-10-23|Polymer Blends from Interpolymer of Ethylene/Alpha-olefin with Improved Compatibility

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KR101243003B1|2013-03-12|Rheology modification of interpolymers of ethylene/alpha-olefins and articles made therefrom

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KR20070117592A|2007-12-12|Thermoplastic vulcanizate comprising interpolymers of ethylene/alpha-olefins

同族专利:

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公开号 | 公开日

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EP2553014A1|2013-02-06|

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WO2011119486A1|2011-09-29|

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KR20130064734A|2013-06-18|

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US20100240818A1|2010-09-23|

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KR20190087649A|2019-07-24|

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CN102906181B|2015-08-12|

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KR102190777B1|2020-12-15|

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EP2553014B1|2018-07-11|

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US8273826B2|2012-09-25|

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KR20180097772A|2018-08-31|

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JP5779229B2|2015-09-16|

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BR112012024303A2|2016-05-24|

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CN102906181A|2013-01-30|

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US20130018150A1|2013-01-17|

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KR101892162B1|2018-08-28|

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KR102002435B1|2019-07-23|

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US9243140B2|2016-01-26|

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JP2013523953A|2013-06-17|

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2019-11-26| B09A| Decision: intention to grant|

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2020-02-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US12/732,950|US8273826B2|2006-03-15|2010-03-26|Impact modification of thermoplastics with ethylene/α-olefin interpolymers|

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PCT/US2011/029201|WO2011119486A1|2010-03-26|2011-03-21|IMPACT MODIFICATION OF THERMOPLASTICS WITH ETHYLENE/α-OLEFIN INTERPOLYMERS|

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