FORMULATED COMPOSITION, MODIFIED COMPOSITION FOR IMPACT AND ARTICLE

专利摘要:
formulated composition, impact modified composition and article embodiments of the invention provide block composites and their use as impact modifiers.
公开号:BR112012007272B1
申请号:R112012007272-2
申请日:2010-10-01
公开日:2021-08-10
发明作者:Edmund M. Carnahan；Collin Lipishan；Kim L. Walton；Gary R. Marchand；Benjamin C. Poon；Phillip D. Hustad；Brian A. Jazdezewski；Didem Oner-Deliormanli
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 modified polypropylene for impact. Invention history
[0002] Many different materials and polymers have been added to polymeric compositions in an attempt to improve or maintain the impact strength of the compositions while improving other properties. For example, US Patent No. 5,118,573 (Hikasa et al.), incorporated herein by reference, discloses thermoplastic elastomer compositions, having low hardness and excellent flexibility and mechanical properties, consisting essentially of a dilute olefinic copolymer rubber blend. in oil and an olefinic plastic. Olefin plastic is polypropylene or a copolymer of polypropylene and an alpha-olefin of 2 or more carbon atoms. Modern Plastics Encyclopedia/89, published mid-October 1988, Volume 65, Number 11, p. 110-117, the disclosure which is incorporated herein by reference, also discusses the use of various thermoplastic elastomers (TPEs) useful for impact modification. These include: elastomeric alloy TPEs, engineering TPEs, olefinic TPEs (also known as thermoplastic olefins or TPOs), polyurethane TPEs, and styrenic TPEs.
[0003] Thermoplastic olefins (TPOs) are often produced from an elastomeric material such as random copolymers based on ethylene, ethylene/propylene rubber (EPM) or ethylene/propylene/diene monomer terpolymer (EPDM) and a material stiffer such as isotactic polypropylene. Other materials or components can be added to the formulation depending on the application, including oil, fillers, and crosslinking agents. TPOs are often characterized by a balance of stiffness (modulus) and low temperature impact, good chemical resistance, and wide usage temperatures. Because of features such as these, TPOs are used in many applications, including automotive instrument panels and wire and cable components, rigid packaging, molded articles, instrument panels, and the like.
[0004] Block copolymers comprise sequences ("blocks") of the same monomeric unit, covalently linked to sequences of different types. The blocks can be connected in a variety of ways, such as structures in AB diblocks and in ABA triblocks, where A represents a block and B represents a different block. In a multiblock copolymer, A and B may be connected in a number of different ways and may be repeated multiple times. It may further comprise additional blocks of different types. star multiblocks (in which all the blocks bind to the same atom or chemical moiety) or comb polymers where the B blocks bind at one end to a main chain of A.
[0005] A block copolymer is created when two or more polymer molecules of different chemical compositions covalently bond to each other. While a wide variety of block copolymer architectures are possible, a number of block copolymers involve covalently bonding hard plastic blocks, which are substantially crystalline or glassy, to elastomeric blocks forming thermoplastic elastomers. Other block copolymers are also possible, such as rubber/rubber (elastomer/elastomer), glass-glass, and glass/crystalline block copolymers.
[0006] One method to prepare block copolymers is to produce a "living polymer". Unlike typical Ziegler-Natta polymerization processes, live polymerization processes involve only initiation and propagation steps and essentially lack terminal side reactions. This allows the synthesis of desired predetermined and well-controlled structures in a block copolymer. A polymer created in a "living" system can have a narrow or extremely narrow molecular weight distribution and be essentially monodisperse (i.e., the essentially single molecular weight distribution). Living catalytic systems are characterized by an initiation rate that is on the order of or exceeds the propagation rate, and the absence of transfer or termination reactions. Furthermore, these catalytic systems are characterized by the presence of a single type of active site. To produce a high yield of block copolymer in a polymerization process, such catalysts must exhibit vivid characteristics to a substantial extent.
[0007] Polypropylene (PP) homopolymers or PP random copolymers provide desirable rigidity and transparency for many applications, but may have unsatisfactory impact properties due to the high glass transition temperature (Tg) (0°C for homopolymer PP, HPP). To overcome this deficiency, PP homopolymer is blended with PP copolymers and/or elastomers to improve its toughness, but often at the expense of its transparency and modulus.
[0008] Ideally, the elastomer or compatibilizer should promote or produce elastomeric particles that are of sufficiently small scale to improve impact performance without adversely affecting the modulus of the mixture.
[0009] One improvement would be to develop a propylene-containing elastomer that exhibits a sufficiently low Tg for the required application and improves impact performance without adversely affecting its transparency. Ideally, the modulus and clarity of the PP/PP-containing elastomer blend product should be comparable to that of the PP homopolymer. Invention Summary
[0010] Formulated compositions have now been found which have this combination of good low temperature impact performance and modulus. The invention provides a formulated composition comprising: (a) polypropylene; (b) a compatibilizer, preferably comprising a composite and blocks; and (c) optionally, an elastomer, wherein the composition exhibits an Izod strength in kJ/m2 as measured by ASTM D256 or ISO 180 at 0°C or 23°C that is at least 10% greater than that of the composition without (b ); and exhibits a flexural modulus that is less than 10% reduced as compared to that of the composition without (b). Brief description of the drawings
[0011] Figure 1 shows the DSC melting curve for Example B1;
[0012] Figure 2 shows the DSC melting curve for Example F1;
[0013] Figure 3 compares the TREF profiles of Examples B1, C1 and D1;
[0014] Figure 4 shows DSC curves from Examples B2 and B3;
[0015] Figure 5 shows DSC curves of Examples F2 and F3;
[0016] Figure 6 shows composite index in blocks for Examples B1, F1, C1, H1, D1 and G1;
[0017] Figure 7 shows composite index in blocks for Examples B1, V1, Z1, C1, W1, AA1, D1, X1, and AB1;
[0018] Figure 8 shows the dynamic-mechanical analysis of Examples B1, C1 and D1;
[0019] Figure 9 shows the dynamic-mechanical analysis of Examples F1, G1 and H1;
[0020] Figure 10 shows a PROFAX ULTRA SG853 polypropylene impact copolymer TEM micrograph at 5 μ m and 1 μ m scales;
[0021] Figure 11 shows TEM micrographs of Examples B1, C1 and D1 at scales of 1 μ m and 0.5 μ m;
[0022] Figure 12 shows TEM micrographs of Examples F1, G1 and H1 at scales of 2 μ m, 1 μ m and 0.5 μ m;
[0023] Figure 13 shows TEM micrographs of Examples B2, D2 and B3 at 0.5 μ m and 0.2 μ m scales;
[0024] Figure 14 shows Example B2 at scales of 1 μ m and 200 nm;
[0025] Figure 15 shows TEM comparisons of modified PROFAX ULTRA SG853 with Examples D2 and C2;
[0026] Figure 16 shows TEM comparisons of modified PROFAX ULTRA SG853 with Example B2;
[0027] Figure 17 shows TEM comparisons of modified PROFAX ULTRA SG853 with Comparative Example A;
[0028] Figure 18 shows stress/strain curves of unmodified and modified PROFAX ULTRA SG853 with Comparative Example A, Example B2 and Example D2;
[0029] Figure 19 shows stress/strain curves of unmodified and modified PROFAX ULTRA SG853 with Comparative Example A, Example B2 and Example D2 of 0-2% strain;
[0030] Figure 20 shows the particle size distribution graphs for unmodified and modified PROFAX ULTRA SG853 with varying amounts of Examples B2 and D2;
[0031] Figure 21 shows transmittance, transparency and opacity for INSPIRE D221 unmodified and modified with Examples H2 and F2, and with Comparative Examples A and B, and for PROFAX ULTRA SG853;
[0032] Figure 22 shows TEM comparisons of unmodified and modified PROFAX ULTRA SG853 and INSPIRE D221 with Comparative Examples A and B and with Examples F2 and H2;
[0033] Figure 23 shows opacity and transparency as a function of average rubber domain size;
[0034] Figure 24 shows stress/strain curves of unmodified and modified INSPIRE D221 with Comparative Examples A and B and with Examples F2 and H2;
[0035] Figure 25 shows modulus and tangent of delta (tg Δ) for
[0036] INSPIRE D221 unmodified and modified with Comparative Examples A and B and with Examples F2 and H2;
[0037] Figure 26 shows Izod impact against temperature for Comparative Example C and Inventive Examples B1 and D1;
[0038] Figure 26 shows Izod impact against temperature for Comparative Example C and Inventive Examples B1 and D1;
[0039] Figure 27 shows Izod impact against temperature for Comparative Example D and Inventive Examples B1 and D1;
[0040] Figure 28 shows Izod impact against temperature for Comparative Example C and Comparative Example A;
[0041] Figure 29 shows Izod impact against temperature for Comparative Example D and Comparative Example A;
[0042] Figure 30 shows High Temperature Liquid Chromatography Separation of Example D1;
[0043] Figure 31 shows High Temperature Liquid Chromatography Separation of Example D2;
[0044] Figure 32 shows High Temperature Liquid Chromatography Separation of Example D3;
[0045] Figure 33 shows Charpy impact strength of inventive and comparative blends; and
[0046] Figure 34 shows TEM micrographs at resolutions of 1 μ m, 0.2 μ m, and 100 nm for inventive and comparative mixtures. Description of embodiments of the invention
[0047] Definitions
[0048] 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.
[0049] 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.
[0050] 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 contained in the same 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.
[0051] 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).
[0052] 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.
[0053] "Hard" segments refer to very crystalline blocks of polymerized units in which the monomer is present in an amount greater than 90 percent, preferably greater than 93 percent by weight, and more preferably greater than 95 mole percent, and most preferably greater than 98 mole percent. In other words, the comonomer content in the hard segments is most preferably less than 2 mole percent, more preferably less than 5 mole percent, and preferably less than 7 mole percent, and less than 10 mole percent. 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% and less than 90 mol%, preferably greater than 20 mol% and less than 80 mol%, and most preferably greater than 33 mol% and less than 75 mol%.
[0054] The block composite polymers of the invention are preferably produced 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 distinct process conditions in two or more reactors operating under steady state polymerization conditions, or in two or more zones operating under continuous flow polymerization conditions.
[0055] 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 (ie 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, chain exchange agent is used as a way of extending the life of a polymer chain such that a substantial fraction of the polymer chain exits 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.
[0056] The following mathematical treatment of the resulting polymers is based on the theoretically derived parameters that are 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 WH Ray, J. Macromol. Sci., Macromol. Chem, C8, 1 (1972) and in AE Hamielec and JF MacGregor, “Polymer Reaction Engineering”, KH Reichert and W. Geisler, Eds., Hanser, Munich, 1983. Chain exchange in a given reactor results in the formation of a single polymeric block, whereas transfer of the chain exchange agent terminated polymer 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. Xi[n]= (l-pi)pi(nl) very likely distribution of block lengths
numerical average block length 1 - pi
[0057] 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:

[0058] for each catalyst i= {1, 2, ...}, where,
[0059] Rp[i]= Local rate of monomer consumption per catalyst i, (mol/L/time)
[0060] Rt = Total rate of chain termination and transfer for catalyst i, (mol/L/time), and
[0061] Ri[i]= Local rate of chain transfer with inactive polymer, (mol/L/time). 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 catalyst concentration i, [Ci], as follows:

[0062] 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:

[0063] 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:

[0064] 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
[0065] 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 propylene and at least one copolymerizable comonomer having 2 or 4 to 20 carbon atoms, or 1-butene and at least one copolymerizable comonomer having 2 or 5 to 20 carbon atoms, 4-methyl-1-pentene and at least one different copolymerizable comonomer having 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-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. 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
[0066] Catalysts and catalyst precursors suitable for use in the present invention include metal complexes such as disclosed in WO 2005/090426, in particular those disclosed beginning on page 20, line 30 through page 53, line 20, which is incorporated herein 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.
[0067] Particularly preferred catalysts are those of the following formula:

[0068] where R20 is an aromatic group or inertly substituted aromatic group having from 5 to 20 atoms not counting 3 hydrogen atoms, or a polyvalent derivative thereof; T 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.
[0069] 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.
[0070] 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.
[0071] 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.
[0072] Other suitable metal complexes are those of the formula:

[0073] 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
[0076] Using the present process, new block composite 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.
[0077] One can measure the comonomer content in the resulting block composite polymers using any appropriate technique, preferring techniques based on nuclear magnetic resonance (NMR) spectroscopy. 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.
[0078] 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), preferably from 20 to 80 percent of relatively hard or crystalline segments and from 80 to 20 percent of amorphous or relatively amorphous segments (soft segments), most preferably from 30 to 70 percent of relatively hard or crystalline segments and from 70 to 30 percent of amorphous or relatively amorphous segments. amorphous (soft segments). Within the soft segments, the mole percent of comonomer may range from 10 to 90 mole percent, preferably from 20 to 80 mole percent, and most preferably from 33 to 75 mole percent. In the case where the comonomer is ethylene, it is preferably present in an amount of from 10 to 90 mole percent, more preferably from 20 to 80 mole percent, and most preferably from 33 to 75 mole percent. Preferably, the copolymers comprise hard segments which are 90 mol% to 100 mol% propylene. The hard segments may be greater than 90 mol%, preferably greater than 93 mol%, more preferably greater than 95 mol%, and most preferably greater than 98 mol% propylene. Such hard segments have corresponding melting points which are greater than or equal to 80°C, preferably greater than or equal to 100°C, more preferably greater than or equal to 115°C, and most preferably greater than or equal to 120°C.
[0079] Composite block polymers can be differentiated from 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 index and block composite index, as described below; of a physical blend by characteristics such as block index, composite block index, better tensile strength, improved fracture toughness, finer morphology, improved optics, and better impact strength at lower temperature; of block copolymers prepared by sequential addition of monomer by molecular weight distribution, rheology, shear decrease, rheology ratio, and by the fact that there is block polydispersion.
[0080] 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 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.
[0082] 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.
[0083] 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.
[0085] The polymers of the invention may be diluted in oil with 5 to about 95 percent, preferably 10 to 60 percent, more preferably 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.
[0086] If the polymers of the invention contain a pendant diene thermomer, in embodiments of the invention any crosslinking agent which is capable of curing EPDM may be used. Suitable curing agents include, but are not limited to, phenolic resins, peroxides, azides, aldehyde/amine reaction products, vinyl silane grafted moieties, hydrosilation, 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.
[0087] An elastomer composition according to embodiments of the invention may also 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.
[0088] Thermoplastic compositions according to embodiments of the invention may also contain organic or inorganic fillers or other additives such as starch, talc, calcium carbonate, glass fibers, glass beads, hollow glass spheres, polymeric fibers (including nylon, rayon, cotton, polyester, and polyaramid), natural organic fibers including wood fiber and cotton, metallic fibers, particles or flakes, layered expandable silicates, phosphates or carbonates, such as clays, mica, silica, alumina, aluminosilicates or aluminophosphates, carbon cokes, carbon fibers, nanoparticles including nanotubes and montmorillonite, wollastonite, graphite, zeolites, and ceramics such as silicon carbide, silicon nitride or titania. Silane-based coupling agents, and other coupling agents can also be employed for better charge binding.
[0089] 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 such as calcium stearate or zinc stearate, poly(alcohols) including glycols, poly(alcohols) ethers, including ether glycols, polyesters, including polyglycol esters, and metal salts, especially Group 1 or 2 or zinc, salt derivatives thereof; plasticizers such as dialkyl dicarboxylic acid esters; antidegradants; softeners; waxes such as polyethylene wax, oxidized polyethylene wax, and montanic acid ester wax; and pigments such as titanium dioxide and iron oxide.
[0090] For conventional TPO applications, carbon black is often the additive of choice for UV absorption and stabilizing properties. Representative examples of carbon black include ASTM N110, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991. These carbon blacks have iodine absorptions ranging from 9 to 145 g/kg and average pore volumes ranging from 10 to 150 cm3/100 g. Generally, carbon blacks with smaller particle sizes are used, to the extent that cost considerations allow. For many such applications the present block composites and mixtures thereof require little or no carbon black, thus allowing considerable design freedom to include alternative pigments or not to include any pigments at all.
[0091] Compositions including thermoplastic mixtures according to embodiments of the invention may also contain antiozonants or antioxidants which are known to commonly trained rubber chemists. Antiozonants can be physical protectants such as wax materials that sit on the surface and protect the part from oxygen or ozone, or they can be chemical protectants that react with oxygen or ozone. Suitable chemical protectants include styrene phenols, butyl octyl phenol, di(dimethyl-benzyl) butyl phenol, p-phenylenediamines, butylated reaction products of p-cresol and di-cyclopentadiene (DCPD), polyphenolic antioxidants, hydroquinone derivatives, quinoline, diphenylene antioxidants, thioester antioxidants, and mixtures thereof. Some representative trade names of such products are: WINGSTAY™ S antioxidant, POLYSTAY™ 100 antioxidant, POLYSTAY™ 100 AZ antioxidant, POLYSTAY™ 200 antioxidant, WINGSTAY™ L antioxidant, WINGSTAY™ LHLS antioxidant, WINGSTAY™ K antioxidant, WINGSTAY™ 29 antioxidant, WINGSTAY™ SN-1 antioxidant, and IRGANOX™ antioxidants. In some applications, the antioxidants and antiozonants used will preferably be non-migratory and non-discoloring.
[0092] To provide additional stability against UV radiation, hindered amine light stabilizers (HALS) or UV absorbers can also be used. Suitable examples include TINUVIN™ 123, TINUVIN™ 144, TINUVIN™ 622, TINUVIN™ 765, TINUVIN™ 770, and TINUVIN™ 780, obtainable from Ciba Specialty Chemicals, and CHEMISORB™ T944, obtainable from Cytex Plastics, Huston, Texas, USA. One can additionally include a Lewis acid with a HALS compound in order to achieve superior surface quality, as disclosed in U.S. Patent No. 6,051,681.
[0093] For some compositions, additional mixing processes can be employed to pre-disperse the antioxidants, antiozonants, carbon black, UV absorbers, and/or light stabilizers to form a masterbatch, and subsequently form polymeric mixtures. with the same.
[0094] Compositions modified for impact
[0095] Impact-modified compositions consist of a matrix polymer hardened via blending with an elastomeric composition. In one embodiment, the matrix polymer is a polypropylene. Any polypropylene known to a person of ordinary skill in the art can be used to prepare the polymer blends disclosed herein. Non-limiting examples of polypropylene include low density polypropylene (LDPP), high density polypropylene (HDPP), high melt strength polypropylene (HMS-PP), high impact polypropylene (HIPP), isotactic polypropylene (iPP), polypropylene syndiotactic (sPP) and the like, and combinations thereof.
[0096] The amount of polypropylene in the polymer mixture can be from about 0.5 to about 99% by weight, from about 10 to about 90% by weight, from about 20 to about 80% by weight, from about 30 to about 70% by weight, from about 5 to about 50% by weight, from about 50 to about 95% by weight, from about 10 to about 50% by weight, or from about 50 to about 90% by weight of the total weight of the polymer blend. In one embodiment, the amount of polypropylene in the polymer blend is about 50%, 60%, 70% or 80% of the total weight of the polymer blend.
[0097] Generally speaking, polypropylene is in the isotactic form of homopolymer polypropylene, although other forms of polypropylene (eg syndiotactic polypropylene or atactic polypropylene) may also be used. In the TPO formulations disclosed herein, polypropylene impact copolymers (for example, those in which a secondary copolymerization step reacting ethylene with propylene) and random copolymers (also reactor-modified and usually containing 1, 5-7% by weight of ethylene copolymerized with propylene A complete discussion of various polypropylene polymers is contained in Modern Plastics Encyclopedia/89, published mid-October 1988, volume 65, number 11, pp. 86-92, the entire disclosure of which is hereby incorporated by reference. The molecular weight and therefore the melt flow rate of polypropylene for use in the present invention varies depending on the application. The melt flow rate for polypropylene useful herein is generally of from about 0.1 gram/10 min (g/10 min) to about 200 g/10 min, preferably from about 0.5 g/10 min to about 150 g/10 min, and especially from about 4 g/10 min at about 100 g/10 min. The polypropylene polymer can be a homopolymer of polypropylene, or it can be a random copolymer or even an impact copolymer (which already contains a rubber phase). Examples of such polypropylene polymers include: impact copolymers, PROFAX ULTRA SG583 from Lyondell Basell Polyolefins or INSPIRE 114 from The Dow Chemical Company; homopolymer, H110N or D221.00 from The Dow Chemical Company; copolymer, 6D43 from The Dow Chemical Company; random propylene/ethylene elastomers and plastomers such as VISTAMAXX™ (manufactured by ExxonMobil), and VERSIFY™ (from The Dow Chemical Company).
[0098] The elastomeric composition used to harden the polypropylene can be any elastomer with sufficient polypropylene compatibility and sufficiently low glass transition temperature to impart impact toughness to the polypropylene. In one embodiment, the elastomer is a randomly copolymerized ethylene/α-olefin copolymer.
[0099] The random ethylene/α-olefin copolymers used as the toughness elastomer in the embodiments of the invention are preferably ethylene copolymers with at least one α-olefin of C3-C20. Copolymers of ethylene and a C3-C20 α-olefin are preferred. Non-limiting examples of such copolymers are linear homogeneously branched copolymers such as EXACT from ExxonMobil and TAFMER from Mitsui, and substantially linear homogeneously branched copolymers such as ENGAGE copolymers from The Dow Chemical Company. The copolymers can further comprise C4-C18 diolefin and/or alkenyl benzene. Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or unconjugated dienes, polyenes, alkenyl benzenes, etc. Examples of such comonomers include C3-C20 α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Especially preferred are: 1-butene and 1-octene. Other suitable monomers include styrene, halogen or alkyl substituted styrenes, vinyl benzo cyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics (for example, cyclopentene, cyclohexene and cyclooctene).
[0100] Although ethylene/α-olefin copolymers are preferred polymers, other ethylene/olefin polymers can also be used. As used herein, the term "olefin" refers to a family of compounds based on unsaturated hydrocarbons with at least one carbon-carbon double bond. Depending on the selection of catalysts, any olefin may be used in embodiments of the invention. Preferably, suitable olefins are: C3-C20 aliphatic and aromatic compounds containing vinyl unsaturation, as well as cyclic compounds such as cyclobutene, cyclopentene, di-cyclopentadiene, and norbornene, including, but not limited to, 5- and 5-substituted norbornene 6 with C1-C20 cyclohydrocarbyl or hydrocarbyl groups. Also included are mixtures of such olefins as well as mixtures of such olefins with C4-C40 diolefin compounds.
[0101] Examples of olefinic monomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene , 4-vinyl-cyclohexene, vinyl-cyclohexane, norbornadiene, ethylidene norbornene, cyclopentene, cyclohexene, di-cyclopentadiene, cyclooctene, C4-C40 dienes including, but not limited to, 1.3 -butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C4-C40 α-olefins, and the like. In certain embodiments, the α-olefin is propylene, 1-butene, 1-hexene, 1-pentene, 1-octene, or a combination thereof. In embodiments of the invention, although any hydrocarbon potentially containing vinyl group may be used, practical problems such as monomer availability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer may become more problematic when the molecular weight of the monomer is too high.
[0102] The polymerization processes described herein are well suited for producing olefinic polymers comprising monovinylidene aromatic monomers including styrene, o-methyl-styrene, p-methyl-styrene, t-butyl-styrene, and the like. In particular, interpolymers comprising ethylene and styrene can be prepared following the teachings herein. Optionally, copolymers comprising ethylene, styrene and a C3-C20 α-olefin can be prepared, optionally comprising a C4-C20 diene, having improved properties.
[0103] Unconjugated dienes monomers can be straight chain, branched or cyclic hydrocarbon dienes having 6 to 15 carbon atoms. Examples of suitable unconjugated dienes include, but are not limited to, straight chain acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, acyclic dienes of branched chain such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene and isomeric mixtures of dihydromyricene and dihydrocinene, alicyclic dienes of a ring single dienes such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and alicyclic bridged or fused multiple-ring dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene, alkenyl norbornenes, alkylidene, cycloalkenyl and cycloalkylidene, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5 -isopropylidene-2-norbornene, 5-(4-cyclopentyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-norbornene, and norbornadiene. Of the dienes typically used to prepare EPDMs, particularly preferred dienes are: 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2 -norbornene (MNB), and di-cyclopentadiene (DCPD). Especially preferred dienes are: 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).
[0104] One class of desirable elastomers that may be prepared in accordance with embodiments of the invention are ethylene elastomers, a C3-C20 α-olefin, especially propylene, and optionally one or more 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, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. A particularly preferred α-olefin is propylene. Polymers containing propylene are generally referred to in the art as EP or EPDM polymers. Suitable dienes for use in the preparation of such polymers, especially polymers of the EPDM type 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.
[0105] In another embodiment, ethylene/α-olefin block interpolymers can be used as a hardening elastomer. The ethylene/α-olefin interpolymer comprises polymerized units of ethylene and α-olefin, and is characterized by an average block index greater than zero and up to about 1.0 and a greater molecular weight distribution, Mw/Mn, that about 1.3. In another aspect, the invention relates to an ethylene/α-olefin interpolymer comprising polymerized units of ethylene and α-olefin, and is characterized by an average block index greater than zero but less than 0.5 and a distribution of molecular weight, Mw/Mn, greater than about 1.3. Preferably, the interpolymer is a linear multiblock copolymer with at least three blocks. Also preferably, the ethylene content in the interpolymer is at least about 50 mole percent. These interpolymers are described in and can be made via polymerization techniques illustrated, for example, in U.S. Patent No. 7,608,668 B2, which is incorporated herein by reference. Another type of block ethylene/α-olefin interpolymers that can be used are those referred to as "mesophase separated". These mesodomains can take the form of spheres, cylinders, lamellae, or other morphologies known for block copolymer. The narrowest dimension of a domain, such as perpendicular to the plane of lamellae, is generally greater than about 40 nm in the mesophase separate block copolymers of the present invention. Examples of such interpolymers can be found, for example, in international publications nos. WO/2009/097560, WO/2009/097565, WO/2009/097525, WO/2009/097529, and WO/2009/097535, all of which here incorporated by reference.
[0106] In another embodiment, selectively hydrogenated block copolymers can be used as a hardening elastomer including block copolymers of conjugated dienes and vinyl aromatic hydrocarbons that exhibit elastomeric properties and that have 1.2-microstructure contents before fence hydrogenation from 7% to about 100%. Such block copolymers can be multiblock copolymers of varying structures containing various ratios of conjugated dienes to vinyl aromatic hydrocarbons including those containing up to about 60 weight percent vinyl aromatic hydrocarbon. Therefore, block copolymers that are linear or radial, symmetrical or asymmetrical and that have the structures represented by the formulas ABA, AB-AB, BA, BAB, BABA, (AB)0,1,2...BA can be used and the like, in which A is a block polymeric of a vinyl aromatic hydrocarbon or a block of conical conjugated diene/vinyl aromatic hydrocarbon copolymer and B is a block polymeric of a conjugated diene.
[0107] Styrenic block copolymers can be produced by any well known copolymerization or ionic block polymerization procedures including the well known sequential monomer addition techniques, incremental monomer addition techniques or coupling techniques such as illustrated, for example , in US Patent Nos. 3,251,905, 3,390,207, and 4,219,627, all of which are incorporated herein by reference. As is well known in the block copolymer art, tapered copolymer blocks can be incorporated into the multiblock copolymer by copolymerizing a mixture of conjugated diene and vinyl aromatic hydrocarbon monomers using the difference in their copolymerization reactivity rates. Several patents describe the preparation of multiblock copolymers containing conical blocks of copolymer including U.S. Patent Nos. 3,251,905, 3,265,765, 3,639,521, and 4,208,356, the disclosures of which are incorporated herein by reference.
[0108] Preferably, the impact-modified compositions of the invention have a weight average elastomer particle size of less than 3.5 µm, preferably less than 2.5 µm, and more preferably less than 2.2 µm.
[0109] Preferably, the impact-modified compositions of the invention have a weight-average elastomer particle size that is more than 20% smaller than that of the impact-modified composition of polypropylene and elastomer alone, more preferably more than 35% smaller than that of the impact-modified composition of polypropylene and elastomer alone, and most preferably more than 50% less than that of the impact-modified composition of polypropylene and elastomer alone.
[0110] Preferably, too, the impact-modified compositions have a ductile-brittle transition temperature of at least 2°C lower, more preferably at least 5°C lower, even more preferably at least 10°C lower, and most preferably at least 20°C lower as compared to the unmodified impact copolymer.
[0111] When the composite block comprises polypropylene hard blocks and ethylene/propylene soft blocks, it is compatible with both the iPP matrix and the elastomer (disperse) phase of an impact copolymer. During blending with the propylene-containing block copolymer, an unexpected and significant reduction in domain size of both the PP and the elastomer phase is observed.
[0112] Preferably, the compatibilizer of the formulated composition comprises a composite in blocks. The block composite may be present in an amount of from 0.50% by weight to 20% by weight, preferably from 0.5% by weight to 15% by weight and more preferably in an amount from 1% by weight to 10% by weight .
[0113] High clarity impact modified polypropylene can be obtained by mixing PP homopolymer or random copolymer and the block composite or by mixing PP homopolymer or random copolymer, an appropriately selected hardener elastomer and the block composite of the invention. The resulting blends produce smaller, more discrete rubber domains than a simple PP/elastomer blend. When rubber domain sizes are smaller than visible light wavelengths (400-700 nm), less light scattering will occur, and the polymer mixture will remain clear. Since the block copolymer of the block composite contains compatibilized rubber, this new impact-modified PP exhibits improved toughness at low temperatures, and has clarity similar to PP homopolymer. Similarly, a hardening elastomer that has been classified via the block composite to a particle size smaller than visible light wavelengths will also scatter less light, and the polymer will remain clear. Likewise, hardening elastomers that have a refractive index combined with a matrix polypropylene will produce improved hardening efficiency in PP when blended with the block composite. For example, a blended refractive index blend of isotactic PP homopolymer with ethylene/1-octene elastomers of density 0.895-0.905 g/cm3 exhibits improved impact hardening when combined with the composite block.
[0114] This new impact-modified PP has the potential use to produce high-clarity PP for freezer packaging (film or rigid packaging) such as clear ice cream containers that are currently not obtainable.
[0115] Methods for preparing mixed compositions
[0116] The blended compositions of the present invention are prepared by any convenient method, including dry blending of the individual components and blending under subsequent melting, either directly in the extruder used to manufacture the finished article (eg, the automotive part), or blending under melting in a separate extruder (eg a Banbury mixer). Typically, blends are prepared by kneading or mixing the respective components at a temperature around or above the melting point temperature of one or both of the components. For most multiblock copolymers this temperature can be above 130°C, most generally above 145°C, and most preferably above 150°C. Typical equipment for mixing or kneading polymer that is capable of reaching the desired temperatures and melt plasticizing the mixture can be employed. These include mills, kneaders, extruders (both single and twin screw), Banbury mixers, calenders and the like. Mixing sequence and method may depend on the final composition. A combination of continuous mixers and Banbury batch mixers can also be employed, such as a Banbury mixer followed by a mill mixer followed by an extruder.
[0117] General article manufacturing
[0118] The compositions of this invention may be employed to fabricate parts, sheets or other article of manufacture, using any conventional extrusion, calendering, blow molding (eg, that described in Modern Plastics Encyclopedia/89, published mid-October 1988, volume 65, number 11, pp. 217-218, "Extrusion-Blow Molding", the disclosure of which is hereby incorporated by reference), injection molding (eg, that described in Modern Plastics Encyclopedia/89, published in mid-October 1988, volume 65, number 11, pp. 264-268, "Introduction to Injection Molding", and on pages 270-271, the disclosures which are incorporated herein by reference), thermoforming or foaming processes . Specific examples of such processes include sheet extrusion, profile extrusion, and injection molding. Such processes can produce articles or products having smooth or curved surfaces. The components of the composition can be fed into the process either pre-mixed or, in a preferred embodiment, the components can be fed directly into process equipment, such as a converting extruder, such that the composition forms in the process of extrusion, calendering, blow molding, foaming or thermoforming. The compositions can also be blended with another polymer prior to manufacturing an article. Such mixing can occur by any of a variety of conventional techniques, one of which is dry mixing pellets of the thermoplastic elastomer compositions of this invention with pellets of another polymer.
[0119] In addition to sheet extrusion processes, the compositions can also be used in extrusion/blow molding processes to form blow molded articles. Furthermore, the inventive compositions can be extruded to form various profiles. The inventive compositions can also be used to form calendered articles.
[0120] A partial, far from complete, list of items that can be manufactured with the compositions of the invention includes automobile body parts, such as instrument panels, instrument panel foam, fuel tanks, automotive containers, banner bumpers, body side moldings, automotive structural framework, internal columns, internal trims, air gates, air ducts, grilles and wheel covers, and non-automotive applications such as polymeric films, polymeric sheets, foams, tubing, fibers, linings, trash cans, storage or packaging containers, including freezer cabinets. Of course, one skilled in the art can also combine polymers to advantageously use refractive index to improve or maintain clarity of end-use items such as freezer cabinets.
[0121] Additional items include garden furniture, lawn mowers and other garden appliance parts, refrigerator and other household appliance parts, trailer (recreational vehicle) parts, golf cart parts, grocery cart parts, desk friezes, toys and boat parts. The compositions can also be used in roofing applications such as roofing articles. The compositions can also be used in civil construction applications such as plastic boards, balconies, external walls, boards, soffit, and other articles for interior and exterior decoration of buildings. The compositions can also be used in the manufacture of shoe components. The compositions can also be used in the manufacture of components for electronic devices that fit in the hands such as cell phones, personal digital players, personal digital assistants, etc. The expert technician can quickly grow this list without undue experimentation. Additional articles include extrusion profiles. Polymerization Methods
[0122] Suitable processes useful for producing 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 incorporated herein by reference. In particular, the polymerization is desirably carried out as a continuous polymerization, preferably a continuous solution polymerization, in which catalyst components, and optionally solvent, adjuvants, scavengers, and polymerization aids are continuously supplied to one or more reactors or zones and the polymeric product 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.
[0123] 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).
[0124] 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.
[0125] 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 catalytic composition before, simultaneously with, or after combining the catalyst with the monomers to be polymerized and any additional reaction diluent.
[0126] 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.
[0127] 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 C4-40 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 .
[0128] 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 least at 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.
[0129] The resulting polymeric product is recovered by eliminating volatile components from the reaction mixture such as residual monomers or diluents 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.
[0130] 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.
[0131] 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. Analytical Test Methods
[0132] The overall composition of each resin is determined by DSC, NMR, GPC, DMS, and TEM morphology. Additionally, xylene fractionation or HTLC fractionation can be used to estimate block copolymer production. Differential Scanning Calorimetry (DSC)
[0133] 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
[0134] 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. Data acquisition parameters
[0135] 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)
[0136] 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.
[0137] 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).
[0138] Polypropylene equivalent molecular weight calculations are performed using Viscotek's TriSEC software version 3.0. Fractionation by fast temperature gradient elution (F-TREF)
[0139] 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)
[0140] 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.
[0141] 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. and IR were detectors built into GPVC2000. The IR5 detector was provided by PolymerChar, Valencia, Spain.
[0142] Columns: The D1 column 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).
[0143] 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.
[0144] 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.
[0145] 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.
[0146] After step 8, the flow rate and mobile phase composition were the same as the initial conditions of the operating gradient.
[0147] 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.
[0148] 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 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.
[0149] The percentage by weight of isolated PP is measured as the area that corresponds to the hard block composition based on the isolated peak and retention volume determined by a composition calibration curve. Analysis by fractionation of solubles in xylene
[0150] 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.
[0151] Alternatively, if the crystallization temperature of the soft block polymer solution is greater than room temperature, the fractionation step can be performed at a temperature of 10-20°C above the soft block crystallization temperature, but below of the crystallization temperature 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 mc (obtainable from PolymerChar, Valencia, Spain). Dynamic-mechanical spectroscopy (DMS)
[0152] 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 electronic microscopy
[0153] Polymer films are prepared by compression molding followed by rapid 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.
[0154] The compression molded films are rectified 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.
[0155] 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. Atomic force microscopy
[0156] The samples were scanned with digital instruments NanoScope V, dimension 3100 AFM in tap mode with phase detection. The software version is 5.30r3. Mikro Mash tips were used in all experiments. Tip parameters: L= 230 μm, tip radius= 5-10 nm, spring constant= 45 N/m, Fo= 170 kHz. Shunt ratio: 0.80. Free amplitude setpoint voltage was set to 3.0 V. Image post-processing was performed using SPIP image analysis software version 5.04. Sample preparation
[0157] Composition by twin screw extrusion and preparation of Examples:
[0158] In this study, the TPO compounds were prepared by mixing Coperion 25 mm WP-25 ZSK co-rotating twin screw extruder melt at a speed of 500 rpm. Polypropylene, elastomer, and additional block composite were fed into the extruder using individual loss/weight feeders. The antioxidant additive was tumble mixed with the elastomer prior to compounding. Talc was fed through a side arm feeder which was introduced into the third zone of the extruder barrel and vacuum was used during extrusion to remove volatiles. The compounding extruder rate was 0.38 kg/minute (50 lb/hour) with a melt temperature of about 220°C (430°F). The extruded row was water cooled and cut into pellets. Composition by Haake Brabender and Preparation of Examples:
The blends were prepared in a Haake batch blender using a 50 or 200 g canister. The components were mixed at 230°C at 50 rpm for fifteen to twenty minutes. During that time, the melt torque was monitored to ensure that it reached a steady state after melting the components. Compression Molding Conditions
[0160] Polymeric films and samples (unless otherwise specified) are prepared by compression molding followed by rapid quenching using a Carver press (such as model #4095-4PR1001R). Polymer is pre-melted at 190°C for 1 minute at 1000 psi and then pressed for 2 minutes at 5000 psi and then tempered between cooled plates (15-20°C) for 2 minutes. injection molding
[0161] Test samples are injection molded using a Toyo injection molding machine and universal insertion tools which allow different insert to be used to prepare dog bone of traction or dart impact test discs with thickness instrument about 0.32 cm (0.125 inch) and about 10 cm (4 inches) in diameter. For instrument dart impact specimens, the injection rate used is 28 cm3/s. The fusing temperature is controlled at approximately 200°C (400°F) and the tool temperature at approximately 37°C (100°F). All samples are conditioned in the laboratory at room temperature for at least seven days prior to testing.
[0162] In recognition that the properties of polypropylene-based systems change with the development of crystallinity, the following aging was used before testing the specimens:
[0163] IZOD Notched and Charpy Test: Notch for Izod testing to be done within 1 to 6 hours after molding and etching for 40 hours at 73°F and 50% relative humidity prior to testing.
[0164] Flexural Modulus Test: After conditioning for 40 hours at 73°F and 50% relative humidity.
[0165] Dart impact with instrument: 7 days aging time of TPO specimen. Physical properties test Density
[0166] Prepare samples for density measurement according to ASTM D1928. Measurements are made within 1 hour of sample pressing using ASTM D792, method B. Melt Flow Rate and Melt Index
[0167] Measure the melt flow rate or I2 of the samples using ASTM D 1238, condition 230°C, 2.16 kg. The melt index is measured using ASTM D 1238, condition 190°C, 2.16 kg. Measure the melt flow rate or I10 of the samples using ASTM D 1238, condition 230°C, 10 kg. The melt index is measured using ASTM D 1238, condition 190°C, 10 kg. Traction test
[0168] Measure stress-strain behavior in uniaxial stress using ASTM D638. Injection molded tensile specimens are used unless stated otherwise. Samples are stretched with an Instron at 50 mm/min at 23°C. Tensile strength and elongation at break are reported for an average of 5 specimens. bending modulus
[0169] Measure 1 or 2 percent bending and bending modulus and rope modulus in accordance with ASTM D-790. Samples are prepared by injection molding draw bars (approximately 165 mm x 19 mm x 3 mm) which are conditioned for at least 40 hours at room temperature. Load under thermal distortion
[0170] Thermal distortion temperature (HDT) is a measure of polymer resistance to distortion under a given load at elevated temperatures. The common ASTM test is ASTM D 648 and a load of 0.455 MPa was used. Injected tensile samples were used for the test. The deflection temperature is the temperature at which the test bar, loaded to the specified bending stress, deflects 0.25 mm (0.010 inch). optical properties
[0171] Opacity (haze) was measured according to ASTM D1003 using 0.5 mm compression molded films. Clarity was measured in accordance with ASTM D1746 using 0.5 mm compression molded films. Polymeric films are prepared by compression molding followed by rapid quenching. Gloss is measured at 60° using a Gardner BYK gloss meter 60° micro-gloss specified in ASTM D-2457. Charpy Impact Resistance
[0172] Notched Charpy impact strength was measured according to ASTM E23. Notched Charpy impact tests were performed on molded ASTM tensile specimens. The samples were notched using a notching device to produce a notch depth of (10.16 ± 0.05) mm in accordance with ASTM E23. Five specimens of each sample were tested using ASTM E23 at room temperature, 23°C, 0°C, -10°C, -20°C, and —30°C. IZOD impact resistance
[0173] Notched Izod impact tests were performed on injection molded ASTM specimens cut from drawbars having dimensions of 62mm x 19mm x 3.175mm. The samples were notched using a notching device to produce a notch depth of (10.16 ± 0.05) mm in accordance with ASTM D256. Five specimens from each sample were tested using ASTM D256 at room temperature, 23°C, 0°C, -10°C, -20°C, and —30°C. Dart impact resistance with instrument
[0174] The instrument dart impact was determined in accordance with ASTM D3763. Injection molded 4” disc specimens from each sample were tested at room temperature, 23°C, 0°C, -10°C, -20°C, and —30°C. A 0.5 inch diameter hemispherical dart was used in an MTS 819 high rate test system equipped with GT 793 bending test system software. diameter and 0.125 inch thick were subjected to test temperature in a commercial box freezer with an accuracy of 2°C. Equilibrium time in the box freezer was a minimum of 4 hours. The specimen discs were placed in the center with a 3-inch diameter opening. The clamping frame was mounted in a Vemco environmental chamber. The specimen clamped on the fixed dart was moved at a constant speed of 6.7 m/s. The total energy absorbed by the specimen during the impact was recorded. Failed disks were also visually inspected and classified as a brittle or ductile failure. The average impact energy for five specimens is recorded. Examples general examples
[0175] Catalyst-1 ([[rel-2',2"'-[(1R,2R)-1,2-cyclohexanediyl bis(methylene oxy-KO)]bis[3-(9H-carbazol-9) -yl)-5-methyl[1,1'-biphenyl]-2-olate-KO]](2-)dimethylhafnium) and co-catalyst 1, a mixture of methyl di(C14-18 alkyl) salts ) ammonium borate tetrakis(penta-phenyl fluorine), prepares by reaction of a long-chain trialkylamine (ARMEEN™ M2HT, obtainable from Akzo-Nobel, Inc.), HCl and Li[B(C6F5)4], substantially such as disclosed in USP 5,919,983, Example 2, are purchased from Boulder Scientific and used without further purification.
[0176] CSA-1 (diethyl zinc or DEZ) and modified methyl aluminoxane (MMAO) were purchased from Akzo Nobel and 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.
[0177] 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).
[0178] 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.
[0179] Examples A1 through AB1 are carried out 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
[0180] 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 1A. To prepare sample B1, the contents of the 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
[0181] 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.

[0182] §- Only products from the 1st reactor. Table 1B Second process conditions for producing copolymers in diblocks B1-D1, F1-H1, V1-X1, Z1-AB1.

[0184] §- Only products from the 1st reactor. Preparation of fractional samples
[0185] 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.
[0186] 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).
[0187] 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.
[0188] 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.
[0189] 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).
[0190] 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. Table 2 - Analytical summary of Examples B1-AB1 and fractions

[0192] 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.
[0193] Figures 4 and 5 show the corresponding DSC curves of the fractions of B2, B3 and F2, F3. 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.
[0194] 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.
[0195] 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
[0196] 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.
[0197] 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. % by weight of total C2 = winsoluble (% by weight of insoluble C2 ) + w soluble (% by weight of soluble C2 ) Equation 1
[0198] Applying equations 2 to 4, it is calculated the amount of soft block (providing the source of extra ethylene) present in the insoluble fraction. 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. % by weight of total or insoluble C2 in xylene = hard wiPP (% by weight of C2iPP) + soft wEP (% by weight of soft C2EP) Equation 2

[0199] 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.
[0200] 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

[0202] 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.
[0203] 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.
[0204] 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.
[0205] 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).
[0206] More specifically, Example H1 contains a total of 14.8% by weight of C2 and the percentage by weight of C2 in the xylene solubles (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.
[0207] 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.
[0208] 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.
[0209] 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.
[0210] 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.
[0211] 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. Dynamic-mechanical analysis
[0212] 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.
[0213] 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.
[0214] 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.
[0215] 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
[0216] 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.
[0217] The TEM micrograph shown at 5 μm scale, shows large EPR domains ranging from 2 to 5 μm.
[0218] 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.
[0219] 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.
[0220] 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.
[0221] It is surprising to see such small, 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.
[0222] The morphology of the copolymer in diblocks was further investigated by examining the polymer fractions obtained from xylene fractionation. As explained above, the insoluble fraction contains iPP/EP diblocks and free iPP homopolymer while the soluble fraction contains the non-crystallizable EP rubber.
[0223] 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.
[0224] 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).
[0225] Preferably, polypropylene, elastomer and block composite compositions show a reduction in particle size of the dispersed phase greater than 50% when compared to the particle size of the mixture of PP and elastomer alone, more preferably greater than 100 %. Preferably also, the compositions show a reduction in particle size to less than 0.5 µm, preferably to less than 300 nm, more preferably to less than 200 nm, and even more preferably to less than 100 nm. Modification studies for impact
[0226] For this study, the xylene-insoluble polymeric fractions of the relevant Examples were used in order to determine BCI present in the fractions. Table 3 shows the analytical properties of the xylene-insoluble fractions (XI) that were used in this study. ProFax Ultra SG853 (Lyondell Basell Polyolefins) impact copolymer (ICP) (MFR 55, 16.8% by weight EP rubber, 58% by weight C2 in EPR) was used as the major component in the blends. Comparative A is a random propylene/ethylene copolymer (MFR 2.15 wt% C2, density 0.863 g/ml, Tg -30°C). The inventive polymeric fractions B2 and D2 and Comparative A are added at the level of 2, 6, and 10% by weight, based on total polymer weight. The blends were prepared in a Haake Minilab II which is a recirculating twin screw extruder (TSE) with a capacity of 5 grams. The materials were mixed together at 190°C for 8 min. The samples were then subsequently compression molded and subjected to TEM imaging.
[0227] Figures 15 and 16 show a comparison of TEM images of ICP mixed with fraction D2 and fraction B2. Micrographs clearly show a continuous PP phase (light colored phase) and a dispersed rubber phase (dark color). When viewed with micrographs from left to right, it can be seen that the size of dispersion of the rubber domains dramatically decreases with increasing concentration of the D2 fraction or the B2 fraction.
[0228] Starting with the ICP alone, the rubber domains are approximately 5 μm in size and show evidence of coalescence and agglomeration. When increasing the concentration of Example D2 from 2 to 10%, the size of the rubber domains decreased to less than 1 µm. Micrographs clearly show that by increasing the amount of Example D2, the rubber size distribution becomes narrower, and the rubber particles disperse better and are more spherical with little evidence of agglomeration. Exceptionally, at the 1 μ m scale, a bimodal-sized population of rubber domains was observed, both micro domains (less than 100 nm) and macro domains (1-5 μ m). It is believed that domains size smaller than 100 nm can be attributed to the iPP/EP diblock while the larger domains are from the ICP. It is evident that the iPP/EP diblock is effective in matching the rubber domains of the ICP.
[0229] Comparing Examples D2 and B2, it appears that B2 is less effective in dispersing and reducing particle size. Although the effect is consistent with the reduction in the size of the rubber domains, there is some agglomeration and non-spherical domains even at the 10% level. The observed differences in effectiveness between Examples D2 and B2 suggest that the amount of iPP block present also contributes to the compatibilization. Example D2 contains nearly equal amounts of iPP and EP while Example B2 contains smaller amounts of iPP blocks (30% of the total length).
[0230] The observed reduction in particle size is consistent with the compatibilization of the PP matrix and rubber domains by the iPP/EP diblock. The iPP/EP diblock reduces the interfacial energy between two distinct phases and promotes particle disintegration and a finer equilibrium morphology.
[0231] Polymeric fractions of Examples D2 and B2 have a BCI of 0.35 and 0.42, with the balance being iPP homopolymer. Therefore, at the 10% addition level, the estimated amount of diblock added for Examples D2 and B2 is only 3.5 and 4.2%, respectively.
[0232] The fact that the morphology of the rubber dispersion is significantly affected at these low levels suggests that the diblock acts as a true compatibilizer and is ultra-efficient in rubber dispersion.
[0233] As a control for the observed results, a mixture of Comparative A with the ICP was also prepared. Figure 17 shows that Comparative A added at the 6% level may also have some influence on the observed rubber morphology. Some of the particles are reduced to the sub-micron level, but a mixture of large and small particles is still observed, as well as some agglomeration of the rubber domains. However, in addition to the reduction in the size of the rubber domains, the iPP matrix showed evidence of “dirty lamellae” which is defined as the intermixing of the P/E rubber domains and the PP matrix. This is seen with the darkened shape of the PP matrix; alternating light and dark regions on the micrograph suggest that the P/E domains are miscible with PP and result in plastification/weakening of the PP matrix. It could be predicted which modulus of this sample would be smaller when compared to the inventive samples.
[0234] Figures 18 and 19 show stress versus strain curves of microtensile test of some of the compression molded films. Figure 18 shows the complete curve to the final breaking point while Figure 19 shows the deformation in the initial region. All samples showed a high modulus indicative of their high PP content. At the 2% modulus, the ICP and the diblock blends are shown to have a similar modulus whereas the blend with Comparative A shows a slightly lower modulus.
[0235] Figure 20 compares particle size distributions of mixtures containing the ICO, Examples B2, C2 and D2 as well as Comparative A. Note that particle sizes are reported as equivalent circular diameters since mixed particles have elongated shapes. The ICP and 6% Comparative A blend both show broad particle size distributions with particles up to 6 μm. With the addition of D2 or B2, the particle size distribution becomes narrower with increasing amount of compatibilizer. For mixtures with D2 or B2, when the level of each compatibilizer increased, the population of large particles with sizes between 2 and 6 μm was reduced or eliminated. Comparing the mixtures with B2 against D2, D2 shows the most dramatic reduction in particle size distribution; the particles were reduced to less than 2 µm. There is also a high population of tiny particles that are below 100 nm, as evidenced by the high tip below 1 μm. This high tip is responsible for the nanodomains or tiny black specifications of iPP/EP block copolymers.
[0236] But based on these findings, one can only use 3-5% pure iPP/EP diblocks to match a PP/EP rubber blend. High Clarity Impact PP
[0237] The nanoscale size of the rubber domains for the inventive blends are unprecedented for a typical PP/elastomer blend and are smaller than visible light wavelengths (400-700 nm). Mixtures of 75% PP homopolymer (D221.00, MFR 35 hPP (The Dow Chemical Company)) and 25% xylene insoluble fractions were prepared containing iPP/EP diblocks and iPP homopolymer which were then tested for its optical and physical properties. For comparison, control blends were also included with Comparative B, an ethylene/octene elastomer (ENGAGE™ 8150 (The Dow Chemical Company), MI 0.5, density 0.868 g/cm3) and Comparative A. The Table 4 shows the properties of these polymers. Table 5 shows the properties of the diblock fractions, Examples F2 and H2.
[0238] The mixtures are prepared in a Haake Minilab II which is a recirculating TSE with a capacity of 5 grams and then compression molded into films for optical measurements, TEM morphology, tensile properties, and dynamic-mechanical analysis. The materials were mixed together at 190°C for 8 min. Table 4 - Properties of D221.00, Comparative B and Comparative A.
Table 5 – Fraction properties.

[0239] Table 6 and Figure 21 show measurements of transmittance, clarity, and opacity for PP films blended with Examples F2 and H2. PP homopolymer and PP/elastomer blends show similar light transmittance between 90-94%. The PP homopolymer exhibits a baseline of 78% clarity and 18% opacity. Notably, the blend with Example H2 exhibits 74% clarity and 18% opacity similar to those of the PP homopolymer. Mixing with Example F2 shows less clarity and opacity than H2, suggesting that better compatibilization is achieved with a diblock that has a composition closer to 50/50 iPP/EP. Blends containing Comparative A have similar clarity but greater opacity than PP homopolymer. Mixtures with Comparative B and with ICP had minimum clarity and maximum opacity. Table 6 - Optical properties of films containing PP/iPP-EP diblocks

[0240] Figure 22 shows the TEM micrographs of the mixtures in the 5 μ m, 1 μ m, and 0.5 μ m scales. Arranged from left to right, the samples are sorted according to increasing lightness and decreasing opacity. Micrographs clearly show that the size and dispersion of the rubber domains are related to the observed optical properties. The blend of PP homopolymer with Comparative B elastomer shows the presence of immiscible and incompatible phases. It is believed that due to the large rubber domain sizes observed (on the order of 5 μm), this film shows minimum clarity and maximum opacity. The blend with Example H2 shows maximum clarity and minimum opacity comparable to PP homopolymer alone. The morphology of this sample shows a very fine dispersion of rubber particles smaller than 100 nm in size. It is believed that because of their smaller size, they act as point sources for Rayleigh scattering that scatter light evenly without deteriorating the brightness and opacity of the PP matrix. The sizes of rubber domains in blends with Comparative B are on the order of 500-1000 nm. Figure 23 shows the relationship of rubber domain size and percentage opacity and percentage lightness of the films. As rubber domain sizes decrease, opacity decreases and film clarity increases. There appears to be a direct relationship between the size of the rubber domain and the observed optical properties. Preferably, the polypropylene and up to about 6% by weight elastomer and block composite compositions have an opacity measurement of less than 20% when measured on a 1 mm thick article.
[0241] Table 7 summarizes the properties of the mixtures. Comparing the 10% tensile modulus, the PP blends with Example H2 or F2 showed a similar modulus (within 10% limits) to the PP homopolymer itself. However, the blends with Comparative B or Comparative A showed tensile curves with elongation of up to 50%. Figure 25 shows the dynamic-mechanical behavior of the various mixtures. G' values at room temperature confirm the tensile test observations. Except for differences in modulus, G' of the samples decreased with increasing temperature up to 140°C which suggests the temperature resistance of the samples is dominated by the iPP homopolymer. An advantage of the inventive Examples which contain an amorphous EP soft block is a lower glass transition temperature when compared to PP homopolymer or even a propylene/ethylene elastomer. These blends have improved impact properties both at room temperature and at temperatures below ambient than PP homopolymer. In the past, the addition of elastomer reduced the modulus and clarity of polypropylene. To obtain clear films, it was necessary to combine the refractive indices of the materials instead of fundamentally reducing the sizes of rubber domains to avoid the scattering of visible light wavelengths. Table 7 - Properties of PP/iPP-EP blends.

[0242] The blends listed in Table 8 were prepared in a twin screw extruder and tested for their physical properties. The TPO blends contain 51.5 to 62% Profax Ultra SG853 (available from Lyondell Basell Polyolefins) which is an MFR 55 impact copolymer with a measured weight percentage of rubber of 17%. Table 8 shows the compositions of hard TPO compounds containing Profax Ultra SG853, Comparatives C and D, and JetFil 700C talc; Compounds TPO-4 to TPO-6 contain 5 and 15% inventive Example B1, Compounds TPO-11 to TPO-14 contain 5 and 15% inventive Example D1. For comparison, Compounds of TPO-1C and TPO-2C, and Compounds of TPO-7 through TPO-10 contain 1% and 3% of Comparative Example A. Comparative C is an ethylene/octene copolymer (ENGAGE™ 8200 (The The Dow Chemical Company), of MI 5.0, density 0.870 g/cm3 ). Comparative D is an ethylene/octene copolymer (ENGAGE™ 8180 (The Dow Chemical Company), MI 0.5, density 0.863 g/cm3 ). Each of the formulations also contains Comparative D or Comparative C elastomer.
[0243] For the compounds containing the inventive examples, the total amount of "active" compatibilizer can be calculated by multiplying the block composite index of the inventive example by the percentage by total weight that is added. For compounds 4 to 6, the inventive compatibilizer weight percentage is estimated to be 0.8 and 2.4% by weight. For compounds 11 to 14, the inventive compatibilizer weight percentage is estimated to be 1.1 and 3.3% by weight. For comparison, the comparative compatibilizer level (Example A) was added at 1 and 3% by weight.
[0244] Table 9 summarizes the MFR, and bending modulus, cord modulus, thermal distortion temperature, and gloss properties of compounds containing Profax Ultra SG853, Comparative C or Comparative D, and B1 or D1 or Comparative Example elastomer A. Table 8 - TPO formulations.
Table 9 - TPO Compound Properties.

[0246] Figure 26 shows the Izod impact energy against temperature for hard TPO compounds containing Inventive Examples B1 and D1 at the 5 and 15% level with Profax Ultra SG853 and Comparative C. Compounds contendi B1 and D1 show impact strength greatly improved at 0°C, -10°C, and -20°C. This indicates that the ductile-brittle fault transition temperature is significantly lower than the comparative compound containing Comparative C. The data show that the impact strength is higher at sub-ambient temperatures for 15% level of B1 and D1 than the level of 5% of B1 and D1. This indicates that the ductile-brittle transition temperature is lower at the 15% level of B1 and D1 than at the 5% level of B1 and D1. Preferably, the compositions have an Izod strength in kJ/m2 measured by ASTM D256 or ISO 180 at 0°C or 23°C that is at least 10% greater than that of the composition without the inventive examples; and exhibit a flexural modulus that is less than 10% reduced as compared to a composition without the inventive examples.
[0247] Figure 27 shows the Izod impact energy against temperature for hard TPO compounds containing inventive examples B1 and D1 at levels of 5 and 15% with Profax Ultra SG853 and Comparative D. Compounds containing B1 and D1 show impact strength greatly improved at 0°C, -10°C, and -20°C. This indicates that the ductile-brittle fault transition temperature is significantly lower than comparative compound containing Comparative D and even lower than in the previous case with Comparative C. The data show that the impact strength is higher at sub-ambient temperatures for the level 15% of B1 and D1 than for the 5% level of B1 and D1. This indicates that the ductile-brittle transition temperature is lower at the 15% level of B1 and D1 than at the 5% level of B1 and D1.
[0248] Figure 28 shows the Izod impact energy against temperature for hard TPO compounds containing 1 and 3% Comparative Example A with Profax Ultra SG853 and Comparative D. The compounds with Comparative Example A showed lower impact strength than 25°C than the compound containing Comparative C. The data show that the ductile-brittle transition temperature was unaffected or worsened with the addition of Comparative Example A.
[0249] Tables 10 and 11 show the impact test performance at 25°C, 0°C, -10°C, -20°C and —30°C when tested by IZOD, Charpy and instrument dart methods . The general trend of impact energy measured by instrument dart method and Charpy is consistent with the IZOD method, showing that compounds containing Inventive Examples B1 and D1 with either Comparative C or Comparative D showed a significant improvement in impact strength at low temperature. Preferably the compositions demonstrate an improvement in impact strength as measured by Izod or Charpy of 10% over the composition without the inventive block composite examples.
[0250] In all cases, the addition of the inventive example significantly improved the impact strength at low temperature. The results are surprising since the percentage by weight of inventive compatibilizer added is between 0.8 and 1.1 wt% for B1 and between 2.4 and 3.3 wt% for D1. This dramatic effect observed at these low levels of compatibilizer suggests that these agents are very effective in compatibilizing the polypropylene and elastomer (ethylene/propylene rubber, and BD Comparatives) present in these compounds. Table 10
Table 11
High Temperature Liquid Chromatography
[0252] Figure 30 shows the HTLC chromatogram of Example D1; the separation of polymer by weight fraction against elution volume is shown. The chromatogram shows a peak eluting between 1.3 mL and 2 mL that corresponds to isotactic polypropylene or a propylene-rich species when the percentage by weight of PP indicates that it is measured by infrared composition; this one is similar in composition to the hard block. The area for this peak is 28.1% by weight. The polymer eluting from 2 ml to 4.5 ml corresponds to the diblock polymer and the ethylene rich polymer which is similar in composition to the soft block.
[0253] Figure 31 shows the HTLC chromatogram of Example D2; the separation of polymer by weight fraction against elution volume is shown. The chromatogram shows a very small polymer between 1.3 ml and 2 ml which indicates low or non-isotactic polypropylene or a species rich in propylene present. The area for this peak is less than 0.1% by weight. The polymer eluting from 2 ml to 4.5 ml corresponds to the ethylene rich polymer which is similar in composition to the soft block.
[0254] Figure 32 shows the HTLC chromatogram of Example D3; the separation of polymer by weight fraction against elution volume is shown. The chromatogram shows a peak eluting between 1.3 mL and 2 mL that corresponds to isotactic polypropylene or a propylene-rich species when the percentage by weight of PP indicates that it is measured by infrared composition; this one is similar in composition to the hard block. The area for this peak is 28.1% by weight. The polymer eluting from 2 ml to 4.5 ml corresponds to the diblock polymer and the ethylene rich polymer which is similar in composition to the soft block. Description of Examples BB1-HH1
[0255] Examples BB1-HH1 were prepared similarly to A1 to AB1 as described in Tables 12A and 12B. Individual reactor conditions were modified to control the lengths and compositions of the diblocks as described below. A catalyst similar to that of Examples A1 to AB1 is used. CSA-1, a similar MMAO cocatalyst, and solvent as in Examples A1 through AB1 are used. All examples have an iPP hard block. Series BB1 through GG1 have a semi-crystalline ethylene/propylene soft block containing 60-65% by weight of C2 while HH1 has an amorphous ethylene/propylene soft block containing 40% by weight of C2. BB1 has an iPP hardblock weight percentage of 30% by weight. CC1, DD1, EE1 have a weight percentage of iPP hard blocks around 60% by weight. FF1, GG1, and HH1 have a weight percentage of iPP hard blocks around 50% by weight. Examples BB1 through HH1 were produced in the presence of hydrogen in the first and second reactors. MMAO was added only in the first reactor. CSA was added in reactor 1 and the flux ranged from 5.6 to 15.0 g/h depending on the MFR of the polymer produced. Tables 13 and 14 show the analytical properties and estimated block composite index for Examples BB1 through HH1. Table 12A. First reactor process conditions for producing BB1 to HH1 diblock copolymers.
Table 12B. Second reactor process conditions for producing BB1 to HH1 diblock copolymers.
Table 13 - Analytical Summary of Examples BB1 to HH1
Table 14 - Block Composite Index Calculations for Examples BB1 to FF1
Elastomer Particle Stability in Molten State
[0257] The following materials were prepared as described in Table 15. The compositions were prepared using a Werner & Pfleiderer 25mm full self-cleaning mesh twin screw extruder. In this study, two types of composite spindle configurations were used. One was a high-shear mixing spindle that contains two kneading sections and 5 distributive mixing sections along the length of the spindle. The second spindle configuration was a soft mixing spindle that had a kneading section and 1 distributive mixing section along the length of the spindle. The composition conditions used are shown in Table 16. The feed rates in table 16 show the setpoint and actual feed rates for each component. Feeder 1 was used to feed the polypropylene resin (D221.00) and feeder 2 was used to feed the rubber (Comparative D and Inventive Example CC1). The combined materials were extruded into rows, quenched with water, and cut. in pellets. Table 15 - Compound formulations
Table 16 - Composition conditions used to prepare the formulated compounds.

[0258] The composite pellets were then fed into an 80 ton Arburg injection molding machine where tensile specimens in the shape of dog bone of standard type ASTM D-638 were prepared. In order to assess the effectiveness of the diblocks as compatibilizers, the injection molding experiment was carried out in such a way that the compound was melted and kept in the molten state in front of the plasticizing spindle in the injection molding barrel, also called a damper, by an extended period of time. This was accomplished by increasing the molding dose as shown in Table 17, where the cycle is increased by a factor of 2 and 3. Thus, the material was kept in the molten state in injection molding for 1 cycle, then it was injection molded in the drawbar test body. The material was held in a molten state in injection molding for 1 + 2 cycles, and then injection molded into the drawbar specimen body. Subsequently, the materials that were kept in the molten state in the injection molding machine for 1 + 2 + 3 cycles, were then molded into drawbar specimens. Table 17 - Injection molding conditions for drawbar specimen

[0260] The resulting morphology of these drawbar specimens was determined using atomic force in derivation mode. The micrograph obtained is then digitized and the weighted average rubber particle size is determined and reported here as the weighted average equivalent rubber particle size diameter, also defined herein as the weight average rubber particle size. The analysis was performed at three separate locations in the core of the drawbar specimen and the reported value was the weighted average rubber particle size of these three locations. The results are summarized in Table 18. Inventive MS-2 achieved a small rubber particle size using the lightweight spindle design. Its size (2.85 μm) was also maintained with respect to the hot melt impregnation time a longer time (during 2 cycles). For Comparative MS-1C, using a high shear mixing spindle, the rubber particle size obtained showed a size increase with respect to the time interval of impregnation in the molten state in 2 cycles, where it appeared to reach a particle size balance rubber of about 5.2 μm. Similarly, using a light mixing spindle, the rubber particle size almost immediately approached the equilibrium rubber particle size. Table 18 - Weighted average rubber particle size of film as a function of hot soak time.

[0262] Table 19 shows the notched Izod impact strength of these specimens as a function of various hot soak times. As noted, the Izod impact strength correlates with the weighted average rubber particle size. The inventive composition MS-2 exhibited ductile Izod impact at room temperature in all process treatments while the comparative composition MS-1C exhibited brittle impact at room temperature in all process treatments. Table 19 - Notched Izod Impact Resistance
Modified blends for high clarity impact
[0264] The blends listed in Table 20 were prepared in a twin screw extruder and tested for their flexural modulus, optical properties, and impact strength. The blends contain from 5.6 to 6.8% by weight of impact modifier added to an MFR 50 PP (R7021-50NA, obtainable from The Dow Chemical Company). Comparative Examples HC-1C and HC-2C use KRATON G1643M (obtainable from Kraton Polymers, USA) and ENGAGE™ 8402 (obtainable from The Dow Chemical Company) as impact modifiers at a level of 6%. Inventive examples HC-3 and HC-4 use either BB1 or CC1 alone or in a mixture with ENGAGE™ 8402 also at a level around 6%.
[0265] Table 21 shows the properties of the mixtures shown in Table 20. The 1% flexural modulus test of the examples shows that the inventive examples HC-3, HC-4, HC-5, and HC-6 have modulus 10% larger than the KRATON G1643M. Comparing the optical properties of clarity, opacity, and transmittance, all mixtures had similar values, except for examples HC-3 and HC-4 which contain 6% diblock BB1 and CC1 alone as an impact modifier.
[0266] Comparison of the impact properties of blends with BB1 and CC1 diblocks alone as impact modifier shows that CC1 diblock has at 23°C an IZOD impact strength greater than Comparative Example HC-2C (with ENGAGE™ 8402) . Despite CC1 having a higher percentage by weight of hard blocks and longer block lengths of hard blocks, it demonstrated better impact and optical properties than BB1.
[0267] Comparing the properties of the mixtures of Examples HC-5 and HC-6 with those of the comparative KRATON G1643M control, the mixtures with 50% BB1 and CC1 with ENGAGE™ 8402 as the impact modifier resulted in higher flexural modulus, similar optics, and similar impact properties at 23°C and 0°C. In fact, Example HC-5 contains 5.6% by weight of the impact modifying polymers which is 0.4% by weight less than the comparative examples. This suggests that properties similar to or better than those of comparative controls can be achieved. Table 20 - Modified Mixtures for High Clarity Impact
Table 21 - Mixture properties
Effect of MFR of inventive diblocks on impact properties of TPO blends
[0268] The blends listed in Table 22 were prepared in a twin screw extruder and tested for their flexural modulus and impact strength. The blends contain 70% Profax Ultra SG853 polypropylene impact copolymer (available from Lyondell Basell Polyolefins) and 20% an impact modifier, and 10% JetFil 700C talc. The control blend contains ENGAGE™ 8180 copolymer alone as the impact modifier while the inventive examples contained a blend of 40% of the inventive diblocks (CC1, DD1, EE1) and 60% of ENGAGE™ 8180. Table 23 shows the properties of the mixtures. Comparative Example TPO-15C has an MFR of 22.3, a rope modulus of 1400 MPa and Charpy impact strength of 7.1 and 6.7 measured at 23°C and 0°C, respectively. All inventive examples TPO-16, TPO-17 and TPO-18 exhibit similar modulus and up to 5% greater than that of the comparative example. All inventive examples exhibit significantly greater Charpy impact strength than the comparative control; 100% to 500% improvements in impact strength are shown at 23°C. Inventive Examples EE1, DD1, and CC1 illustrate the effect of diblock MFR on impact properties. The CC1 diblock has an MFR of 1.7 and when used as an impact modifier in the mixture shows an impact strength at 23°C of 51 kJ/m2. The DD1 diblock has an MFR of 8 and when used as an impact modifier in the mixture shows an impact strength at 23°C of 19.8 kJ/m2. The EE1 diblock has an MFR of 35 and when used as an impact modifier in the mixture shows an impact strength at 23°C of 16.2 kJ/m2. In general, these data show that inventive diblocks can have a significant improvement in impact strength of these blends, however, inventive diblocks with an MFR less than 8 have the maximum improvement. Table 22 - Mixtures for TPO
Table 23 - Effect of MFR of the inventive diblock on impact properties of TPO blends.
Impact modifier compatibility of a PP impact copolymer with MFR greater than 100
[0269] The blends listed in Table 24 were prepared in a twin screw extruder and tested for their flexural modulus and impact strength. The blends contain 91-100% Profax Ultra SC973 (obtainable from Lyondell Basell Polyolefins) which is an impact copolymer of MFR 105 with a measured weight percentage of rubber of 15%. MFR 105 impact copolymer was blended and compatibilized with 3, 6, and 9% inventive example FF1. The properties of the compatibilized blends are compared to those of Profax Ultra SC973 which was compounded alone in the extruder with the same antioxidant level as the inventive blends.
[0270] Table 25 shows the properties of the mixtures in Table 24. The inventive examples HFIM-1, HFIM-2, and HFIM-3 show that with increasing diblock level from 0 to 9%, the IZOD impact strength at 23°C and 0°C it increased dramatically. Compared to the comparative example, at 23°C, the impact strength was improved by 34%, 70%, and 90% with the addition of 3%, 6%, and 90% of the inventive diblock, respectively. Table 24 - Mixtures
Table 25 - Properties
Effect of diblock soft block composition on impact properties of TPO blends
[0271] The blends listed in Table 26 were prepared in a twin screw extruder and tested for their flexural modulus and impact strength. TPO blends contain 59 to 62% Profax Ultra SG853 (available from Lyondell Basell Polyolefins) which is an MFR 55 impact copolymer with a measured weight percentage of rubber of 17%. Comparative and inventive examples have been modified for impact with an amorphous random ethylene/propylene copolymer which has been polymerized with a metallocene catalyst. The mixes also contain 20% JetFil talc. The inventive examples TPO-20, TPO-21, AND TPO-22 show the effect of adding 7.5% inventive diblocks GG1, HH1, and a 50/50% by weight mixture of GG1 and HH1, respectively. Table 27 shows the properties of the blends in Table 26. Compared to the comparative blend without any compatibilizer, the inventive blends showed a decrease in modulus of less than 6%. However, very impressively, Figure 33 shows that Charpy impact strength dramatically improves with the addition of the inventive diblock. At 23°C and 0°C, the impact strength of the inventive blends is 30-35% greater than that of the comparative blend. At -10°C, the blend with inventive HH1 diblock shows a 140% improvement over that of the comparative blend. It is understood that the observed decrease in impact strength between 23°C and -30°C is due to differences in the ductile-brittle transition temperatures of the individual mixtures; in these examples, when compared to the control mixture, the addition of the inventive diblock compatibilizer results in a decrease in the ductile-brittle transition temperature of at least 5 to 15°C. Table 26
Table 27 - Impact properties of TPO mixtures with diblocks of different compositions
Modified properties for impact of ethylene/butene rubber in TPO blends
[0273] The blends listed in Table 28 were prepared in a twin screw extruder and tested for their melt flow, flexural modulus and impact strength. Blends contain 57 to 62% Profax Ultra SG853 polypropylene impact copolymer (available from Lyondell Basell Polyolefins) and 12.4 to 17.5% of an ethylene/butene elastomer, ENGAGE™ 7467 (available from The Dow Chemical Company, MI = 1.2, density = 0.862 g/cm 3 , and 30% JetFil 700C talc. The control blend contains ENGAGE™ 7467 alone as the impact modifier while the inventive example contains a blend of 10% diblock CC1 and 12.4% ENGAGE™ 7467. The total basis weight of the ethylene/alpha-olefin elastomer present in the comparative mixture and the inventive mixture is 28% and 26%, respectively. This includes the amount of ethylene/propylene rubber from the impact copolymer, the ethylene/butene rubber added, and the ethylene/propylene rubber from the soft block of the inventive diblock. Table 29 shows the properties of the blends in Table 28. Comparing the modulus of the comparative blend to the modulus of the inventive blend, a slight decrease in modulus, a decrease of less than 6%, was observed. Comparing the impact strength of Charpy comparative blend and the inventive blend, the inventive blend shows greater impact strength at all temperatures tested (23°C to -20°C). At 0°C, the inventive blend has 200% greater impact strength than the comparative blend. The observed decrease in impact strength between 23°C and -20°C is believed to occur due to differences in the ductile-brittle transition temperatures of the individual blends; in this example, when compared to the control mixture, the addition of the inventive diblock compatibilizer results in a decrease in the ductile-brittle transition temperature of at least 10 to 15°C. Table 28 - Mixtures
Table 29 - Modified properties for impact of ethylene/butene rubber in TPO blends
SEBS Compatibility
[0275] The mixtures listed in Table 30 were prepared using a Haake Brabender. 1 mm compression molded films were then prepared for morphology analysis by transmission electron microscopy. The comparative blend, SEBS 1, contains 80% polypropylene H110N (homopolymer of MFR=1, obtainable from The Dow Chemical Company) and 20% SEBS KRATON™ G1643M (obtainable from Kraton Polymers, USA). The inventive blend, SEBS 2, contains 72% PP H110N, 20% G1643M, and 7.5% inventive example FF1.
[0276] Figure 34 compares the micrographs at resolutions of 1 μ m, 0.2 μ m, and 100 nm for the comparative mixture of PP/SEBS and for the inventive mixture containing the additional FF1 diblock. The samples were dyed with a 2% aqueous solution of ruthenium tetroxide for 3 hours at room temperature. It is evident that the dispersion of the SEBS polymer improves with the addition of the inventive diblock. The micrograph of the inventive blend shows a finer dispersion and dispersion of SEBS particles similar to that seen in a polypropylene impact copolymer containing ethylene rubber/alpha-olefin.
[0277] Table 31 shows that the maximum dispersed particle size in the inventive mixture was 0.65 μ m and its size reduced by 49% from 0.43 μ m to 0.22 μ m when compared to the comparative mixture.
[0278] Similar to the improvements in properties seen in polypropylene impact copolymers containing the inventive diblock it is expected that these compatibilized PP/SEBS blends will show an improvement in impact strength greater than 10%, improved clarity and reduced opacity, and greater modulus than the comparative mixture without the diblock compatibilizer. Table 30 - Formulations with SEBS
Table 31 - Scattered Particle Sizes

权利要求:
Claims (8)
[0001]
1. Formulated composition, characterized by the fact that it comprises: (a) polypropylene; (b) compatibilizer, comprising a block composite; and (c) an elastomer, wherein the composition exhibits an Izod strength in kJ/m2 as measured by ASTM D256 or ISO 180 at 0°C or 23°C that is at least 10% greater than that of the composition without (b ); and exhibits a flexural modulus that is less than 10% reduced compared to that of the composition without (b), the block composite comprising a soft copolymer, a hard polymer and a block copolymer comprising two or more chemically distinct blocks connected in a linear manner and having a soft segment and a hard segment, the hard segment of the block copolymer having the same composition as the hard polymer in the block composite and the soft segment of the block copolymer having the same composition as that of the soft copolymer of the block composite; wherein (b) is a block composite having a block composite index > 0.10, the block composite comprising a diblock having an isotactic polypropylene block and an ethylene-propylene block.
[0002]
2. Composition according to claim 1, characterized in that (b) has Tm >100°C and the composition has a particle size percent by weight of dispersed rubber <1 μm.
[0003]
3. Composition according to claim 1, characterized in that the isotactic polypropylene block is present in an amount from 25% by weight to 75% by weight, preferably from 40% by weight to 60% by weight.
[0004]
4. Composition according to claim 1, characterized in that the ethylene content of the ethylene/propylene block is from 40% by weight to 85% by weight.
[0005]
5. Composition according to claim 1, characterized in that the composite in blocks has a melt flow rate at 230°C and 2.16 kg of 0.5 to 8 dg/min.
[0006]
6. Composition modified for impact, characterized by the fact that it comprises: (a) polypropylene; and (b) a block composite wherein the block composite comprises a soft copolymer, a hard polymer and a block copolymer comprising two or more chemically distinct blocks linearly connected and having a soft segment and a hard segment, being that the hard segment of the block copolymer has the same composition as the hard polymer of the block composite and the soft segment of the block copolymer has the same composition as the soft copolymer of the block composite; wherein (b) is a block composite having a block composite index > 0.10, the block composite comprising a diblock having an isotactic polypropylene block and an ethylene-propylene block; wherein the block composite is present in an amount of 0.5% by weight to 20% by weight and the composition has a ductile-brittle transition temperature of at least 2°C lower as compared to the composition without (b ).
[0007]
7. Composition according to any one of claims 1 or 6, characterized in that the polypropylene is selected from the group consisting of low density polypropylene, high density polypropylene, high melt strength polypropylene, high impact polypropylene, polypropylene isotactic, syndiotactic polypropylene and combinations thereof.
[0008]
8. Article, characterized in that it comprises the composition as defined in any one of claims 1 to 7.

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同族专利:

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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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2021-02-17| 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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US24817009P| true| 2009-10-02|2009-10-02|

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US61/248,170|2009-10-02|

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PCT/US2010/051154|WO2011041696A1|2009-10-02|2010-10-01|Block composites and impact modified compositions|

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