THERMOPLASTIC VULCANIZED AND ARTICLE

专利摘要:
vulcanized thermoplastic and article. embodiments of the invention provide block composites and their use in thermoplastic vulcanized compounds.
公开号:BR112012007275B1
申请号:R112012007275-7
申请日:2010-10-01
公开日:2021-08-10
发明作者:Kim L. Walton；Brian W. Walther；Robert T. Johnston；José M. Rego；Xiaosong Wu
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

field of invention
[0001] This invention relates to composites in blocks and their use in thermoplastic vulcanizates. Invention history
[0002] Elastomers are defined as materials that experience large reversible deformations under relatively low stress. Some examples of commercially obtainable elastomers include natural rubber, ethylene/propylene copolymers (EPM), ethylene/propylene/diene copolymers (EPDM), styrene/butadiene copolymers, chlorinated polyethylene, and silicone rubber.
[0003] Thermoplastic elastomers are elastomers that have thermoplastic properties. That is, thermoplastic elastomers are optionally molded or shaped differently and reprocessed at temperatures above their melting or softening point. An example of a thermoplastic elastomer is styrene/butadiene/styrene block copolymer (SBS). SBS block copolymers exhibit two phase morphologies consisting of glassy polystyrene domains connected by rubbery butadiene segments.
[0004] Thermoset elastomers are elastomers having thermoset properties. That is, thermoset elastomers irreversibly solidify or “set” when heated, usually due to an irreversible crosslinking (crosslinking) reaction. Two examples of thermoset elastomers are crosslinked ethylene/propylene copolymer (EPM) rubber and crosslinked ethylene/propylene/diene copolymer (EPDM) rubber. EPM materials are typically cured with peroxides to cause crosslinking, and thus produce thermosetting properties. EPDM materials are linear interpolymers of ethylene, propylene, and an unconjugated diene such as 1,4-hexadiene, di-cyclopentadiene, or ethylidene norbornene. EPDM materials are typically vulcanized with sulfur to produce thermosetting properties, although they can also be cured with peroxides While thermosetting EPM and EPDM materials are advantageous in having applicability in higher temperature applications, EPM and EPDM elastomers have strength in relatively low green (at lower ethylene contents), relatively low oil resistance, and relatively low resistance to surface modification.
[0005] Thermoplastic vulcanizates (TVP's) comprise thermoplastic matrices, preferably crystalline, through which the thermoset elastomers are, in general, uniformly distributed. Examples of thermoplastic vulcanizates thermosetting materials of ethylene/propylene monomer rubber and ethylene/propylene/diene monomer rubber distributed in a crystalline polypropylene matrix. An example of a commercial TVP is SATOPRENE® thermoplastic rubber manufactured by Advanced Elastomer Systems and which is a mixture of crosslinked EPDM particles in a crystalline polypropylene matrix. These materials are useful in many applications that previously used vulcanized rubber, for example, hoses, gaskets, and the like.
[0006] Typically, commercial TVP's are based on vulcanized rubbers in which a curing system by sulfur or phenolic resin is used to vulcanize, i.e. crosslink, a diene copolymer rubber (or more generally, a polyene) by means of of dynamic vulcanization, which is crosslinking during mixing (typically vigorously) in a thermoplastic matrix.
[0007] Although numerous types of thermoplastic vulcanizates are known, there is still a need for improved thermoplastic materials having elastomeric properties. Specifically, there is a need for a method to produce thermoplastic vulcanizates having improved properties relating to tensile, elongation, compression set, and/or oil resistance. Invention Summary
[0008] Thermoplastic vulcanizates with improved elastomeric properties, particularly improved compression deformation at elevated temperatures, have now been found. These new thermoplastic vulcanizates are obtained from a reaction mixture comprising: (I) a thermoplastic polyolefin; (II) a vulcanizable elastomer; (III) a cross-linking agent; and, (IV) a composite in blocks. Brief description of the drawings
[0009] Figure 1 shows the DSC melting curve for Example B1;
[0010] Figure 2 shows the DSC melting curve for Example F1;
[0011] Figure 3 compares the TREF profiles of Examples B1, C1
[0012] and D1; Figure 4 shows DSC curves from Examples B2 and B3;
[0013] Figure 5 shows DSC curves of Examples F2 and F3;
[0014] Figure 6 shows composite index in blocks for Examples B1, F1, C1, H1, D1 and G1;
[0015] Figure 7 shows composite index in blocks for Examples B1, V1, Z1, C1, W1, AA1, D1, X1, and AB1
[0016] Figure 8 shows dynamic-mechanical analysis of Examples B1, C1 and D1;
[0017] Figure 9 shows dynamic-mechanical analysis of Examples F1, G1 and H1.
[0018] Figure 10 shows a PROFAX ULTRA SG853 polypropylene impact copolymer TEM micrograph at 5 μm and 1 μm scales;
[0019] Figure 11 shows TEM micrographs of Examples B1, C1 and D1 at scales of 2 μ m, 1 μ m and 0.5 μ m;
[0020] Figure 12 shows TEM micrographs of Examples F1, G1 and H1 in scales of 2 μ m, 1 μ m and 0.5 μ m;
[0021] Figure 13 shows TEM micrographs of Examples B2, D2 and B3 at 0.5 μ m and 0.2 μ m scales;
[0022] Figure 14 shows Example B2 at scales of 1 μ m and 200 nm; and
[0023] Figure 15 shows AFM images of Comparative Example T1 on the left and Example T4 on the right. Description of embodiments of the invention
[0024] Definitions
[0025] All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements published and registered, by CRC Press, Inc., 2003. Likewise, any references to a Group or Groups shall be to a Group or Groups shown in this Table Periodical of the Elements using the IUPAC system to number groups. Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure. For purposes of US patent practice, the contents of any patent, patent application, or publication referred to herein are hereby incorporated by reference in their entirety (or the equivalent US version thereof is also incorporated by reference) especially with regarding disclosure of synthetic techniques, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge in the art.
[0026] The term "comprising" and its derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not specifically disclosed. For the avoidance of doubt, all compositions claimed herein by the use of the term "comprising" may include any additional additive, adjuvant, or compound, polymeric or not, unless stated otherwise. In contrast, the term “consisting essentially of” excludes from the scope of any subsequent mention any other component, step or procedure, except those that are not essential to operability. The term “consisting of” excludes any component, step or procedure not specifically described or listed. Unless otherwise stated, the term “or” refers to members listed individually as well as in any combination.
[0027] The term "polymer" includes both conventional homopolymers, that is, homogeneous polymers prepared from a single monomer, and copolymers (herein interchangeably referred to as interpolymers), meaning polymers prepared by reacting at least two monomers or differently , containing in them, chemically differentiated segments or blocks, even if formed from a single monomer. More specifically, the term "polyethylene" includes ethylene homopolymers and ethylene copolymers and one or more C3-8 α-olefins in which ethylene comprises at least 50 mole percent. The term "propylene copolymer" or "propylene interpolymer" means a copolymer comprising propylene and one or more copolymerizable comonomers, in which a plurality of polymerized monomeric units of at least one block or segment in the polymer (the crystalline block) comprises propylene, preferably at least 90 mole percent, more preferably at least 95 mole percent, and most preferably at least 98 mole percent. A polymer prepared primarily with a different α-olefin such as 4-methyl-1-pentene would be similarly named. If used, the term "crystalline" refers to a polymer or polymer block that has a crystalline melting point or first order transition (Tm) determined by differential scanning calorimetry (DSC) or equivalent technique. The term can be used interchangeably with the term “semi-crystalline”. The term "amorphous" refers to a polymer lacking a crystalline melting point. The term "isotactic" is defined as polymer repeating units having at least 70 percent pentads terminated by 13 C NMR analysis. "Very isotactic" is defined as polymers having at least 90 percent isotactic pentads.
[0028] The term "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 end-to-end with respect to polymerized ethylenic functionality rather than pendant or grafted mode. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated therein, density, amount of crystallinity, crystallite size attributable to a polymer of such composition, type and degree of tacticity (isotactic or syndiotactic), regioregularity or regio-irregularity, amount of branching, including long-chain branching or hyper-branching, homogeneity, or for any other chemical or physical property. Block copolymers are characterized by unique distributions of polydispersion index (PDI or Mw/Mn), block length distribution, and/or block number distribution due, in a preferred embodiment, to the effect of the agent(s) ) of exchange in combination with the catalyst(s).
[0029] The term "block composite" refers to the new polymers of the invention comprising a soft copolymer, a hard polymer and a block copolymer having a soft segment and a hard segment, the hard segment of the block copolymer having the same composition of the hard polymer in the block composite and the soft segment of the block copolymer has the same composition as the soft copolymer of the block composite. Block copolymers can be linear or branched. More specifically, when produced in a continuous process, block composites desirably have PDI from 1.7 to 15, preferably from 1.8 to 3.5, more preferably from 1.8 to 2.2, and most preferably from 1, 8 to 2.1. When produced in a batch or semi-batch process, block composites desirably have PDI from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to 1.8.
"Hard" segments refer to very crystalline blocks of polymerized units in which the monomer is present in an amount greater than 95 percent by weight, and preferably greater than 98 percent by weight. In other words, the comonomer content in the hard segments is less than 5 mole percent, and preferably less than 2 percent by weight. In some embodiments, the hard segments comprise all or substantially all propylene units. On the other hand, "soft" segments refer to amorphous, substantially amorphous or elastomeric blocks of polymerized units in which the comonomer content is greater than 10 mol%.
[0031] The term "thermoplastic vulcanizate" (TPV) refers to an engineering thermoplastic elastomer in which a cured elastomeric phase is dispersed in a thermoplastic matrix. Typically, the thermoplastic vulcanizate comprises at least one thermoplastic material and at least one cured (i.e., crosslinked) elastomeric material. Preferably, the thermoplastic material forms the continuous phase, and the cured elastomer forms the discrete phase; that is, the cured elastomer domains disperse in the thermoplastic matrix. Preferably, the domains of the cured elastomer are completely and evenly dispersed with the average domain size in the range from about 0.1 micron (μm) to about 100μm, from about 0.1μm to about 50μm m, from about 0.1 μ m to about 25 μ m, from about 0.1 μ m to about 10 μ m, or from about 0.1 μ m to about 5 μ m. In some embodiments, the matrix phase of TPV is present in less than about 50% by volume of the TPV, and the dispersed phase is present in at least about 50% by volume of the TPV. In other words, the crosslinked elastomeric phase is the major phase in TPV, while thermoplastic polymer powder is the minor phase. TPV's with such a phase composition have good compression deformation. However, TPV's can also be prepared with the major phase being the thermoplastic polymer and the minor phase being the crosslinked elastomer. Generally, the cured elastomer has a portion that is insoluble in cyclohexane at 23°C. The amount of the insoluble portion is preferably greater than about 75% or about 85%. In some cases, the insoluble amount is greater than about 90%, greater than about 93%, greater than about 95%, or greater than about 97% by weight of the total elastomer.
[0032] The branching index quantifies the degree of long-chain branching in a selected thermoplastic polymer. Preferably, the branching index is less than about 0.9, 0.8, 0.7, 0.6 or 0.5. In some embodiments the branching index is in the range of about 0.01 to about 0.4. In other embodiments, the branching index is less than about 0.01, less than about 0.001, less than about 0.0001, less than about 0.0001, or less than about 0.000001. The branch index is defined by the following equation:
wBr ivLhl where g' is the branching index, IVBr is the intrinsic viscosity of the branched thermoplastic polymer (eg polypropylene) and IVLin is the intrinsic viscosity of the corresponding linear thermoplastic polymer having the same weight average molecular weight as the branched thermoplastic polymer and, in the case of copolymers and terpolymers, substantially the same proportion or relative molecular proportions of monomeric units.
[0033] Intrinsic viscosity, also known as threshold viscosity number, is, in its most general sense, a measure of the ability of a polymer molecule to improve the viscosity of a solution. This depends on both the size and shape of the dissolved polymer molecule. Hence, when comparing a non-linear polymer with a linear polymer of substantially the same weight average molecular weight, it is an indication of the configuration of the non-linear polymer molecule. In fact, the above ratio of intrinsic viscosities is a measure of the degree of branching of the non-linear polymer. A method for determining intrinsic viscosity of propylene polymer material is described in Elliott et al., J. App. Poly. Sci., 14, pp. 2947-2963 (1970). In this description, the intrinsic viscosity with the polymer dissolved in decahydronaphthalene at 135°C is determined in each case. Another method for measuring the intrinsic viscosity of a polymer is ASTM D5225-98 - "Standard Test Method for Measuring Solution Viscosity of Polymers with a Differential Viscometer" ("Standard test method for measuring viscosity in polymer solution with a differential viscometer"), which is here incorporated by reference in its entirety.
[0034] Embodiments of the invention provide a kind of thermoplastic vulcanizate (TPV) composition and a process for preparing various TPV's. Such TPV's have lower compression deformation, higher tensile strength, elongation, tear strength, abrasion resistance, better dynamic properties and/or oil resistance. First, a typical thermoplastic vulcanizate composition comprises a mixture or reaction product of (1) a thermoplastic polymer; (2) a vulcanizable elastomer; and (3) a crosslinking agent capable of vulcanizing the elastomer. Preferably, the crosslinking agent does not substantially degrade or crosslink the thermoplastic polymer. Alternatively, the thermoplastic vulcanizate composition of the invention comprises a mixture or reaction product of (1) a thermoplastic polymer; (2) a vulcanizable elastomer; (3) a compatibilizer; and (4) a crosslinking agent capable of vulcanizing the elastomer, block composites being used as compatibilizers between the thermoplastic polymer and the vulcanizable elastomer. When used as a compatibilizer, the block composite is present in the TPV in an amount less than 50 percent but greater than zero percent by weight of the total composition. Preferably, the composite block is present in an amount less than 40 percent, but greater than zero percent by weight, less than 30 percent, but greater than zero percent by weight, less than 20 percent, but greater than zero percent by weight, less than 10 percent, but greater than zero percent by weight, less than 8 percent, but greater than zero percent by weight, less than 6 percent, but greater than zero percent by weight, or less than 5 percent, but greater than zero percent by weight.
Preferably, the composite block polymers are prepared by a process comprising contacting an addition polymerizable monomer or mixture of monomers under addition polymerization conditions with a composition comprising at least one addition polymerization catalyst, a co-catalyst and a chain exchange agent, said process being characterized by the formation of at least some growing polymer chains under different process conditions in two or more reactors operating under steady state polymerization conditions or in two or more zones of a reactor operating under continuous flow polymerization conditions.
[0036] In a preferred embodiment, the block composites of the invention comprise a block polymer fraction having a very likely distribution of block lengths. According to the invention, preferred polymers are block copolymers containing 2 or 3 blocks or segments. In a polymer containing three or more segments (i.e. blocks separated by a distinguishable block) each block may be the same or chemically different and generally characterized by a distribution of properties. In a process for preparing the polymers, a chain exchange agent is used as a way of extending the life of a polymer chain such that a substantial fraction of the polymer chains exit at least the first reactor of a series of multiple reactors or from the first zone in a multizone reactor operating substantially under continuous flow conditions in the form of polymer terminated with a chain exchange agent, and the polymer chain experiences different polymerization conditions in the next reactor or polymerization zone. Different polymerization conditions in the respective reactors or zones include the use of different ratios of monomers, comonomers, or monomers/comonomers, different polymerization temperatures, pressures or partial pressures of various monomers, different catalysts, different monomer gradients, or any other difference that leads to the formation of a distinguishable polymeric segment. Accordingly, at least a portion of the polymer comprises two, three or more, preferably two or three distinct polymeric segments arranged intramolecularly.
[0037] The following mathematical treatment of the resulting polymers is based on the theoretically derived parameters believed to apply and demonstrate that, especially in two or more zones or continuous reactors connected in series in steady state, having different polymerization conditions at which the polymer in growth is exposed, the block lengths of polymer forming in each reactor or zone will conform to a very likely distribution, derived in the following manner, in which pi (π) is the probability of polymer propagation in a reactor with respect to sequence of catalyst blocks i. The theoretical treatment is based on standard hypotheses and methods known in the art and used to predict the effects of polymerization kinetics on molecular architecture, including the use of mass action reaction rate expressions that are not affected by block lengths or chains, and the hypothesis that the polymer chain growth is completed in a very short time compared to the average residence time in the reactor. Such methods have previously been disclosed in W.H. Ray, J. Macromol. Sci., Macromol. Chem, C8, 1 (1972) and in A.E. Hamielec and J.F. MacGregor, "Polymer Reaction Engineering", K.H. Reichert and W. Geisler, Eds., Hanser, Munich, 1983. Furthermore, it is assumed that each incidence of the chain exchange reaction in a given reactor results in the formation of a single polymeric block, whereas the transfer of the finished polymer by chain exchange agent to a different zone or reactor and exposure to different polymerization conditions results in the formation of a different block. For catalyst i, the fraction of sequences of length n that takes place in a reactor is given by Xi[n], where n is an integer from 1 to infinity representing the total number of monomeric units in the block.
[0038] Xi[n]= (l-pi)pi(n-l) very likely distribution of block lengths: 1 Ni= numerical average block length 1 - pi
[0039] If more than one catalyst is present in a reactor or zone, each catalyst will have a propagation probability (pi) and, therefore, will have a single average block length and distribution for the polymer being prepared in that reactor or zone. In a very preferred embodiment, the propagation probability is defined as:
for each catalyst i= {1, 2, ...}, where, Rp[i]= Local rate of monomer consumption per catalyst i, (mol/L/time) Rt= Total rate of chain termination and transfer for catalyst i, (mol/L/time), and Ri[i]= Local rate of chain transfer with inactive polymer, (mol/L/time).
[0040] For a given reactor, the polymer propagation rate, Rp[i], is defined using an apparent rate constant, kpi, multiplied by a total monomer concentration, [M], and multiplied by the local concentration of catalyst i, [Ci], as follows:

[0041] It is determined transfer rate, termination and chain exchange as a function of chain transfer to hydrogen (H2), beta hydride elimination, and chain transfer chain exchange agent (CSA). The quantities [H2] and [CSA] are molar concentrations and each subscript k value is a rate constant for the reactor or zone:

[0042] Inactive polymer chains are created when a polymer moiety transfers to a CSA and each of all reacting CSA moieties is assumed to be paired with an inactive polymer chain. The exchange rate of inactive polymer chain with catalyst I is given below, where [CSAf] is the feed concentration of CSA, and the amount ([CSAf]-[CSA]) represents the concentration of inactive polymer chains:

[0043] As a result of the theoretical treatment above, it can be seen that the overall block length distribution for each block of the resulting block copolymer is the sum of the block length distribution given previously by Xi[n], weighted by the rate of local polymer production for catalyst i. This means that a polymer prepared in at least two different polymer-forming conditions will have at least two distinguishable blocks or segments each having a very likely block length distribution. Monomers
[0044] Suitable monomers for use in preparing the copolymers of the present invention include any addition polymerizable monomers, preferably any olefin or diolefin monomer, more preferably any α-olefin, and most preferably ethylene and at least one copolymerizable comonomer, propylene and at least at least one comonomer having from 4 to 20 carbon atoms, or 1-butene and at least one copolymerizable comonomer having from 2 or 5 to 20 carbon atoms, or 4-methyl-1-pentene and at least one different copolymerizable comonomer having to 4 to 20 carbon atoms. Preferably the copolymers comprise propylene and ethylene. Examples of suitable monomers include straight or branched chain α-olefins of 2 to 30, preferably 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1 - hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cycloolefins of 3 to 30, preferably of 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8- dimethane-1,2,3,4,4a,5,8,8a-octahydro-naphthalene; di and polyolefins such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, di-cyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8- methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene; aromatic vinyl compounds such as mono- or poly-alkyl-styrenes (including styrene, o-methyl-styrene, m-methyl-styrene, p-methyl-styrene, o,p-dimethyl-styrene, o-ethyl-styrene, m -ethyl-styrene and p-ethyl-styrene), and functional group-containing derivatives, such as methoxy-styrene, ethoxy-styrene, vinyl benzoic acid, methyl vinyl benzoate, benzyl vinyl acetate, hydroxy styrene, o-chloro-styrene , p-chloro-styrene, divinyl benzene, 3-phenyl-propene, 4-phenyl-propene and α-methyl-styrene, vinyl chloride, 1,2-difluoro-ethylene, 1,2-dichloro-ethylene, tetrafluoro- ethylene, and 3,3,3-trifluoro-1-propene, provided that the monomer is polymerizable under the conditions used.
[0045] Preferred monomers or monomer mixtures for use in combination with at least one CSA include herein ethylene; propylene; mixtures of ethylene with one or more monomers selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and styrene; and mixtures of ethylene, propylene and a conjugated or unconjugated diene. Chain Exchange Catalysts and Agents
[0046] Catalysts and catalyst precursors suitable for use in the present invention include metal complexes such as those disclosed in WO 2005/090426, in particular, those disclosed beginning on page 20, line 30 through page 53, line 20, as hereinbefore incorporates by reference. Suitable catalysts are also disclosed in US 2006/0199930, US 2007/0167578, US 2008/0311812, US 7,355,089 B2, or WO 2009/012215, which are incorporated herein by reference with respect to catalysts.
[0047] Particularly preferred catalysts are those of the following formula:
where R20 is an aromatic group or inertly substituted aromatic group having from 5 to 20 atoms not counting hydrogen atoms, or a polyvalent derivative thereof; T3 is a hydrocarbylene or silane group having 1 to 20 atoms not counting hydrogen atoms, or an inertly substituted derivative thereof; M3 is a Group 4 metal, preferably zirconium or hafnium; G is an anionic, neutral or dianionic linking group, preferably a halide, hydrocarbyl or dihydrocarbylamide group having up to 20 atoms not counting hydrogen atoms; g is a number from 1 to 5 indicating the number of such G groups; and electron-donating bonds and interactions are represented, respectively, by lines and arrows.
[0048] Preferably, such complexes correspond to the formula:
in which, T3 bivalent bridging group of 2 to 20 atoms not containing hydrogen atoms, preferably a substituted or unsubstituted C3-6 alkylene group; and each occurrence of Ar2 is independently an alkyl or aryl substituted arylene or arylene group of 6 to 20 atoms not counting hydrogen atoms; M3 is a Group 4 metal, preferably zirconium or hafnium; each occurrence of G is independently an anionic, neutral or dianionic linking group; g is a number from 1 to 5 indicating the number of such X groups; and electron donor interactions are represented by arrows.
[0049] Preferred examples of metal complexes of the above formula include the following compounds:
where M3 is Hf or Zr; Ar4 is C6-20 aryl or inertly substituted derivatives thereof, especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, or anthracen-5-yl , and each occurrence of T4 independently comprises C3-6 alkylene group, C3-6 cycloalkylene group, or an inertly substituted derivative 21 thereof; each occurrence of R is independently hydrogen, halogen, trihydrocarbyl silyl, or trihydrocarbyl silyl hydrocarbyl of up to 50 atoms not counting hydrogen atoms; and each occurrence of G is independently halogen or hydrocarbyl or trihydrocarbyl silyl group of up to 20 atoms not containing hydrogen atoms, or 2 G groups together form a bivalent derivative of the above hydrocarbyl or trihydrocarbyl silyl groups.
[0050] Compounds of the formula are especially preferred:
in which Ar4 is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, or anthracen-5-21yl, R is hydrogen, halogen, or alkyl of C1-4, especially methyl, T4 is propane-1,3-diyl or butane-1,4-diyl, and G is chlorine, methyl or benzyl.
[0051] Other suitable metal complexes are those of the formula:
Or

The above polyvalent Lewis base complexes are conveniently prepared by standard ligand exchange and metallization procedures involving a Group 4 metal source and the neutral polyfunctional ligand source. In addition, the complexes can also be prepared by a hydrocarbylation and amide elimination process starting from the corresponding Group 4 metal tetra-amide and a hydrocarbylation agent such as trimethyl aluminum. Other techniques can also be used. These complexes are known from the disclosures of, inter alia, U.S. Patent Nos. 6,320,005, 6,103,657, 6,953,764 and from International Publication Nos. WO 02/38628 and WO 03/40195.
Suitable co-catalysts are those disclosed in WO 2005/090426, in particular those disclosed on page 54, line 1 to page 60, line 12, which are hereby incorporated by reference.
Suitable chain exchange agents include those disclosed in WO 2005/090426, in particular those disclosed on page 19, line 21 to page 20, line 12, which are hereby incorporated by reference. Particularly preferred chain exchange agents are dialkyl zinc compounds. Composite polymer product in blocks
[0055] Using the present process, new composite block polymers are quickly prepared. Preferably, the composite block polymers comprise propylene, 1-butene or 4-methyl-1-pentene and one or more comonomers. Preferably, the block polymers of the block composites comprise, in polymerized form, propylene and ethylene and/or one or more C4-20 α-olefin comonomers, and/or one or more additional copolymerizable comonomers or they comprise 4-methyl -1- pentene and ethylene and/or one or more C4-20 α-olefin comonomers, or they comprise 1-butene and ethylene, propylene and/or one or more C4-20 α-olefin comonomers and/or one or more additional copolymerizable comonomers. Additional comonomers are selected from diolefins, cyclic olefins, and cyclic diolefins, halogenated vinyl compounds, and vinylidene aromatic compounds.
[0056] One can measure the comonomer content in the resulting block composite polymers using any appropriate technique, with techniques based on nuclear magnetic resonance (NMR) spectroscopy being preferred. It is most desirable that some or all polymeric blocks comprise amorphous or relatively amorphous polymers such as copolymers of propylene, 1-butene or 4-methyl-1-pentene and a comonomer, especially random copolymers of propylene, 1-butene or 4-methyl -1-pentene with ethylene, and any remaining polymeric blocks (hard segments), if any, predominantly comprise propylene, 1-butene or 4-methyl-1-pentene in polymerized form. Preferably such segments are polypropylene, polybutene or poly(4-methyl-1-pentene) very crystalline or stereo specific, especially isotactic homopolymers.
[0057] Still preferably, the block copolymers of the invention comprise from 10 to 90 percent of relatively hard or crystalline segments and from 90 to 10 percent of amorphous or relatively amorphous segments (soft segments). Within the soft segments, the mole percentage of comonomer can range from 5 to 90 mole percent, preferably from 10 to 60 mole percent. In the case where the comonomer is ethylene, it is preferably present in an amount of 10% by weight to 75 percent by weight, more preferably from 30% by weight to 70 percent by weight.
[0058] Preferably, the copolymers comprise hard segments that are 80% by weight to 100% by weight of propylene. The hard segments can be more than 90% by weight, preferably more than 95% by weight, and more preferably more than 98% by weight propylene.
[0059] Composite block polymers can be differentiated from conventional random copolymers, physical polymer blends, and conventional block copolymers prepared via sequential addition of monomer. Block composites can be distinguished from random copolymers by characteristics such as higher melting temperatures for a comparable amount of comonomer, block composite index as described below; of a physical blend by characteristics such as composite block index, better tensile strength, improved fracture toughness, finer morphology, improved optics, and greater impact strength at lower temperature; of block copolymers prepared by sequential addition of monomer by molecular weight distribution, rheology, shear decrease, rheology ratio, and because there is block polydispersion.
[0060] In some embodiments, the block composites of the invention have a composite block index (BCI), defined below, that is greater than zero, but less than about 0.4 or from about 0.1 to about of 0.3. In other embodiments, BCI is greater than about 0.4 and up to about 1.0. Additionally, the BCI can range from about 0.4 to about 0.7, from about 0.5 to about 0.7, or from about 0.6 to about 0.9. In some embodiments, the BCI is in the range of from about 0.3 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, of about 0.3 to about 0.6, about 0.3 to about 0.5, or about 0.3 to about 0.4. In other embodiments, BCI is in the range of from about 0.4 to about 1.0, from about 0.5 to about 1.0, or from about 0.6 to about 1.0, from 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.
Block composites preferably have a Tm greater than 100°C, preferably greater than 120°C, and more preferably greater than 125°C. Preferably, the MFR (230°C, 2.16 kg) of the block composite is from 0.1 to 1000 dg/min, more preferably from 0.1 to 50 dg/min and most preferably from 0.1 to 30 dg /min and can also be from 1 to 10 dg/min.
[0062] Other desirable compositions according to the present invention are elastomeric block copolymers of propylene, 1-butene or 4-methyl-1-pentene with ethylene, and optionally one or more α-olefins or diene monomers. Preferred α-olefins for use in this embodiment of the present invention are designated by the formula CH2=CHR*, where R* is a linear or branched alkyl group of 1 to 12 carbon atoms. Examples of suitable α-olefins include, but are not limited to, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene (when copolymerized with propylene), and 1-octene. Suitable dienes for use in the preparation of such polymers, especially multiblock EPDM-type polymers include conjugated and unconjugated, straight or branched chain, cyclic or polycyclic dienes containing from 4 to 20 carbon atoms. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, di-cyclopentadiene, cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferred diene is 5-ethylidene-2-norbornene. The resulting product may comprise alternating isotactic homopolymer segments with elastomeric copolymer segments, prepared in place during polymerization. Preferably, the product may comprise only the elastomeric block copolymer of propylene, 1-butene or 4-methyl-1-pentene with one or more comonomers, especially ethylene.
[0063] Since diene-containing polymers contain alternating segments or blocks containing greater or lesser amounts of diene (including no amount) and α-olefin (including none), the total amount of diene and α-olefin can be reduced without loss of subsequent polymeric properties. That is, as diene and α-olefin monomers are preferentially incorporated into a block type of polymer rather than uniformly or randomly throughout the polymer, they are used more efficiently and subsequently the crosslink density of the polymer can be better controlled . Such crosslinkable elastomers and cured products have advantageous properties, including greater tensile strength and better elastic recovery.
Still preferably, the block composites of this embodiment of the invention have a weight average molecular weight (Mw) from 10,000 to about 2,500,000, preferably from 35,000 to about 1,000,000 and more preferably from 50,000 to about 300,000 , preferably from 50,000 to about 200,000.
[0065] The polymers of the invention may be diluted in oil with from 5 to about 95 percent, preferably from 10 to 60 percent, more preferably from 20 to 50 percent of a processing oil, based on the total weight of the composition. Suitable oils include any oil that is conventionally used in preparing dilute EPDM rubber formulations. Examples include both naphthenic oils and paraffinic oils, with paraffinic oils being preferred.
In the embodiments of the invention any crosslinking agent which is capable of curing EPDM can be used. Suitable curing agents include, but are not limited to, phenolic resins, peroxides, azides, aldehyde/amine reaction products, vinyl silane grafted moieties, hydrosylation, substituted ureas, substituted guanidines, substituted xanthates, substituted dithiocarbamates, sulfur-containing compounds such as thiazoles, imidazoles, sulfenamides, thiuramids, paraquinone dioxime, dibenzo paraquinone dioxime, sulfur, and combinations thereof. Appropriate crosslinking agents such as those disclosed in U.S. Patent No. 7,579,408 at column 31, line 54 to column 34, line 52, which is incorporated herein by reference, may also be used.
[0067] An elastomer composition according to this embodiment may include carbon black. Preferably, the carbon black is present in an amount of 10 to 80 percent, more preferably 20 to 60 percent, based on the total weight of the composition.
[0068] Additional components of the present formulations usefully employed in accordance with the present invention include various other ingredients in amounts that do not detract from the properties of the resulting composition. These ingredients include, but are not limited to, activators such as calcium or magnesium oxide; fatty acids such as stearic acid and salts thereof; fillers and builders such as calcium or magnesium carbonate, silica, and aluminum silicates; plasticizers such as dialkyl dicarboxylic acid esters; antidegradants; emollients; waxes; and pigments. Polymerization Methods
Suitable processes useful for making the block composites of the invention can be found, for example, in U.S. Patent Application Publication No. 2008/0269412, published October 30, 2008, which is hereby incorporated by reference. In particular, the polymerization is desirably carried out as a continuous polymerization, preferably a continuous solution polymerization, in which the catalytic components, and optionally solvent, adjuvants, scavengers, and polymerization aids are continuously supplied to one or more reactors or zones and the polymeric product is continuously removed from them. Within the scope of the terms "continuous" or "continuously" when used in this context are those processes in which intermittent additions of reagents and removal of products occur at small regular or irregular intervals, so that, over time, the overall process is substantially continuous. In addition, as explained above, the exchange agent(s) can be added at any point during the polymerization including in the first reactor or zone, at the exit or just before the exit of the first reactor, between the first reactor or zone and the second or any subsequent reactor or zone, or even only in the second or any subsequent reactor or zone. Due to the difference in monomers, temperatures, pressures or other difference in polymerization conditions between at least two of the reactors or zones connected in series, polymer segments of different composition are formed in the different reactors or zones such as comonomer content, crystallinity, density , tacticity, regioregularity, or other chemical or physical difference, within the same molecule. The size of each segment or block is determined by continuous polymer reaction conditions, and preferably is a very likely distribution of polymer sizes.
[0070] Each reactor in series can be operated under polymerization conditions in high pressure, in solution, in slurry (slurry), or in gas phase. In multizone polymerization, all zones operate in the same type of polymerization, such as in solution, slurry (slurry), or gas phase, but under different process conditions. For a solution polymerization process, it is desirable to employ homogeneous dispersions of the catalyst components in a liquid diluent in which the polymer is soluble under the polymerization conditions employed. Such a process using extremely fine silica or similar dispersing agent to produce such a homogeneous catalytic dispersion in which normally the metal complex or co-catalyst is only sparingly soluble is disclosed in US-A-5,783,512. Usually, a process is carried out at high pressure at temperatures from 100°C to 400°C and at pressures above 50 MPa (500 bar). A slurry (slurry) process typically uses an inert hydrocarbon diluent and temperatures from 0°C to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. In a slurry (slurry) polymerization the preferred temperatures are from 30°C, preferably from 60°C to 115°C, preferably up to 100°C. Typically, pressures range from atmospheric (100 kPa) to 3.4 MPa (500 psi).
[0071] In all of the above processes, preferably continuous or substantially continuous polymerization conditions are employed. The use of such polymerization conditions in especially continuous solution polymerization processes allows the use of high reactor temperatures which results in cost-effective production of the present block copolymers in high yields and efficiencies.
[0072] The catalyst can be prepared as a homogeneous composition by adding the required metal complex or multiple complexes in a solvent in which to carry out the polymerization or in a diluent compatible with the final reactant mixture. The desired activator or co-catalyst and, optionally, the exchange agent, can be combined with the catalyst composition before, simultaneously with, or after combining the catalyst with the monomers to be polymerized and any additional reaction diluents.
[0073] At all times, individual ingredients as well as any active catalyst composition must be protected from oxygen, moisture and other catalyst poisons. Therefore, the catalyst, exchange agent and activated catalyst components must be prepared and stored in an oxygen and moisture free atmosphere, preferably in dry inert air such as nitrogen.
[0074] Without in any way limiting the scope of the invention, a means of carrying out such a polymerization process is as follows. In one or more well stirred tank or circulating reactors operating under solution polymerization conditions, the monomers to be polymerized are continuously introduced together with any solvent or diluent into a part of the reactor. The reactor contains a relatively homogeneous liquid phase composed substantially of monomers together with any solvent or diluent and dissolved polymer. Preferred solvents include C4-10 hydrocarbons or mixtures thereof, especially alkanes such as hexane or mixture of alkanes, as well as one or more of the monomers employed in the polymerization. Examples of suitable loop reactors and a variety of operating conditions suitable for use with them, including the use of multiple loop reactors operating in series, are found in US Patent Nos. 5,977,251, 6,319,899 and 6,683,149 .
[0075] Catalyst together with co-catalyst and optionally chain exchange agent are introduced continuously or intermittently into the liquid reactor phase or any recycled portion thereof at at least one location. Reactor temperature and pressure can be controlled by adjusting the solvent/monomer ratio, catalyst addition rate, as well as by using cooling or heating coils, jackets, or both. The rate of polymerization is controlled by the rate of addition of catalyst. The content of a given monomer in the polymer product is influenced by the ratio of monomers in the reactor, which is controlled by manipulating the respective feed rates of these components into the reactor. The molecular weight of the polymeric product is optionally controlled by controlling other polymerization variables such as temperature, monomer concentration, or by the aforementioned chain exchange agent, or a chain terminating agent such as hydrogen, as is well known in the art. A second reactor is connected to the reactor discharge, optionally via conduit or other transfer means, such that the reactant mixture prepared in the first reactor is discharged into the second reactor without substantial termination of polymer growth. Between the first and second reactors, a differential is established in at least one process condition. Preferably for use in forming a copolymer of two or more monomers, the difference is the presence or absence of one or more comonomers or a difference in monomer concentration. Additional reactors can also be provided, each arranged similarly to the second reactor in the series. At the exit of the last reactor in the series, the effluent is contacted with a catalyst extinguishing agent such as water, water vapor or an alcohol with a coupling agent.
[0076] The resulting polymeric product is recovered by eliminating volatile components from the reaction mixture such as residual monomers or diluent under reduced pressure, and, if necessary, performing additional devolatilization in equipment such as a devolatilization extruder. In a continuous process the average residence time of catalyst and polymer in the reactor is generally 5 minutes to 8 hours, and preferably 10 minutes to 6 hours.
[0077] Alternatively, the above polymerization can be carried out in a continuous flow reactor with a monomer, catalyst, exchange agent, temperature or other gradient established between different zones or regions thereof, optionally, accompanied by separate addition of catalysts and/or chain exchange agent, and operating under adiabatic or non-adiabatic polymerization conditions.
[0078] The catalytic composition can also be prepared and employed as a heterogeneous catalyst by adsorbing the indispensable components onto an inert organic or inorganic particulate solid, as discussed above. In a preferred embodiment, a heterogeneous catalyst is prepared by co-precipitating the metal complex and reaction product from an inert inorganic compound and an activator containing active hydrogen, especially the reaction product from a tri(C1-4 alkyl) compound aluminum and an ammonium salt of a hydroxy aryl tris(pentafluor-phenyl) borate, such as an ammonium salt of a (4-hydroxy-3,5-ditertiobutyl-phenyl) tris(pentafluor-phenyl) borate. When prepared in a heterogeneous or supported form, the catalytic composition can be employed in a slurry (slurry) or gas phase polymerization. As a practical limitation, slurry polymerization (slurry) takes place in liquid diluents in which the polymeric product is substantially insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane in whole or in part can be used as the diluent. When with a solution polymerization, α-olefin comonomer or a mixture of different α-olefin monomers can be used in whole or in part as the diluent. Most preferably at least a major part of the diluent comprises the α-olefin monomer or monomers to be polymerized.
[0079] TPV Compositions
[0080] TPV compositions comprise at least one thermoplastic polymer as matrix phase. Suitable thermoplastic polymers include, but are not limited to, polyethylene, polypropylene, polycarbonate, olefinic block copolymers, polystyrene, poly(ethylene terephthalate), nylon, branched polyethylene (such as high density polyethylene), branched polypropylene, branched polycarbonate , branched polystyrene, branched poly(ethylene terephthalate), and branched nylon. Still suitable thermoplastic polyolefins are those disclosed, for example, in U.S. Patent No. 7,579,408, column 25, line 4 through column 28, line 28, which is incorporated herein by reference.
[0081] TPV compositions also comprise at least one vulcanizable elastomer. Any vulcanizable elastomer can be used to form a TPV, as long as it can be cross-linked (ie, vulcanized) by a cross-linking agent. Vulcanizable elastomers, although thermoplastic in the uncured state, are normally classified as thermoset because they undergo an irreversible process of thermoset to an unprocessable state. Preferred vulcanizable elastomers include those such as those disclosed in U.S. Patent No. 7,579,408, column 29, line 61 through column 31, line 40, which is incorporated herein by reference. Particularly preferred vulcanizable elastomers are EPDM, ethylene/α-olefin copolymers, olefinic block copolymer and can also be block composites as defined herein.
[0082] Any crosslinking agent that is capable of curing an elastomer, preferably without degrading and/or substantially curing the thermoplastic polymer used in a TPV, can be used in embodiments of the invention. A preferred crosslinking agent is phenolic resin. Other curing agents include, but are not limited to, peroxides, azides, aldehyde/amine reaction products, vinyl silane grafted moieties, hydrosylation, substituted ureas, substituted guanidines, substituted xanthates, substituted dithiocarbamates, sulfur containing compounds such as thiazoles , imidazoles, sulfenamides, thiuramids, paraquinone dioxime, dibenzo paraquinone dioxime, sulfur, and combinations thereof. Appropriate crosslinking agents such as those disclosed in U.S. Patent No. 7,579,408 at column 31, line 54 to column 34, line 52, which is incorporated herein by reference, may also be used.
[0083] The properties of a TPV can be modified, either before or after vulcanization, by adding ingredients that are conventional in the composition of EPDM rubber, thermoplastic polymer resin and combinations thereof. Examples of such ingredients include particulate filler such as carbon black, amorphous precipitated silica, fumed colloidal silica, titanium dioxide, colored pigments, clay, talc, calcium carbonate, wollastonite, mica, montmorillonite, glass beads, hollow glass spheres , glass fibers, zinc oxide and stearic acid, stabilizers, antidegradants, flame retardants, processing aids, adhesives, tackifiers, plasticizers, waxes, staple fibers such as wood cellulose fibers and extender oils. Additional additives are those disclosed in U.S. Patent No. 7,579,408, column 34, line 54 through column 35, line 39, which is incorporated herein by reference.
[0084] Typically, thermoplastic vulcanizates are prepared by mixing plastic rubbers and cured by dynamic vulcanization. The compositions can be prepared by any method suitable for mixing rubbery polymers including mixing in a rubber laminator or in internal mixers such as a Banbury mixer. Additional details on suitable methods are those disclosed in U.S. Patent No. 7,579,408, column 35, line 40 to column 39, line 16, which is incorporated herein by reference.
[0085] Thermoplastic vulcanizate compositions are useful for fabricating a variety of articles such as tires, hoses, belts, gaskets, moldings or molded parts. They are particularly useful in applications that require high melt strength such as large piece blow molding, foams, and wire and cable. They are also useful for modifying thermoplastic resins, in particular thermoplastic polymeric resins. Additional TPV applications are disclosed in U.S. Patent No. 7,579,408, column 39, line 25 through column 40, line 45, which is incorporated herein by reference. Test Methods
[0086] The overall composition of each resin is determined by DSC, NMR, GPC, DMS, and TEM morphology. Additionally, xylene fractionation can be used to estimate block copolymer production. Differential Scanning Calorimetry (DSC)
[0087] Differential Scanning Calorimetry (DSC) is performed on a TA Instruments DSC Q1000 equipped with an RSC cooling accessory and an automatic sampler. A nitrogen purge gas flow of 50 mL/min is used. The sample is pressed into a thin film and melted in the press at about 190°C and then cooled in air to room temperature (25°C). Then 3-10 mg of material is cut, accurately weighed, and placed in a lightweight aluminum pan (ca. 50 mg), which is then closed and crimped. The thermal behavior of the sample is investigated with the following temperature profile: the sample is rapidly heated to 190°C and held isothermally for 3 minutes in order to remove any previous thermal history. The sample is then cooled to -90°C at a cooling rate of 10°C/min and held at -90°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. 13C Nuclear Magnetic Resonance (NMR) Sample preparation
Samples were prepared by adding approximately 2.7 g of 50/50 mixture of tetrachloroethane-d2/ortho-dichloro-benzene which is 0.025M in chromium acetyl acetonate (relaxing agent) to 0.21 g of sample in a 10 mm NMR tube. Samples are dissolved and homogenized by heating the tube and its contents to 150°C.
[0089] Data acquisition parameters
[0090] Data are collected using a Bruker 400 MHz spectrometer equipped with Bruker's DUL double high temperature cryogenic probe. Data is acquired using 320 transients per data file, a 7.3 s relaxation delay (6 s delay and 1.3 s acquisition time), 90 degree rotation angles, and inverse constrained decoupling with a temperature of 125°C sample. All measurements are taken from rotation samples in locked mode. Samples are homogenized immediately prior to insertion into the heated (130°C) NMR sample changer, and remain in the probe for 15 minutes to achieve thermal equilibrium prior to data acquisition. Gel Permeation Chromatography (GPC)
[0091] The gel permeation chromatographic system consists of one of a Model PL-210 or Model PL220 instrument from Polymer Laboratories. The carousel compartment and the column compartment are operated at 140°C. Three 10 Mixed-B columns from Polymer Laboratories are used. The solvent is 1,2,4-trichlorobenzene. Samples are prepared at a concentration of 0.1 g polymer in 50 ml solvent containing 200 ppm butylated hydroxytoluene (BHT). Samples are prepared by gently shaking for 2 hours at 160°C. The injection volume used is 100 μL and the flow rate is 1.0 mL/min.
[0092] The calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards, with molecular weights ranging from 580 to 8,400,000 g/mol, arranged in 6 “cocktail” mixtures with at least one ten separation between individual molecular weights. Standards were purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared in 0.025 g in 50 mL solvent for molecular weights greater than or equal to 1,000,000, and 0.05 g in 50 mL solvent for molecular weights less than 1,000,000. Polystyrene standards are dissolved at 80°C with gentle agitation for 30 minutes. Narrow standard blends are used first, and in descending order from the highest molecular weight component, to minimize degradation. Polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation (described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): Polyethylene = 0.645 (Mpolystyrene).
Polypropylene equivalent molecular weight calculations are performed using Viscotek's TriSEC software version 3.0.
[0094] Fractionation by rapid temperature gradient elution (F-TREF)
[0095] In the analysis by F-TREF, the composition to be analyzed is dissolved in ortho-dichloro-benzene and allowed to crystallize in a column containing an inert support (stainless steel granule) slightly reducing the temperature to 30°C ( at a preferred rate of 0.4°C/min). The column is equipped with an infrared detector. Then, an F-TREF chromatogram curve is generated by eluting the crystallized polymer sample from the column by slightly increasing the temperature of the eluting solvent (o-dichlorobenzene) from 30 to 140°C (at a preferred rate of 1.5 °C/min). High Temperature Liquid Chromatography (HTLC)
[0096] HTLC is performed according to the methods disclosed in US Patent Application Publication No. 2010-0093964 and US Patent Application No. 12/643111, filed December 21, 2009, both of which are hereby incorporate by reference. Samples are analyzed using the methodology described below.
[0097] A Waters GPCV2000 high temperature SEC chromatograph was reconfigured to develop the HT-2DLC instrumentation. Two Shimadzu LC-20AD pumps were connected to the injector valve via a binary mixer. The first dimension HPLC column (D1) was connected between the injector and a 10 inlet switch valve (Valco Inc.). The second dimension SEC column (D2) was connected between the 10-inlet valve and IR (concentration and composition), RI (index of refraction), and IR (intrinsic viscosity) LS (Varian Inc.) detectors. RI and IV were detectors built into GPVC2000. The IR5 detector was provided by PolymerChar, Valencia, Spain.
Columns: Column D1 was a HYPERCARB high temperature graphite column (2.1 x 100 mm) purchased from Thermo Scientific. Column D2 was a PLRapid-H column purchased from Varian (10 x 100 mm).
Reagents: HPLC grade trichlorobenzene (TCB) was purchased from Fischer Scientific. Decane, 1-decanol and 2,6-ditertiarybutyl-4-methyl-phenol (IONOL) were purchased from Aldrich.
[0100] Sample preparation: 0.01-0.15 g of polyolefin sample was placed in a small 10 ml bottle of Waters automatic sampler. Then, 7 ml of 1-decanol or decane with 200 ppm IONOL was added in the small vial. After spraying helium in the small sample vial for about 1 minute, the small sample vial was placed on a heated shaker with a temperature set at 160°C. The dissolution was carried out by shaking the small flask at a temperature of 160°C for 2 hours. Then, by injection, the small vial was transferred to the automatic sampler. Note that the actual volume of the solution was greater than 7 mL due to thermal expansion of the solvent.
[0101] HT-2DLC: The flow rate of D1 was 0.01 ml/min. The mobile phase composition was 100% weak eluent (1-decanol or decane) for the first 10 minutes of run. Then the composition was increased to 60% strong eluent (TCB) in 489 min. Data were collected for 489 min as the duration of the raw chromatogram. The 10 inlet valve was changed every three minutes producing 489/3=163 SEC chromatograms. A post-operation gradient after data acquisition time of 489 min was used to clean and balance the column for the following operation: Clean steps: 1.490 min: flow= 0.01 min; //Keep constant flow rate of 0.01 mL/min from 0-490 min. 2. 491 min: flow= 0.20 min; //Increase flow rate to 0.20 mL/min. 3. 492 min: %B=100; // Increase mobile phase composition to 100% TCB. 4. 502 min: %B=0; // Wash column using 2 mL of TCB. Equilibration steps: 5. 503 min: %B=0; // Change mobile phase composition to 100% 1-decanol or decane. 6. 513 min: %B=0; // Equilibrate the column using 2 mL of weak eluent. 7. 514 min: flow=0.2 ml/min; // Keep the flow constant at 0.2 mL/min from 491-514 min. 8. 515 min: flow= 0.01 ml/min; // Decrease flow rate to 0.01 mL/min.
[0102] After step 8, the flow rate and mobile phase composition were the same as the initial conditions of the operating gradient.
[0103] The flow rate of D2 was 2.51 ml/min. Two 60 µL rings were installed on the 10 inlet switch valve. 30 µL of the eluent from column D1 was loaded onto the SEC column with each valve switch.
[0104] IR, LS15 (15° light scattering signal), LS90 (90° light scattering signal), and IR (intrinsic viscosity) signals were collected by EZChrom through an analogue conversion box for digital SS420X. The chromatograms were exported in ASCII format and imported into MATLAB domestic software for data reduction. An appropriate calibration curve of polymer composition and retention volume is used for polymers that are similar in nature to the hard block and soft block contained in the block composite under analysis. Calibration polymers must be narrow in composition (both in molecular weight and chemical composition) and span a reasonable range of molecular weights to cover the composition of interest during analysis. Analysis of the raw data was calculated as follows: The first dimension HLPC chromatogram was reconstructed by plotting the IR signal of each slice (from the total SEC chromatogram of IR of the slice) as a function of the elution volume. The IR against D1 elution volume was normalized by total IR sign to obtain the plot of weight fraction against D1 elution volume. The methyl/IR measurement ratio was obtained from the reconstructed IR measurement and the methyl IR measurement chromatograms. The ratio to composition was converted using a calibration curve of wt% PP (by NMR) against methyl/measure obtained from SEC experiments. Mw was obtained from the reconstructed IR and LS measurement chromatograms. The ratio was converted to Mw after calibration of both the IR and LS detectors using a PE standard.
[0105] The percentage by weight of isolated PP is measured as the area corresponding to the hard block composition based on the isolated peak and retention volume determined by a composition calibration curve.
[0106] Dynamic-mechanical spectroscopy (DMS)
[0107] Dynamic-mechanical measurements (loss and storage modulus against temperature) are measured in ARES from TA Instruments. Dynamic modulus measurements are performed in torsion on a solid bar of ca. 2 mm thick, 5 mm wide and approx. 10 mm long. Data is recorded at a constant frequency of 10 rad/s and a heating/cooling rate of 5°C/min. Temperature scans are performed from -90°C to 190°C at 5°C/min. Transmission Electron Microscopy (TEM)
[0108] Polymer films are prepared by compression molding followed by quick quenching. The polymer is pre-melted at 190°C for 1 minute at 1000 psi and then pressed for 2 minutes at 500 psi and then tempered between chilled plates (15-20°C) for 2 minutes.
[0109] The compression molded films are ground so that they can be collected close to the core of the films. Ground samples are cold polished prior to staining by removing sections from the blocks at -60°C to prevent undue staining of the elastomer phases. The cold polished blocks are dyed with the vapor phase of an aqueous solution of 2% ruthenium tetroxide for 3 hours at room temperature. The dyeing solution is prepared by weighing 0.2 g of hydrated ruthenium(III) chloride (RuCl3.xH2O) into a glass bottle with a screw cap and adding 10 mL of 5.25% aqueous sodium hypochlorite solution to the bottle. Samples are placed in the glass bottle using a glass slide having double-sided tape. The blade is placed in the bottle to suspend the blocks about 1 inch above the dye solution. At room temperature, sections approximately 90 nm thick are collected using a diamond knife on a Leica EM UC6 microtome and placed on blank 600 mesh TEM screens for observation.
[0110] Image Collection - Images of tEM are collected on a JEOL JEM-1230 operated at 100 kV accelerating voltage and collected on Gatan-791 and 794 digital cameras.
[0111] Analysis by fractionation of solubles in xylene
[0112] A weighed amount of resin is dissolved in 200 mL of o-xylene under reflux conditions for 2 hours. Then, the solution is cooled in a temperature-controlled water bath at 25°C to allow crystallization of the xylene-insoluble fraction (XI). When the solution cools and the insoluble fraction precipitates out of solution, the separation of the xylene-soluble fraction (XS) from the xylene-insoluble fraction (XI) is done by filtration through a paper filter. The remaining o-xylene solution is evaporated from the filtrate. Both fractions XS and XI are dried in a vacuum oven at 100°C for 60 minutes and then weighed. Alternatively, if the solution crystallization temperature of the soft block polymer is greater than room temperature, the fractionation step can be carried out at a temperature of 10-20°C above the soft block crystallization temperature, but below the temperature of crystallization of hard blocks. The separation temperature can be determined by TREF and CRYSTAF measurements described in the reference “TREF and CRYSTAF Technologies for Polymer Characterization” (“TREF and CRYSTAF Technologies for Polymer Characterization”), Encyclopedia of Analitical Chemistry, published in 2000, pages 8074-8094. This fractionation can be performed in a laboratory heated filtration and dissolution apparatus or a fractionation instrument such as PREPARATORY mc2 (obtainable from PolymerChar, Valencia, Spain). Melt Flow Rate and Melt Index
[0113] The melt index, or I2, is measured in grams per 10 minutes, according to ASTM D 1238, condition 190°C/2.6 kg. The MFR of PP resins is measured according to ASTM D 1238, condition 230°C/2.16 kg. Shore A hardness
[0114] Shore A hardness was measured according to ASTM D2240. Compression deformation
[0115] Measure deformation by compression according to ASTM D 395 at 70°C. Traction related properties
[0116] Performs maximum tensile strength and elongation in accordance with ASTM D 412, Atomic Force Microscopy (AFM)
[0117] Samples are polished under cryogenic conditions using a Leica UCT/FCS microtome operated at -120°C. A few thin sections (about 160 nm) are cut from the sample and placed on a mica surface for AFM analysis. Topography and phase images are captured at room temperature using Digital Instruments multimode AFM (now Veeco) equipped with a NanoScope IV controller. For the object imaging phase, nanosensor probes with a spring constant of 55 N/m and a resonant frequency close to 167 kHz are used. Sample imaging occurs at a frequency of 0.5-2 Hz and a setpoint ratio of ~0.8. Test Methods for TPV Compositions Gel Content
[0118] The gel content is measured by the small-scale Soxhlet extraction method. Samples are cut into small pieces ranging from about 35 mg to 86 mg. Three pieces of each sample are individually weighed with four-digit precision on an electronic analytical balance. Each piece is placed inside a small cylinder composed of aluminum window screen. The ends of the cylinders are closed with pieces of plain paper. Six aluminum cylinders are placed inside a fritted glass extraction cone. Extraction cones are placed in jacketed Soxhlet extractors and extracted overnight with refluxing xylenes. At the end of the minimum 12-hour extraction, the still hot cones are rapidly cooled in methanol. Methanol precipitates the gels making them easier to remove intact from the cylinders. Cylinders containing precipitated gels are briefly purged with nitrogen to separate free methanol. The gels are removed from the aluminum cylinders with tweezers and placed on aluminum pans for weighing. The gel pans are vacuum dried for 1 hour at 125°C. Cold, dry gels are removed from the aluminum weighing pans and weighed directly onto the top loading analytical balance. Divide the dry extracted gel weight by the starting weight to give the percentage gel content. Atomic force microscopy (AFM)
[0119] Samples are polished under cryogenic conditions using a Leica UCT/FCS microtome operated at -120°C. A few thin sections (about 160 nm) are cut from the sample and placed on a mica surface for AFM analysis. Topography and phase images are captured at room temperature using Digital Instruments multimode AFM (now Veeco) equipped with a NanoScope IV controller. For the object imaging phase, nanosensor probes with a spring constant of 55 N/m and a resonant frequency close to 167 kHz are used. Sample imaging occurs at a frequency of 0.5-2 Hz and a setpoint ratio of ~0.8. Differential Scanning Calorimetry (DSC)
[0120] Differential Scanning Calorimetry (DSC) is performed on a TA Instruments DSC Q1000 equipped with an RSC cooling accessory and an automatic sampler. A nitrogen purge gas flow of 50 mL/min is used. The sample is pressed into a thin film and melted in the press at about 190°C and then cooled in air to room temperature (25°C). Then 3-10 mg of material is cut, accurately weighed, and placed in a lightweight aluminum pan (ca. 50 mg), which is then closed and crimped. The thermal behavior of the sample is investigated with the following temperature profile: the sample is rapidly heated to 190°C and held isothermally for 3 minutes in order to remove any previous thermal history. The sample is then cooled to -90°C at a cooling rate of 10°C/min and held at -90°C for 3 minutes. The sample is then heated to 150°C at a heating rate of 10°C/min. The first cooling curve and the second heating curve are recorded.
[0121] Constant temperature dynamic frequency curves in the frequency range of 0.1 to 100 rad/s in nitrogen purge are run using an advanced TA Instruments Rheometric Expansion (ARES) system equipped with 25 parallel plates. mm. TPV or TPO samples are die cut from injection molded plates into circular specimens 1 inch diameter x 3 mm thick. The sample is placed on the plate and allowed to melt for 5 minutes. The plates are then confined to 2.1 mm, the sample trimmed, and the slit closed to 2.0 mm before starting the test. The method has a built-in 5-minute delay to allow for temperature equilibrium. Both TPV and TPO samples are measured at 230°C. The deformation amplitude is kept constant at 10%. The voltage response is recorded as storage modulus (G’), loss modulus (G”) and complex viscosity (n*). Thermodynamic-mechanical analysis (DMTA)
[0122] Measure the dynamic mechanical properties of solid state materials in a dynamic rheometric analyzer (RDA III) in rectangular torsional module on a rectangular bar. Specimens 3 mm thick and 12.5 mm wide are die cut from compression or injection molded plates. The slit is adjusted to 10 mm for all samples. The temperature ranges from -100°C to 200°C at a rate of 5°C/min, and the storage module (G') and the loss module (G') are monitored at a constant rate of 10 rad/s ). When samples expand during heating, adapt the slit to minimize the normal load on the sample. It is allowed to vary the deformation range from 0.05% at low temperature to 4% at high temperature. Shore A hardness
[0123] Hardness measurements are performed with a Shore A durometer. The durometer is placed on a plate approximately 3 mm thick prepared by compression molding or injection molding. Compression deformation
[0124] Compression strain is measured according to ASTM D 395 at 70°C and 120°C. 20 mm disks (± 0.5 mm) are extracted from the compression or injection molded plates of approximately 3 mm thickness. For each sample, four discs are inspected for notches, irregular thickness and inhomogeneity, and are stacked such that the total height is 12.5 mm (± 0.5 mm), equating to the compressive deformation of 25%. Deformation by compression is performed on two specimens for each sample at two temperatures.
[0125] Stacked discs are placed in the compression device and locked in place; the device is then placed at the appropriate temperature for the specified time (22 h for 70°C and 72 h for 120°C). In this test, the voltage is released at the test temperature and the thickness of the sample is measured after an equilibrium period of 30 min at room temperature.
[0126] Compression strain is a measure of the degree of recovery of a sample following compression and is calculated according to the equation: CS= (H0-H2)/(H0-H1), where H0 is the original thickness of the sample , H1 is the thickness of the spacer bar used and H2 is the final thickness of the sample after removal of the compressive force. Stress/strain properties
[0127] Tensile properties are measured at room temperature according to ASTM D412, on micro-tensile specimens that are die-cut from the same compression molded or injection molded plates in the rolling direction. Tensile strain is calculated from the ratio of the increment in length between staples to the initial standard length. Tensile stress is determined by dividing the tensile load by the initial cross section of the specimen.
[0128] Table A shows a summary of all characterization methods used in this study and specific conditions. Table A. Summary of characterization methods and conditions
Examples general examples
[0129] Catalyst-1 ([[rel-2',2"'-[(1R,2R)-1,2-cyclohexanediyl bis(methylene oxy-κO)]bis[3-(9H-carbazol-9-yl) )-5-methyl[1,1'-biphenyl]-2-olate-κO]](2-)dimethylhafnium) and cocatalyst 1, a mixture of methyl di(C14-18 alkyl) ammonium salts of borate of tetrakis (penta-fluor phenyl), prepared by reacting a long-chain trialkylamine (ARMEEN™ M2HT, obtainable from Akzo-Nobel, Inc.), HCl and Li[B(C6F5)4], substantially as disclosed in USP 5,919,983, Example 2, are purchased from Boulder Scientific and used without further purification. CSA-1 (diethyl zinc or DEZ) and modified methyl aluminoxane (MMAO) were purchased from Akzo Nobele used without further purification. The solvent for the polymerization reactions is a mixture of hydrocarbons (SBP 100/140) obtainable from Shell Chemical Company and purified through beds of 13-X molecular sieves prior to use.
[0130] All examples except A1, E1, U1 and Y1 have an iPP hard block. Series B to D have a semi-crystalline ethylene/propylene soft block containing 60-65% by weight of C2 while series F to H have an amorphous ethylene/propylene soft block containing 40% by weight of C2. Increasing the alphabetical order independently controls the weight fraction and length of the iPP hard block from 30 to 60 percent by weight increasing the production rate in the reactor (in this case, reactor 2).
[0131] Examples V1, W1, X1 and Y1, Z1, AA are similar in design to B, C, D, but prepared under different reactor conditions. The effect of higher conversion of propylene and reactor temperature will be discussed later.
[0132] All examples run without hydrogen. The CSA concentration in Reactor 1 for all examples is 153 mmol/kg. The MMAO concentration in Reactor 2 for all examples is 6 mmol/kg. Samples A1-D1
[0133] Inventive propylene/ethylene copolymers were prepared using two continuous stirred tank reactors (CSTR) connected in series. Each reactor is hydraulically filled and tuned to operate under steady-state conditions. Sample A1 is prepared by flowing monomers, solvent, catalyst-1, cocatalyst-1, and CSA-1 into the first reactor according to the process conditions outlined in Table 1. To prepare sample B1, the contents of first reactor described in Table 1A flowed into a second reactor in series. More catalyst-1 and co-catalyst-1 were added in the second reactor, as well as a small amount of MMAO as a scavenger. Samples C1 and D1 were prepared by controlling the conditions of the two reactors as described in Tables 1A and 1B. Samples E1-AB1
[0134] Each set of samples of diblocks F1-H1, V1-X1, Y1-AB1 was prepared as above for Examples B1-D1, but according to the process conditions outlined in Tables 1A and 1B. For each set, a first reactor product (E1, U1, Y1) is prepared aiming at the first composition in blocks. Table 1A. First reactor process conditions for producing copolymers in B1-D1, F1-H1, V1-X1, Z1-AB1 diblocks. §- Only products from the 1st reactor.
Table 1B Second process conditions for producing copolymers in diblocks B1-D1, F1-H1, V1-X1, Z1-AB1.
§- Only products from the 1st reactor. Preparation of fractional samples
[0135] Two to four grams of polymer are dissolved in 200 mL of o-xylene under reflux conditions for 2 hours. Then, the solution is cooled in a temperature-controlled water bath at 25°C to allow crystallization of the xylene-insoluble fraction. When the solution cools and the insoluble fraction precipitates out of solution, the separation of the xylene-soluble fraction from the xylene-insoluble fraction is done by filtration through a paper filter. The remaining o-xylene solution is evaporated from the filtrate. Both fractions XS (soluble in xylene) and XI (insoluble in xylene) are dried in a vacuum oven at 100°C for 60 minutes and then weighed.
[0136] For each set of samples, the number insoluble in xylene is given the number “2” and for the soluble fraction in xylene the number “3”. For example, sample B1 is subjected to the extraction procedure to produce sample B2 (the fraction insoluble in xylene) and sample B3 (the fraction soluble in xylene).
[0137] Table 2 shows the analytical results for series B1 to AB1. The molecular weight distributions of the polymers are relatively narrow with Mw/Mn ranging from 2.1-2.3 for samples B1 through D1 and 2.2-2.8 for samples F1 through H1. For samples V1 through AB1, Mw/Mn ranges from 2.1-2.5. For the corresponding xylene-soluble and insoluble fractions for each of the series (designated by the number 2 or 3), Mw/Mn ranges from 2.0 to 2.8.
[0138] Table 2 also shows the percentage by weight of isolated PP identified by separation by high temperature liquid chromatography. The amount of PP isolated indicates the amount of PP that is not incorporated into the block copolymer. The weight fraction of isolated PP and the weight fraction of solubles in xylene subtracted from 1 can be related to the yield of polymer in diblocks produced.
[0139] The molecular weight distributions of polymers are relatively narrow with Mw/Mn ranging from 2.1-2.3 for samples B1 to D1, and ranging from 2.2-2.8 for samples F1 to H1. For samples V1 to AB1, Mw/Mn ranges from 2.1-2.5. For the corresponding xylene soluble and insoluble fractions for each of the series (designated by the number 2 or 3), Mw/Mn ranges from 2.0 to 2.8. Table 2 - Analytical summary of Examples B1-AB1 and fractions

[0140] Figure 1 shows the DSC melting curve for sample B1. The peak at 130°C corresponds to the “hard” polymer of iPP and the broader peak at 30°C corresponds to the “soft” polymer of EP; the glass transition temperature at -46°C also corresponds to the "soft" EP polymer containing 64% by weight of ethylene (C2).
[0141] Figure 2 shows the DSC melting curve for sample F1. The peak at 135°C corresponds to the "hard" iPP polymer and the absence of crystallinity below room temperature corresponds to the "soft" EP polymer containing 40% by weight of C2. A Tg of -50°C confirms the presence of the "soft" EP polymer containing 40% by weight of C2.
[0142] The presence of block copolymer can change the crystallization characteristics of a polymer chain if measured by TREF or solution fractionation. Figure 3 compares sample TREF profiles B1 through D1. The TREF profiles are consistent with the DSC results, showing a very crystalline fraction (elution above 40°C) and a soluble fraction of low crystallinity (remaining material eluting below 40°C). The elution temperature increases with the amount of iPP present. An EP block attached to an iPP block can improve the solubility of chains in the solvent and/or interfere with crystallization of the iPP block.
[0143] Figures 4 and 5 show the corresponding DSC curves of the fractions of B2, B3 and F2, F3.
[0144] In this analysis, the fraction soluble in xylene is an estimate of the amount of soft non-crystallizable polymer. For the xylene-soluble fractions of samples B1-D1, the percentage by weight of ethylene is between 61 and 65% by weight of ethylene without detection of residual isotactic propylene. DSC of the xylene-soluble fraction confirms that no high crystallinity polypropylene is present.
[0145] On the other hand, the insoluble fraction (designated as number 2) may contain an amount of iPP polymer and iPP/EP diblocks. Since the crystallization and elution of the polymer chain is governed by its longer crystallizable propylene sequence, the diblock copolymer will precipitate along with the iPP polymer. This is verified by the NMR and DSC analyzes which show an appreciable, and otherwise inexplicable amount of ethylene present in the “insoluble” fraction. A typical separation of a mixture of iPP and EP rubber will be completely separated by this analysis. The fact that there is additional ethylene present in the insoluble fraction confirms that a diblock fraction is present. By calculating the total monomer mass balance between the fractions, it is possible to estimate the composite index in blocks.
[0146] Another indication of the presence of diblocks is the increase in the molecular weight of insoluble fractions with the increase in the amount of iPP. Since the polymer chains are coordinated in a coordinated fashion during the passage from the first reactor to the second reactor, it is expected that the molecular weight of the polymer will increase. Table 3 shows that the molecular weight of the soluble fractions remains relatively constant (12,140 kg/mol). This is to be expected because the reactor conditions for preparing the EP soft block have not changed from series to series. However, the molecular weight of the insoluble fractions increases with increasing reactor 2 production rate to create longer iPP blocks. Composite Index Calculation in Blocks
[0147] The inventive examples show that the insoluble fractions contain an appreciable amount of ethylene that, on the contrary, would not be present if the polymer were simply a mixture of iPP homopolymer and EP copolymer. To explain this “extra ethylene”, a mass balance can be performed to calculate a block composite index of the amount of insoluble and soluble fractions in xylene and the percentage by weight of ethylene present in each of the fractions.
[0148] The sum of the ethylene weight percentages of each fraction according to Equation 1 results in the total ethylene weight percentage (in the polymer). This mass balance equation can also be used to determine the amount of each component in a binary mixture or extended to a quaternary mixture, or even to a mixture of “n” components. %

[0149] Applying equations 2 to 4, the amount of soft block (providing the source of extra ethylene) present in the insoluble fraction is calculated. By substituting the percentage by weight of C2 of the insoluble fraction in the first member of equation 2, one can calculate the percentage by weight of hard iPP and the percentage by weight of soft EP using equations 3 and 4. Note that the percentage in weight of ethylene in the soft EP is adjusted to be equal to the percentage by weight of ethylene in the xylene-soluble fraction. The weight percent of ethylene in the iPP block is set to zero or if known otherwise from its DSC melting point or other measure of composition, the value can be put in its place.


[0150] After explaining the "additional" ethylene present in the insoluble fraction, the only way to have an EP copolymer present in the insoluble fraction, the EO polymer chain must be bonded to an iPP polymer block (or otherwise it it would have been extracted from the xylene-soluble fraction). Therefore, when the iPP block crystallizes, it prevents the EP block from solubilizing.
[0151] To calculate the composite index in blocks, the relative amount of each block must be taken into account. To approximate this, the ratio between the soft EO and iPP duct is used. One can calculate the ratio of EP soft polymer to iPP hard polymer using Equation 2 of the mass balance of the total ethylene measured in the polymer. Alternatively, it can also be calculated from the mass balance of monomer and comonomer consumption during polymerization. Table 3 refers to the calculated ratio of iPP and EP present in the diblock copolymer for all series. The weight fraction of hard iPP and the weight fraction of soft EP are calculated using Equation 2 and it is assumed that the hard iPP does not contain any ethylene. The percentage by weight of ethylene of the soft EP is the amount of ethylene present in the xylene-soluble fraction. Table 3 - Block Composite Index Calculations for Examples B1 to AB3

[0152] For example, if an inventive iPP/EP polymer contains a total of 47% by weight of C2 and is prepared under the conditions to produce a soft EP polymer with 67% by weight of C2 and an iPP homopolymer containing zero of ethylene, the amount of mole EP and iPP duct will be 70% by weight and 30% by weight, respectively (calculated using Equations 3 and 4). If the percentage of EP is 70% by weight and that of iPP is 30% by weight, the relative ratio of the EP:iPP blocks can be expressed as 2.33:1.
[0153] Therefore, if a person skilled in the art were to perform a polymer extraction with xylene and recover 40% by weight of insolubles and 60% by weight of solubles, this would be an unexpected result and would lead to the conclusion that a fraction of the block copolymer inventiveness was present. If the ethylene content of the insoluble fraction is subsequently measured to be 25% by weight of C2, Equations 2 to 4 can be solved to account for this additional ethylene and result in 37.3% by weight of soft EP polymer. and 62.7% by weight of iPP hard polymer present in the insoluble fraction.
[0154] Since the insoluble fraction contains 37.3% by weight of EP copolymer, it would bind an additional 16% by weight of iPP polymer based on the EP:iPP block ratio of 2.33: 1. This leads to an estimated amount of diblocks in the insoluble fraction of 53.3% by weight. For the entire polymer (unfractionated), the composition is described as having 21.3% by weight of iPP/EP diblocks, 18.7% by weight of iPP polymer, and 60% by weight of EP polymer. . As the compositions of these polymers are new, the term block composite index (BCI) is defined herein as equal to the weight percentage of diblocks divided by 100% (i.e., weight fraction). The composite block index value can range from 0 to 1, where 1 would equal 100% inventive diblocks and zero would be for a material such as a traditional blend or random copolymer. For the example described above, the block composite index for the block composite is 0.213. For the insoluble fraction, the BCI is 0.533, and for the soluble fraction, the BCI is designated as zero.
[0155] Depending on the estimates made of the total polymer composition and the error in the analytical measurements that are used to estimate the composition of the hard and soft blocks, a relative error of 5 to 10% is possible in the computed value of the composite block index. Such estimates include the weight percent C2 in the hard block iPP measured from the melting point of DSC, analysis by NMR, or process conditions, the average weight percent C2 in the soft block estimated from the composition of the xylene solubles, or by NMR, or by soft block DSC melting point (if detected). But the global block composite index calculation is reasonably responsible for the unexpected amount of "additional" ethylene present in the insoluble fraction, the only way to have an EP copolymer present in the insoluble fraction, the EP polymer chain must bind to an iPP polymer block (or else it would have been extracted into the xylene-soluble fraction).
[0156] More specifically, Example H1 contains a total of 14.8% by weight of C2 and the percentage by weight of C2 in the solubles in xylene (H3) was measured to be 38.1% by weight (as a representation of composition of EP mole polymer) and an iPP homopolymer containing zero ethylene, the amount of EP mole and iPP hard is 61% by weight and 39% by weight, respectively (calculated using Equations 3 and 4). If the percentage of EP is 61% by weight and that of iPP is 39% by weight, the relative ratio of EP blocks:iPP can be expressed as 1.56:1.
[0157] After extraction of polymer H1 with xylene, 60.6% by weight of insoluble polymer (H2) and 39.4% by weight of soluble polymer (B3) are recovered. Subsequently, the insoluble fraction B2 is measured to have 4.4% by weight of C2, Equations 2 to 4 can be solved to account for this additional ethylene and result in 11.5% by weight of soft EP polymer and 88.5% by weight of iPP hard polymer.
[0158] Since the insoluble fraction contains 11.5% by weight of EP copolymer, it would bind an additional 7.35% by weight of iPP polymer based on the EP:iPP block ratio of 1, 56:1. This leads to an estimated amount of diblocks in the insoluble fraction of 29.6% by weight. For the entire polymer (unfractionated), the composition is described as having 18% by weight iPP/EP diblocks, 42.6% by weight iPP polymer, and 39.4% by weight EP polymer. . For example H1 described above, the block composite index for the block composite is 0.18. For the insoluble fraction (H2), the BCI is 0.29, and for the soluble fraction the BCI is designated by the value zero.
[0159] Table 3 and figure 6 show the block composite indices for series B1 to AB1. For series B1, C1, and D1, the BCI values are, respectively, 0.16, 0.17, and 0.22. For the associated xylene-insoluble fractions B2, C2, and D2, the BCI values are, respectively, 0.42, 0.34, and 0.35. For series F1, G1, and H1, the BCI values are, respectively, 0.10, 0.5, and 0.18. For the associated xylene-insoluble fractions, F2, G2, and H2 fractions, the BCI values are, respectively, 0.29, 0.29, and 0.29.
[0160] Table 3 and Figure 7 show for series V1, W1, X1 that increasing the propylene reactor conversion from 90 to 95% increases the BCI from 0.03 to 0.09 to result in BCI values of 0 .18, 0.24, and 0.25.
[0161] Table 3 and Figure 7 show that for series Z1, AA1, AB1, the increase in reactor temperature from 90 to 120°C resulted in BCI values of 0.12, 0.18, and 0.24 , respectively.
[0162] Dynamic-mechanical analysis
[0163] Figure 8 shows the dynamic-mechanical properties of samples B1 to D1; the values of G’ and tangent of delta against temperature are shown. As the amount of iPP increases, the G’ modulus increases and the high temperature plateau extends. Sample D1 shows that the modulus decreases with increasing temperature to up to about 140°C before softening completely after its melt transition.
[0164] For each sample, the delta tangent curve shows a characteristic Tg between -48 to -50°C for the ethylene/propylene copolymer and a second Tg at about 0°C for the isotactic polypropylene. Above 50°C, the delta tangent response remains constant until melting starts and the modulus rapidly decreases.
[0165] Figure 9 shows the dynamic-mechanical properties of samples F1 to H1; the values of G’ and tangent of delta against temperature are shown. Similar to the case of 65% by weight of C2, increasing the amount of iPP, the G' modulus increases and the high temperature plateau extends. Sample H1 shows that the modulus decreases with increasing temperature to up to about 140°C before softening completely after its melt transition.
[0166] For these examples, the delta tangent curves also show a characteristic Tg between -48 to -50°C for the ethylene/propylene copolymer and a second Tg at about 0°C relative to isotactic polypropylene. Above 50°C, the delta tangent response remains constant for samples G1 and H1 until melting starts and the modulus rapidly decreases. Morphology Discussion
[0167] The samples are analyzed by TEM to observe the influence of diblocks on the total morphology of iPP/EPR rubber. Figure 10 shows the TEM image of ProFax Ultra SG853 impact copolymer (Lyondell Basell Polyolefins) consisting of a continuous phase of isotactic PP and 17% by weight rubber phase, containing 58% by weight of C2 in the rubber.
[0168] The TEM micrograph shown at 5 μm scale, shows large EPR domains ranging from 2 to 5 μm.
[0169] At 1 μm magnification, the EPR domain has a heterogeneous distribution of ethylene and propylene composition as shown by the light and dark color domains present within the particle. This is a classic example of a dispersed morphology containing two phases (iPP and EP rubber) that are immiscible with each other.
[0170] Figure 11 shows TEM micrographs of compression-molded films from B1, C1, and D1, at scales of 2, 1, and 0.5 μ m. In complete contrast to the impact copolymer image, all three polymers show a finer dispersion of particles with very small domains. For B1, a continuous EPR phase is observed along with elongated PP domains of the order of 80-100 nm in width. For C1, a mixed continuity was observed between the iPP and EPR phases with domain sizes in the order of 200-250 nm. For D1, a continuous PP phase is observed along with spherical and some elongated EPR domains of size 150-300 nm.
[0171] Figure 12 shows TEM micrographs of F1, G1, and H1 compression-molded films at scales of 2, 1, and 0.5 μ m. In complete contrast to the impact copolymer image, all three polymers show a finer dispersion of particles with very small domains. For F1, a continuous phase of EPR is observed along with elongated PP domains of the order of 200-400 nm in width. For G1, a mixed continuity was observed between the iPP and EPR phases with domain sizes in the order of 200-300 nm. For H1, a continuous PP phase is observed along with spherical and some elongated EPR domains of size 150-300 nm.
[0172] It is surprising to observe such small and well-dispersed domains shown in these micrographs of polymers that have been compression molded from pellets. Typically to obtain fine morphology (not close to the scales shown here), specialized composition and extrusion histories are required. Even if size scales are approximated using blending, morphologies may not be stable; grain growth and phase agglomeration can occur with thermal aging, shown by the impact copolymer in which the rubber domains are elongated and some of them linked together by chains.
[0173] The morphology of the copolymer in diblocks was further investigated by examining the polymeric fractions obtained from the fractionation by xylene. As explained above, the insoluble fraction contains iPP/EP diblocks and free iPP homopolymer while the soluble fraction contains the non-crystallizable EP rubber.
[0174] Figure 13 shows TEM micrographs of the insoluble fractions of B1 and D1 and also the soluble fraction of B1. Notably, the morphology observed in the insoluble fraction is even finer and more distinct from that observed in the entire polymer. The insoluble fraction of B1 shows a mixture of spherical and spiral-like EPR domains, at the size scale of 50 nm in width. The insoluble fraction of D1 shows small spherical domains that are also about 50 nm in diameter. For reference, the xylene-soluble fraction of B1 shows the typical granular lamellar structure expected of an EP elastomer containing 65% by weight of C2. Again, the morphologies of the insoluble fractions are distinct and appear to be separated by microphases.
[0175] It is interesting to observe the TEM micrographs of the insoluble fraction of B1, figure 15, with those of a sPP/EP/sPP triblock containing 71% by weight of sPP, such as that shown in figure 7 of Macromolecules, volume 38 , no. 3, page 857, 2005. In this figure, the sPP/EP/sPP triblock was produced via anionic polymerization and the micrograph is an annealed film at 160°C for about a week. The sample was melt annealed for a total of 8 days - the first 4 days at 200°C to erase any previous thermal history and then the additional 4 days at a final temperature of 160°C. High vacuum ovens (< 10-7 mbar) were used to prevent oxidation degradation. Mold morphology was preserved by quickly quenching samples after annealing. The article's authors associated the phase-separated microstructure to hexagonally packed cylinders (figure 14). TPV formulations and mechanical properties Raw materials:
[0176] Table 4 shows the raw materials. NORDEL MG resin contains 28 parts carbon black to 100 parts EPDM elastomer. Carbon black adheres to the resin in the form of core-film morphology. Table 5 shows the composition and physical characteristics of all polymeric ingredients. Table 4. Materials
Table 5. Composition and material characteristics of polymeric ingredients.

[0177] Example 1 of TPV (continuous TPV process in twin screw extruder using NORDEL MG as the rubber phase). Preparation steps:
[0178] Process oil, EPDM resin, polypropylene powder, OCB resin, wax, and powder additives were combined in a 15 mm Coperion co-rotating twin screw extruder (TSE). Part of the process oil is fed into the second barrel section using a positive displacement sprocket pump and an injection valve that minimizes backflow. An appropriate amount of SP 1045 phenolic curing resin molten in 3000 g of process oil is slowly added at a minimum temperature of 90°C with stirring. More oil is injected into a barrel and the phenolic curing resin is melted into additional process oil. All oil streams are preheated using a jacketed sump and heat transfer lines. Low molecular weight volatile components are removed by devolatilization holes. The material is then cooled and pelletized using a row or underwater pelletizer at the end of the extruder.
[0179] The extruder has twelve barrel sections, resulting in a total length to diameter (L/D) ratio of 49. The feed system for this extrusion line has two loss-in-weight feeders. NORDEL MG resin pellets, wax and 1 percent process oil are pre-mixed in a plastic bag before adding to the main feed throat of the extruder using a K-Tron KCLQX3 single screw feeder. Powder additives are fed alone or pre-mixed with powdered polypropylene. Polypropylene powder is mixed with all other powder additives and tumble mixed into a plastic bag before measuring material using a K-Tron KCLKT20 twin screw feeder.
[0180] Process oil is added to the extruder using a Leistritz sprocket pump cart with two heat driven liquid feed systems.
[0181] A vacuum system is used to remove residual volatile melt components near the end of the extruder. Two ejection pots in series are loaded with dry ice and isopropyl alcohol to condense the volatile components. For composite pellets, polymer discharged from the extruder is cooled in a 10 foot long water bath and cut into cylinders with a Conair Model 304 row pelletizer. Discharge temperatures are measured using a hand held thermocouple probe placed directly into the melt stream.
[0182] Formulations of properties of NORDEL MG examples: Table 6

[0183] Table 6 shows the example formulations of TPV using NORDEL MG as the rubber phase. Examples include a control example, Comparative T1, which is prepared without OBC compatibilizers, and two inventive examples, Examples T4 and T5, of TPV prepared with 5% by weight of Examples B1 and C1, based on the total polymer base, as compatibilizers. Table 7 lists their key mechanical properties. A comparison of Example T4 with Example T1 shows that the addition of Example B1 resulted in a softer composition with a significant decrease in compression set at 70°C and 120°C while the tensile strength was preserved. Example T5 had similar hardness, tensile strength, elongation, and compression set at 70°C to Example T1, but showed improved compression set at 120°C. Table 7. Mechanical properties of TPV samples from the inventive examples and the comparative example.

[0184] Figure 15 shows images of AFM phases of Comparative Example T1 and Example T4. The darker phase corresponds to the crosslinked particles, and the lighter phases are polypropylene. The morphology of TPV's is typically a crosslinked rubber phase dispersed in a thermoplastic matrix. It can be seen that a finer morphology is achieved in the inventive example than in the comparative example, which demonstrates better compatibility between EPDM and the PP phase.
[0185] TPV Example 2 (Batch TPV process in internal mixer using NORDEL IP as the rubber phase):
[0186] Preparation steps:
[0187] EPDM (NORDEL IP 4570) was soaked with oil in a glass vessel at 50°C for at least 24 hours. Oil soaked EPDM elastomer, thermoplastic (polypropylene) and compatibilizer (OBC) were added to a Haake mixer bowl at 190°C and 35 rpm. Materials were mixed for 4 minutes at 75 rpm. The curing pack (ZnO, SnCl2 and SP 1045) phenolic resin was added to the molten mixture, and mixing continued for a further 3 minutes. Antioxidant was added, mixing continued for another 1 minute. The melt was removed from the internal mixer, and allowed to further mix in a 2-roll mill at 190°C. The melt passed through the blender and the resulting sheet was rolled into a cigar-shaped specimen before being placed lengthwise and passed through the rolling mill. The procedure was repeated 6 times, and then the sample was taken from the laminator as a sheet. The sheet from the laminator was preheated in a heat press (190°C) for two minutes at a pressure of 2000 psi. Then, the sheet was compression molded at 190°C at a pressure of 55,000 psi for 4 minutes and then cooled for 4 minutes at a pressure of 55,000 psi. This procedure produced good 1/6-inch and 1/8-inch thick test plates with no visible cracks. NORDEL IP formulations and properties:
[0188] Table 8 shows the formulations of numerous examples of TPV using NORDEL IP as the rubber phase. In each formulation, 75 pph of HYDROBRITE oil, 3 pph of SP 1045 phenolic resin, 6 pph of stannous chloride, 2 pph of KADOX 720 (zinc oxide) and 1 pph of IRGANOX 225 were added. The examples include two comparative examples. and 6 inventive examples of TPV prepared with Examples B1 and C1 at three different concentration levels. Examples C11 was a control example prepared without any compatibilizer. Examples C12 was a comparative example prepared with 6% by weight random ethylene/octene copolymer as compatibilizer. Example C17 was prepared with 2% by weight of Example B1 on a total polymeric basis. Example C09 was prepared with 6% by weight of Example B1 on a total polymeric basis. Example C18 was prepared with 10% by weight of Example B1 on a total polymeric basis. Example C06 was prepared with 2% by weight of Example C1 on a total polymeric basis. Example C08 was prepared with 6% by weight of Example C1 on a total polymeric basis. Example C01 was prepared with 10% by weight of Example C1 on a total polymeric basis. Table 8

[0189] Table 9 shows physical properties of the formulations given in Table 8. As can be seen, breaking strength, tensile strength and maximum elongation increased for Comparative Example C12 and for Inventive Examples C06, C08 and C01. However, only the inventive examples show significantly less compressive deformation, indicating better elastic recovery. Table 9

[0190] Table 10 shows another set of examples of TPV using NORDEL IP as the rubber phase and a high molecular weight PP as the thermoplastic phase. Examples include a control example, which was prepared without OBC compatibilizers, and 6 inventive TPV examples prepared with Examples B1 and C1 at three different levels. Example TM1 was a control example prepared without OBC compatibilizer. Examples C04, CO2 and C19 were prepared respectively with 2% by weight, 6% by weight and 10% by weight of Example B1 on a total polymeric basis. Examples C20, C16 and C05 were prepared respectively with 2% by weight, 6% by weight and 10% by weight of Example C1 on a total polymeric basis. Table 10. TPV inventive example formulations and TPV comparative examples

[0191] In each formulation, 75 pph of HYDROBRITE oil, 3 pph of phenolic resin SP 1045, 6 pph of stannous chloride, 2 pph of KADOX 720 (zinc oxide) and 1 pph of IRGANOX 225 were added. shows the mechanical properties of the TPV samples. A comparison of physical properties between Example C04 and Example TM1 shows, by adding 2% by weight of OBC, that a stiffer TPV with dramatically higher elongation, higher tensile strength and lower compression set was achieved. All other inventive examples with OBC's show similar effect to Example C04 with improvement of all properties. Table 11. Key mechanical properties of TPV samples from the Inventive Examples and the Comparative Example.

权利要求:
Claims (13)
[0001]
1. Thermoplastic vulcanizate, characterized in that it comprises or is obtained from a reagent mixture comprising: (a) a vulcanizable elastomer; (b) a thermoplastic polyolefin; (c) a cross-linking agent; and, (d) a composite in blocks; wherein the thermoplastic vulcanizate has a reduction in compression strain at 70°C of more than 5% when compared to a thermoplastic vulcanizate without (d), as measured according to ASTM D395 at 70°C, the block composite comprises a soft copolymer, a hard polymer and a block copolymer having a soft segment and a hard segment, the hard segment of the block copolymer having the same composition as the hard polymer of the block composite and the soft segment of the copolymer The block composite has the same composition as the soft copolymer of the block composite and the hard segment comprises 80% by weight to 100% by weight of propylene, and the block composite is present in an amount of 1% by weight to 30% by weight.
[0002]
2. Vulcanized, according to claim 1, characterized by the fact that (d) has a composite block index > 0.10.
[0003]
3. Vulcanized according to any one of claims 1 or 2, characterized in that the block composite comprises diblock copolymers having isotactic polypropylene blocks and ethylene/propylene blocks.
[0004]
4. Vulcanized according to claim 3, characterized in that the isotactic polypropylene blocks are present in an amount of 10% by weight to 90% by weight.
[0005]
5. Vulcanized according to claim 3, characterized in that the ethylene content of the ethylene/propylene blocks is 35% by weight to 70% by weight.
[0006]
6. Vulcanized according to any one of claims 1 to 5, characterized in that the composite in blocks is present in an amount from 1% by weight to 15% by weight.
[0007]
7. Vulcanized, according to any one of claims 1 to 6, characterized in that the melt flow rate of the composite in blocks, measured at 230°C and weight of 2.16 kg, is 0.1 dg /min at 50 dg/min as measured according to ASTM D 1238.
[0008]
8. Vulcanized according to any one of claims 1 to 7, characterized in that the vulcanizable elastomer is selected from the group consisting of EPDM, ethylene/α-olefins, olefinic block copolymers and block composites.
[0009]
9. Vulcanized according to any one of claims 1 to 8, characterized in that the thermoplastic polyolefin is selected from the group consisting of polyethylene, polypropylene homopolymers, polypropylene copolymers and block composites.
[0010]
10. Vulcanized according to claim 6, characterized in that the composite in blocks is present in an amount of 3% by weight to 10% by weight.
[0011]
11. Vulcanized, according to claim 7, characterized in that the melt flow rate of the composite in blocks is from 0.1 dg/min to 30 dg/min.
[0012]
12. Vulcanized according to claim 11, characterized in that the melt flow rate of the composite in blocks is from 1 dg/min to 10 dg/min.
[0013]
13. Article, characterized in that it comprises the thermoplastic vulcanizate as defined in any one of claims 1 to 12.

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同族专利:

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公开号 | 公开日

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BR112012007275A2|2020-08-11|

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法律状态:
2020-08-25| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-09-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-02-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 01/10/2010, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |

优先权:

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申请号 | 申请日 | 专利标题

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US24814709P| true| 2009-10-02|2009-10-02|

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US61/248,147|2009-10-02|

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PCT/US2010/051160|WO2011041699A1|2009-10-02|2010-10-01|Block composites in thermoplastic vulcanizate applications|

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