COMPOSITION, ARTICLE AND ROTOMOLDED ARTICLE

专利摘要:
compatibilized polyolefin blends. one comprising includes one or more polyethylene, one or more polypropylene, one or more polyolefin elastomer, and a crystalline block composite having the following three components: (i) a crystalline ethylene-based polymer, (ii) a propylene-based polymer crystalline, and (iii) a block copolymer having a crystalline ethylene based block and a crystalline propylene block. the composition of component (i) is the same as the crystalline ethylene based block of the block copolymer and the composition of component (ii) is the same as the crystalline propylene block of the block copolymer. the composition is useful for forming rotomolded articles.
公开号:BR112016007421B1
申请号:R112016007421-1
申请日:2014-10-07
公开日:2021-09-14
发明作者:Gary R. Marchand；Russell P. Barry；Yushan Hu；Kim L. Walton；Colin LiPiShan；Raymond L. Laakso Jr.
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

FIELD
[001] The invention relates to compatibilized polyolefin blends, and in particular, these blends used in rotational molding applications. INTRODUCTION
[002] Rotational molding or rotational molding involves adding an amount of material to a mold, heating and rotating the mold so that the material lines the mold walls, cooling the mold to produce a formed article, and releasing the article. Traditionally, polyolefins used for these applications include polypropylene or polyethylene and in particular MDPE, but generally not blends of these incompatible polymers. Polypropylene and polyethylene blends often result in phase separation causing poor mechanical properties such as impact strength. SUMMARY
[003] Modalities can be carried out by providing a composition including one or more polyethylene, one or more polypropylene, one or more polyolefin elastomer, and a crystalline block composite having the following three components (i) a polymer based on crystalline ethylene (CEP ), (ii) a polymer-based crystalline alpha-olefin (CAOP) and (iii) a block copolymer having a crystalline ethylene block (CEB) and a crystalline alpha-olefin block (CAOB). The block copolymer CEB has the same composition as the CEP in the block composite and the block copolymer CAOB has the same composition as the block composite CAOP. DESCRIPTION OF THE FIGURES
[004] Figure 1 shows the Izod impact strength vs tensile modulus for Examples 1-5 and Comparative Examples A-E.
[005] Figure 2 shows the TEM morphology for Ex B and Ex 1.
[006] Figure 3 shows SEM morphology of compression-molded plates in the core. The bright phase is PP, the darkest phase is HDPE, and the darkest phase is OBC1.
[007] Figure 4 shows optical microscopy characterizations of bubble formation for Ex. 9-11. DETAILED DESCRIPTION
[008] The invention provides a composition comprising one or more polyethylene, one or more polypropylene; one or more polyolefin elastomers; and is a crystalline block composite comprising three components: (i) a polymer based on crystalline ethylene (CEP), (ii) a polymer based on crystalline alpha-olefin (CAOP) and (iii) a block copolymer having a block of crystalline ethylene (CEB) and a crystalline alpha-olefin block (CAOB). The block copolymer CEB has the same composition as the CEP in the block composite and the block copolymer CAOB has the same composition as the block composite CAOP. Polyethylene
[009] Any polyethylene can be used in the invention. Preferably, the polyethylene is selected from ultra-low density polyethylene (ULDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), high density polyethylene. high density, high melt strength (HMS-HDPE), ultra high density polyethylene (UHDPE), and combinations thereof. Exemplary polyethylene is discussed in Publication Nos. WO 2010/042304, WO 2011/159649, and WO 2013/148035.
[0010] Exemplary ULDPEs are available from The Dow Chemical Company under the trade name ATTANE™, such as ATTANE™ 4201G and ATTANE™ 4203, and ATTANE™ 4404 G. ULDPE resins can be characterized as having a density between 0.89 g/ cc to 0.915 g/cc. ULDPEs can have a melt mass flow rate of 0.5 to 10.0 g/10 min. Exemplary LDPEs are available from The Dow Chemical Company under the trade name DOW™ Low Density Polyethylene (LDPE), such as DOW™ LDPE 132l, DOW™ LDPE 5004l, and DOW™ LDPE PG 7004. LDPE resins can be characterized as having a density of 0.910 g/cc to 0.940 g/cc. LDPE can have a melt mass flow rate of 0.2 to 100.0 g/10 min. Exemplary LLDPEs are available from The Dow Chemical Company under the trade name DOW™ Linear Low Density Polyethylene (LLDPE), as DOW™ LLDPE DFDA-7047 NT7. LLDPE resins can be characterized as having a density of 0.915 g/cc to 0.925 g/cc and a substantially linear polymer (for example, they differ from LDPE due to the minimization or exclusion of low chain branching). LLDPE can have a melt mass flow rate of 0.2 to 50.0 g/10 min. MDPEs are available from The Dow Chemical Company under the trade name DOW™ Medium Density Polyethylene (MDPE), such as DOW™ MDPE 8818, DOW™ DMDA-8962 NT 7, and DOWLEX™ 2432E. MDPE resins can be characterized as having a density of 0.926 g/cc to 0.940 g/cc. HDPEs are available from The Dow Chemical Company under the trade name DOW™ High Density Polyethylene (HDPE), as DOW™ HDPE 25055E and DOW™ HDPE KT 10000 EU, and under the trade name UNIVAL™, as UNIVAL™ DMDD-6200 NT 7 HDPE resins can be characterized as having a density greater than 0.940 g/cc (for example, up to 0.970 g/cc). Exemplary modalities include HDPE having a density greater than 0.940 g/cc and/or greater than 0.950 g/cc and up to 0.970 g/cc. For example, the polyethylene component of the composition can consist essentially of HDPE. Polypropylene
[0011] Any polypropylene can be used in the invention. Polypropylene can be in the form of a copolymer or a homopolymer. For example, polypropylene is selected from random copolymer polypropylene (rcPP), impact copolymer polypropylene (hPP + at least one elastomeric impact modifier) (ICPP) or high impact polypropylene (HIPP), high melt strength polypropylene (HMS-PP), isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), and combinations thereof. Exemplary polypropylene is discussed in Publication Nos. WO 2011/159649 and WO 2013/148035. Exemplary embodiments include a polypropylene homopolymer, for example, the polypropylene component of the composition can consist essentially of the polypropylene homopolymer. Crystalline Block Composite
[0012] The term "crystalline block composite" (CBC) refers to polymers having three components: a polymer based on crystalline ethylene (CEP), a polymer based on crystalline alpha-olefin (CAOP), and a block copolymer having a crystalline ethylene block (CEB) and a crystalline alpha-olefin block (CAOB), wherein the CEB of the block copolymer has the same composition as the CEP in the block composite and the CAOB of the block copolymer has the same composition than the CAOP of the block composite. Furthermore, the composition split between the amount of CEP and CAOP will be essentially the same as that between the corresponding blocks in the block copolymer. When produced in a continuous process, the crystalline block composites desirably have PDI from 1.7 to 15, preferably from 1.8 to 10, preferably from 1.8 to 5, more preferably from 1.8 to 3.5. Such crystalline block composites are described in, for example, U.S. Patent Application Publication Nos. 2011-0313106, 20110313108 and 2011-0313108, all published December 22, 2011, and incorporated herein by reference with respect to descriptions of crystalline block composites, processes for preparing the same, and methods for analyzing the same. The term "block copolymer" or "segmented copolymer" refers to a polymer comprising two or more chemically distinct segments or regions (referred to as "blocks") joined in a linear fashion, that is, a polymer comprising chemically differentiated units that are joined (covalently bonded) end to end with respect to polymerized functionality, rather than pendant or grafted. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated herein, the density, the amount of crystallinity, the type of crystallinity (eg, polyethylene versus polypropylene), the crystallite size attributable to a polymer of that composition, the type or degree of tacticity (isotactic or syndiotactic), regioregularity or regioirregularity, the amount of branching, including long-chain branching or hyperbranching, homogeneity, or any other physical or chemical property. The block copolymers of the invention are characterized by unique polymer polydispersity distributions (PDI or Mw/Mn) and block length distribution, due, in a preferred embodiment, to the effect of carriers in combination with catalysts as more described below.
[0013] CAOB refers to the highly crystalline blocks of polymerized alpha olefin units in which the monomer is present in an amount greater than 90% mol, preferably greater than 93 percent mol, more preferably greater than 95 percent mol. mol, and preferably greater than 96% by mol. In other words, the comonomer content in CAOBs is less than 10 mol percent, and preferably less than 7 mol percent, and more preferably less than 5 mol percent, and most preferably less than 4% mol CAOBs with propylene crystallinity have corresponding melting points which are 80°C and above, preferably 100°C and above, more preferably 115°C and above, and most preferably 120°C and above. In some embodiments, the CAOB comprises all or substantially all of the propylene units. CEB, on the other hand, refers to blocks of polymerized ethylene units wherein the comonomer content is 10 mol% or less, preferably between 0 mol% and 10 mol%, more preferably between 0 mol% and 7% by mol and more preferably between 0% by mol and 5% by mol. Such CEB have corresponding melting points which are preferably 75°C and above, more preferably 90°C, and 100°C and above.
[0014] Preferably, the crystalline block composite polymers comprise propylene, 1-butene or 4-methyl-1-pentene and one or more comonomers. Preferably, 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 comprise 4-methyl-1-pentene and ethylene and/ or one or more C4-20 α-olefin comonomers, or comprise 1-butene and ethylene, propylene and/or one or more C5-C20 α-olefin comonomers and/or one or more additional copolymerizable comonomers. Additional suitable comonomers are selected from diolefins, cyclic olefins, and cyclic diolefins, halogenated vinyl compounds, and vinylidene aromatic compounds. Preferably, the monomer is propylene and the comonomer is ethylene.
[0015] The comonomer content in crystalline block composite polymers can be measured using any suitable technique, with techniques based on preferred nuclear magnetic resonance (NMR) spectroscopy.
[0016] Block composites and crystalline block composites preferably have a Tm greater than 100 °C, preferably greater than 120 °C, and more preferably greater than 125 °C. Preferably, the Tm is in the range 100°C and 250°C, more preferably 120°C to 220°C and also preferably in the range 125°C to 220°C. Preferably, the MFR of block composites and crystalline block composites 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.
[0017] Most preferably, block composites and crystalline block composites 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 from 300,000, preferably from 50,000 to about 200,000.
[0018] Preferably, the crystalline block composite polymers of the invention comprise from 0.5 to 95% by weight of CEP, from 0.5 to 95% by weight of CAOP and from 5 to 99% by weight of block copolymer . More preferably, the crystalline block composite polymers comprise from 0.5 to 79% by weight of CEP, from 0.5 to 79% by weight of CAOP and from 20 to 99% by weight of block copolymer and more preferably from 0.5 to 49% by weight CEP, 0.5 to 49% by weight CAOP and 50 to 99% by weight block copolymer. Weight percentages are based on the total weight of the crystalline block composite. The sum of the CEP, CAOP, and block copolymer weight percentages equals 100%.
[0019] Preferably, the block copolymers of the crystalline block composite comprise from 5 to 95 percent by weight of crystalline ethylene blocks (CEB) and from 95 to 5 percent by weight of crystalline alpha-olefin blocks (CAOB) . They may comprise 10% by weight to 90% by weight CEB and 90% by weight to 10% by weight CAOB. More preferably, the block copolymers comprise 25 to 75% by weight CEB and 75 to 25% by weight CAOB, and even more preferably comprise 30 to 70% by weight CEB and 70 to 30% by weight CAOB. According to an exemplary embodiment, block copolymers include 40 wt% to 60 wt% crystalline propylene blocks (eg, isotactic polypropylene), and a balance of blocks based on crystalline ethylene (eg, ethylene and propylene, at least 85% by weight of which is ethylene), based on the total weight of the block copolymers.
[0020] In some embodiments, crystalline block composites have a Crystalline Block Composite Index (CBCI), as defined below, that is greater than zero but less than about 0.4 or from about 0.1 to about 0.3. In other modalities, CBCI is greater than about 0.4 and even about 1.0. In some embodiments, CBCI is in the range of about 0.1 to about 0.9, about 0.1 to about 0.8, about 0.1 to about 0.7, or about 0 .1 to about 0.6. In addition, the CBCI 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, CBCI 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, from about from 0.3 to about 0.6, from about 0.3 to about 0.5, or from about 0.3 to about 0.4. In other embodiments, CBCI 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.
[0021] The block composite and crystalline block composite polymers are preferably prepared by a process comprising contacting an addition polymerizable monomer or blend of monomers under addition polymerization conditions with a composition comprising at least one addition polymerization catalyst, a cocatalyst and a chain transport agent, said process being characterized by the formation of at least some of the growing polymer chains under differentiated process conditions in two or more reactors operating under steady state polymerization conditions or in two or more zones of a reactor operating under plug flow polymerization conditions. The term, "transport agent" refers to a compound or mixture of compounds that is capable of causing polymeryl exchange between at least two active catalyst sites under the conditions of polymerization. That is, the transfer of a polymer fragment occurs to and from one or more of the active catalyst sites. In contrast to a transport agent, a "chain transfer agent" causes polymer chain growth termination and amounts for a single transfer of the growing polymer from the catalyst to the transfer agent. In a preferred embodiment, block composites and crystalline block composites comprise a fraction of the block polymer that has a more likely distribution of block lengths.
[0022] Suitable processes useful in the production of block composites and crystalline block composites can be found, for example, in US Patent Application Publication No. 2008/0269412, published October 30, 2008, which is incorporated herein as reference. In particular, the polymerization is desirably carried out as a continuous polymerization, preferably a continuous, solution polymerization, in which catalyst components, monomers and, optionally, solvent, adjuvants, scavengers, and polymerization aids are continuously supplied to one or more reactors or zones and polymer product continuously removed therefrom. Within the scope of the terms "continuous" and "continuously" as used in this context are those processes in which there are intermittent additions of reactants and removal of products at small regular or irregular intervals, so that, over time, the overall process is substantially continuous. Chain transport agents can be added at any time during polymerization, including in the first reactor or zone, at the exit, or just before the exit of the first reactor, or between the first reactor or zone and the second or any reactor or subsequent 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 such as comonomer content, crystallinity, density, tacticity, regioregularity, or another physical or chemical difference, within the same molecule are formed in different reactors or zones. The size of each segment or block is determined by continuous polymer reaction conditions, and preferably is a more likely distribution of polymer sizes.
[0023] By producing a block polymer having a crystalline ethylene block (CEB) and a crystalline alpha-olefin block (CAOB) in two reactors or zones it is possible to produce the CEB in the first reactor or zone and the CAOB in the second reactor or zone or to produce the CAOB in the first reactor or zone and the CEB in the second reactor or zone. It is more advantageous to produce CEB in the first reactor or zone with added fresh chain transport agent. The presence of increased levels of ethylene in the reactor or zone producing CEB will normally lead to a much higher molecular weight in that reactor or zone than in the zone or reactor producing CAOB. The fresh chain transport agent will reduce the MW of polymer in the reactor or CEB producing zone, thus leading to a better overall balance between the CEB and CAOB segment length.
[0024] When operating reactors or zones in series, it is necessary to maintain different reaction conditions so that one reactor produces CEB and the other reactors produce CAOB. The transfer of ethylene from the first reactor to the second reactor (in series) or from the second reactor back to the first reactor via a solvent and monomer recycling system is preferably minimized. There are many possible unit operations to remove this ethylene, but because ethylene is more volatile than higher alpha-olefins, a simple way is to remove much of the unreacted ethylene through a vaporization step by reducing the reactor effluent pressure. producing CEB and evaporating the ethylene. A more preferred approach is to avoid additional unit operations and use the much higher reactivity of ethylene versus higher alpha olefins so that the ethylene conversion through the CEB reactor approaches 100%. The total conversion of monomers between the reactors can be controlled by keeping the alpha-olefin conversion at a high level (90 to 95%).
[0025] Suitable catalysts and catalyst precursors for use in the present invention include metal complexes as disclosed in WO2005/090426, 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.
[0026] Particularly preferred catalysts are those of the following formula:
where: R20 is an inertly or aromatically substituted aromatic group containing from 5 to 20 atoms not counting hydrogen, or a polyvalent derivative thereof; T3 is a hydrocarbylene or silane group having 1 to 20 atoms not counting hydrogen, 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; g is a number from 1 to 5 indicating the number of these G groups; and electron-donating bonds and interactions are represented by lines and arrows, respectively.
[0027] Preferably, these complexes correspond to the formula:
wherein: T3 is a divalent bridging group of 2 to 20 atoms not containing hydrogen, preferably a substituted or unsubstituted C3-6 alkylene group; and Ar2 is independently at each occurrence an arylene or an alkyl or substituted aryl group of 6 to 20 atoms not counting hydrogen; M3 is a Group 4 metal, preferably hafnium or zirconium; G is independently at each occurrence an anionic, neutral or dianionic ligand group; g is a number from 1 to 5 indicating the number of these X groups; and electron donor interactions are represented by arrows.
[0028] 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 T4 independently at each occurrence comprises a C3-6 alkylene group, a C3-6 cycloalkylene group or an inertly substituted derivative thereof; R21 is independently at each occurrence hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atoms not counting hydrogen; and G is independently at each occurrence a halo or hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2 groups G together are a bivalent derivative of the above hydrocarbyl or trihydrocarbylsilyl groups.
[0029] Especially preferred are compounds of the formula:
where Ar4 is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, or anthracen-5-yl, R21 is hydrogen, halo or C1-4 alkyl, especially methyl T4 is propan-1,3-diyl or butan-1,4-diyl, and G is chlorine, methyl or benzyl.
[0030] Other suitable metal complexes are those of the formula:

[0031] The above polyvalent Lewis base complexes are conveniently prepared by standard metallation and ligand exchange procedures involving a Group 4 metal source and the polyfunctional neutral ligand source. In addition, the complexes can also be prepared by an amide hydrocarbylation process from the corresponding Group 4 metal tetra-amide and a hydrocarbylation agent such as trimethylaluminum. Other techniques can also be used. These complexes are known from the disclosures of, among others, U.S. Patent Nos. 6,320,005, 6,103,657, 6,953,764 and International Publication Nos. WO 02/38628 and WO 40195/03.
Suitable cocatalysts are those disclosed in WO2005/090426, in particular those disclosed on page 54, line 1 to page 60, line 12, which is incorporated herein by reference.
Suitable chain transport agents are those disclosed in WO2005/090426, in particular those disclosed on page 19, line 21 to page 20, line 12, which is incorporated herein by reference. Particularly preferred chain transport agents are dialkyl zinc compounds. Polyolefin Elastomers
[0034] The inventive composition also includes one or more polyolefin elastomers. The polyolefin elastomer can be a homogeneously branched ethylene/alpha-olefin copolymer. Such copolymers can be prepared with a single-site catalyst such as a metallocene catalyst or constrained geometry catalyst and typically have a melting point of less than 105, preferably less than 90, more preferably less than 85, even more preferably less than 80 and even more preferably less than 75°C. Melting point is measured by differential scanning calorimetry (DSC) as described, for example, in USP 5,783,638. The α-olefin is preferably a linear, branched or cyclic C3-20 α-olefin. Examples of C3-20 α-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1- octadecene. α-Olefins can also have a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane. Although not α-olefins in the classical sense of the term, for purposes of this invention, certain cyclic olefins, such as norbornene and related olefins, are α-olefins and can be used in place of some or all of the α-olefins described above. Likewise, styrene and its related olefins (eg, α-methylstyrene, etc.) are α-olefins for the purposes of this invention. Illustrative homogeneously branched ethylene/alpha-olefin copolymers include ethylene/propylene, ethylene/butene, ethylene/1-hexene, ethylene/1-octene, ethylene/styrene, and the like. Illustrative terpolymers include ethylene/propylene/1-octene, ethylene/propylene/butene, ethylene/butene/1-octene, and ethylene/butene/styrene. More specific examples of homogeneously branched ethylene/alpha-olefin interpolymers useful in this invention include linear, homogeneously branched ethylene/α-olefin copolymers (e.g., TAFMER® by Mitsui Petrochemicals Company Limited and EXACT® by Exxon Chemical Company ), and substantially linear, homogeneously branched ethylene/α-olefin polymers (eg, polyethylene AFFINITY™ and ENGAGE™ available from The Dow Chemical Company). Substantially linear ethylene copolymers are especially preferred, and are more fully described in USP 5,272,236, 5,278,272 and 5,986,028. Blends of any of these interpolymers can also be used in the practice of this invention. In the context of the present invention, homogeneously branched ethylene/alpha-olefin interpolymers are not olefin block copolymers. Olefin Block Copolymer
[0035] The term "olefin block copolymer" or "OBC" means a multiblock ethylene/α-olefin copolymer and includes ethylene and one or more copolymerizable α-olefin comonomer in polymerized form, characterized by various blocks or segments of two or more polymerized monomer units differing in physical or chemical properties. The terms "interpolymer" and "copolymer" are used interchangeably herein. When referring to amounts of "ethylene" or "comonomer" in the copolymer, this is understood to mean polymerized units thereof. In some embodiments, the multiblock copolymer can be represented by the following formula: (AB)n where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or greater, “A” represents a hard block or segment and “B” represents a soft block or segment. Preferably, As and Bs are connected in a substantially linear fashion, as opposed to a substantially branched or substantially star-shaped form. In other embodiments, A blocks and B blocks are randomly distributed along the polymer chain. In other words, block copolymers typically do not have a structure as follows. YYY-YY-BBB-BB
[0036] In yet other embodiments, block copolymers generally do not have a third type of block, which comprises different comonomers. In still other embodiments, each A block and B block has substantially randomly distributed monomers or comonomers within the block. In other words, neither the A block nor the B block comprise two or more subsegments (or subblocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.
[0037] Preferably, ethylene comprises the majority molar fraction of the entire block copolymer, i.e., ethylene comprises at least 50 mole percent of the entire polymer. More preferably, ethylene comprises at least 60 mole percent, at least 70 mole percent, or at least 80 mole percent, with the substantial remainder of the entire polymer comprising at least one other comonomer which is preferably an α-olefin having 3 or more carbon atoms. In some embodiments, the olefin block copolymer may comprise 50 mol% to 90 mol% ethylene, preferably 60 mol% to 85 mol%, more preferably 6 mol% to 80 mol%. For many ethylene/octene block copolymers, the preferred composition comprises an ethylene content greater than 80 mole percent of the entire polymer and an octene content of 10 to 15, preferably 15 to 20 mole percent of the entire polymer. .
[0038] Olefin block copolymer includes various amounts of "hard" and "soft" segments. "Hard" segments are blocks of polymerized units in which ethylene is present in an amount greater than 95 percent by weight, or greater than 98 percent by weight based on polymer weight, up to 100 percent by weight. In other words, the comonomer content (non-ethylene monomer content) in the hard segments is less than 5% by weight, or less than 2 percent by weight based on polymer weight, and can be as low as zero. In some embodiments, the hard segments include all, or substantially all, ethylene-derived units. "Soft" segments are blocks of polymerized units in which the comonomer content (monomer content other than ethylene) is greater than 5 percent by weight, or greater than 8% by weight, greater than 10 percent by weight, or greater than 15 percent by weight based on the weight of the polymer. In some embodiments, the comonomer content in the soft segments can be greater than 20 percent by weight, greater than 25 percent by weight, greater than 30 percent by weight, greater than 35 percent by weight, greater than 40 percent by weight, greater than 45 percent by weight, greater than 50 percent by weight, or greater than 60 percent by weight, and may be up to 100 percent by weight.
The soft segments may be present in an OBC from 1 percent by weight to 99 percent by weight of the total weight of OBC, or from 5 percent by weight to 95 percent by weight, from 10 percent by weight to 90 percent by weight, from 15 percent by weight to 85 percent by weight, from 20 percent by weight to 80 percent by weight, from 25 percent by weight to 75 percent by weight, from 30 percent by weight to 70 percent by weight, from 35 percent by weight to 65 percent by weight, from 40 percent by weight to 60 percent by weight, or from 45 percent by weight to 55 percent by weight total OBC. On the other hand, hard segments can be present in similar bands. The soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR. These methods and calculations are disclosed in, for example, US Patent No. 7,608,668 entitled “Ethylene/α-Olefin Block Inter-polymers,” filed March 15, 2006, in the name of Colin LP Shan, Lonnie Hazlitt, et. al. and assigned to Dow Global Technologies Inc., the disclosure of which is incorporated herein by reference in its entirety. In particular, hard and soft segment weight percentages and comonomer content can be determined as described in Column 57 through Column 63 of U.S. 7,608,668.
[0040] Olefin block copolymer is a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") preferably linearly joined, that is, a polymer comprising chemically differentiated units that are joined end to end with regarding polymerized ethylenic functionality rather than pendant or grafted form. In one embodiment, the blocks differ in the amount or type of comonomer incorporated, density, amount of crystallinity, crystallite size attributable to a polymer of such composition, type or degree of tacticity (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching (including long chain branching or hyperbranching), homogeneity or any other physical or chemical property. Compared to prior art block interpolymers, including interpolymers produced by sequential monomer addition, fluxional catalysts, or anionic polymerization techniques, the present OBC is characterized by unique polymer polydispersity distributions (PDI or Mw/Mn or MWD), block length distribution, and/or block number distribution, due, in one embodiment, to the effect of carriers in combination with various catalysts used in their preparation.
[0041] In one modality, the OBC is produced in a continuous process and has a polydispersity index, PDI, from 1.7 to 3.5, or from 1.8 to 3, or from 1.8 to 2.5 or from 1.8 to 2.2. When produced in a batch or semi-batch process, OBC has a PDI from 1.0 to 3.5, or from 1.3 to 3, or from 1.4 to 2.5, or from 1.4 to 2.
[0042] Furthermore, the olefin block copolymer has a PDI fit of Schultz-Flory distribution, rather than a Poisson distribution. The present OBC has a polydisperse block distribution as well as a polydisperse block size distribution. This results in the formation of polymer products having improved and distinct physical properties. The theoretical benefits of a polydisperse block distribution were previously modeled and discussed in Potemkin, Physical Review E (1998) 57(6), pp. 6902-6912, and Dobrynin, J. Chem. Phvs. (1997) 107 (21), pp 9234-9238.
[0043] In one embodiment, the present olefin block copolymer has a more likely distribution of block lengths. In one embodiment, the olefin block copolymer is defined as having: (A) Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density , d, in grams/cubic centimeter, where the numerical values of Tm and d correspond to the ratio: Tm > -2002.9 + 4538.5(d) - 2422.2(d)2, and/or (B) Mw/Mn of 1.7 to 3.5, and is characterized by a heat of fusion, ΔH in J/g, and a delta amount, ΔT, in degrees Celsius defined as the temperature difference between the highest peak of DSC and the highest peak of Crystallization Analysis Fractionation (“CRYSTAF”), in which the numerical values of ΔT and ΔH have the following relationships: ΔT > -0.1299 ΔH) + 62.81 for ΔH greater than zero and up to 130 J/g, ΔT > 48°C for ΔH greater than 130 J/g where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C; and/or (C) elastic recovery, Re, in percent at 300 percent stress and 1 cycle measured with a compression-molded film of ethylene/α-olefin interpolymer, and has a density, d, in grams/cubic centimeter , where the numerical values of Re and d satisfy the following relationship when ethylene/α-olefin interpolymer is substantially free of a crosslinked phase: Re > 1481 - 1629 (d); and/or (D) has a molecular fraction that elutes between 40°C and 130°C when fractionated using TREF, characterized in that the fraction has a molar comonomer content greater than or equal to the amount (- 0.2013 ) T + 20.07, more preferably greater than or equal to the amount (-0.2013) T + 21.07, where T is the numerical value of the peak elution temperature of the TREF fraction, measured in °Celsius; and/or, (E) has a storage module at 25°C, G' (25°C), a storage module at 100°C, G'(100°C), where the ratio of G'( 25°C) to G'(100°C) is in the range of 1:1 to 9:1.
[0044] Olefin block copolymer may also have: (F) a molecular fraction that elutes between 40°C and 130°C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1 and a molecular weight distribution, Mw/Mn, greater than about 1.3; and/or (G) mean block index greater than zero and up to 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3. It is understood that the olefin block copolymer may have one, some, all, or any combination of (A)-(G) properties. The Block Index can be determined as described in detail in U.S. Patent No. 7,608,668 incorporated herein by reference thereto. Analytical methods for determining properties (A) to (G) are disclosed in, for example, US Patent No. 7,608,668, Col. 31, line 26 to Col. 35, line 44, which is incorporated herein by reference to that end. .
[0045] Suitable monomers for use in preparing the present OBC include ethylene and one or more addition polymerizable monomers other than ethylene. Examples of suitable comonomers include straight or branched chain α-olefins from 3 to 30, preferably 3 to 20, carbon atoms such as 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 from 3 to 30, preferably 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-octahydronaphthalene; di and polyolefins such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 ,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene- 8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene; and 3-phenylpropene, 4-phenylpropene, 1,2-difluoroethylene, tetrafluoroethylene, and 3,3,3-trifluoro-1-propene.
[0046] Olefin block copolymer has a density of 0.850 g/cc to 0.925 g/cc, or 0.860 g/cc to 0.88 g/cc or 0.860 g/cc to 0.879 g/cc. The OBC has a Shore A value of 40 to 70, preferably 45 to 65, and more preferably 50 to 65. In one embodiment, the olefin block copolymer has a melt index (MI) of 0.1 g /10 min to 30 g/10 min, or from 0.1 g/10 min to 20 g/10 min, or from 0.1 g/10 min to 15 g/10 min, as measured by ASTM D 1238 (190° C/2.16 kg). The olefin block copolymer is present in an amount of 1% by weight to 45% by weight, preferably 2% by weight to 30% by weight, more preferably 5% by weight to 25% by weight. For example, the range is from 10% by weight to 25% by weight and/or 14.5% by weight to 20.5% by weight. The composition can comprise more than one olefin block copolymer. Olefin Block Copolymer can also be present in an amount of 1% by weight to 20% by weight. All weight percentages are based on the total weight of the composition.
[0047] The OBCs of the present invention can also be 'mesophase-separated' meaning that the polymeric blocks are locally segregated to form ordered mesodomains. The crystallization of ethylene segments in these systems is mainly restricted to the resulting mesodomain. These mesodomains can take the form of spheres, cylinders, lamellae, or other morphologies known for block copolymers. Such OBCs and processes for making them are disclosed in, for example, U.S. Patent No. 7.947,793, which is incorporated herein by reference. The narrowest dimension of a domain, such as perpendicular to the plane of lamellae, is generally greater than about 40 nm in the separate mesophase block copolymers of the present invention. Domain sizes are typically in the range of about 40 nm to about 300 nm, preferably in the range of about 50 nm to about 250 nm, and more preferably in the range of about 60 nm to about 200 nm, as measured by the smallest dimension as perpendicular to the plane of lamellae or the diameter of spheres or cylinders. In addition, domains can have smaller dimensions that are larger than about 60 nm, larger than about 100 nm, and larger than about 150 nm. Separated mesophase polymers comprise olefin block copolymers wherein the amount of comonomer in the soft segments compared to the hard segments is such that the block copolymer undergoes mesophase separation in the melt. The amount of comonomer required can be measured in mole percent and varies with each comonomer. A calculation can be made for any desired comonomer in order to determine the amount needed to achieve mesophase separation. The minimum level of incompatibility, expressed in XN, to achieve mesophase separation in these polydispersed block copolymers is predicted to be XN=2.0 (II Potemkin, SV Panyukov, Phys. Rev. E. 57, 6902 (1998)) . Recognizing that fluctuations generally push the order-disorder transition in trading block copolymers to XN a little higher, an XN=2.34 value is used as the minimum in the calculations below. Following the approach of D.J. Lohse, W.W. Graessley, Polymer Blends Volume 1: Formulation, ed. D.R. Paul, C.B. Bucknall, 2000, XN can be converted to the product of w/v and M/w, where v is a reference volume, M is the number average block molecular weight, and p is the melt density. The melt density is taken to be 0.78 g/cm3 and a typical block molecular weight value is approximately 25,500 g/mol based on a diblock at a total molecular weight of 51,000 g/mol. p/v for cases where the comonomer is butene or propylene is determined using 130 °C as the temperature and then performing an interpolation or extrapolation of the data given in Table 8.1 in the reference by Lohse and Graessley. For each type of comonomer, a linear regression on percentage of mole comonomer was performed. For cases where octene is the comonomer, the same procedure was performed with data from Reichart, GC et al, Macromolecules (1998), 31, 7886. The entanglement molecular weight at 413 K (about 140 °C) in kg /mol is taken to be 1.1. Using these parameters, the minimum difference in comonomer content is determined to be 20.0, 30.8, or 40.7 mole percent, respectively, when the comonomer is octene, butene, or propylene. In some embodiments, the difference in comonomer content is greater than 18.5 mole percent. In some cases, separated mesophase ethylene/α-olefin interpolymer films reflect light through a band of wavelengths in the range from about 200 nm to about 1200 nm. For example, certain films appear blue through reflected light but yellow through transmitted light. Other compositions reflect light in the ultraviolet (UV) range from about 200 nm to 400 nm, while others reflect light in the infrared (IR) range from about 750 nm to about 1000 nm.
[0048] In some embodiments, mesophase separated olefin block copolymers are characterized by average molecular weight greater than 40,000 g/mol, a molecular weight distribution, Mw/Mn, in the range of about 1.4 to about 2.8, and a mole percent difference in α-olefin content between the soft block and the hard block greater than about 18.5 mole percent. In some modalities, OBCs have a Block Index of 0.1 to 1.0.
[0049] In some embodiments, the olefin block copolymer has a density of 0.850 g/cc to 0.925 g/cc, or 0.860 g/cc to 0.88 g/cc or 0.860 g/cc to 0.879 g/ cc. In some embodiments, the OBC has a Shore A value of 40 to 70, preferably 45 to 65, and more preferably 50 to 65. In one embodiment, the olefin block copolymer has a melt index (MI) of 0.1 g/10 min to 30 g/10 min, or from 0.1 g/10 min to 20 g/10 min, or from 0.1 g/10 min to 15 g/10 min, as measured by ASTM D 1238 (190°C/2.16 kg). The olefin block copolymer is present in an amount of 1% by weight to 45% by weight, preferably 2% by weight to 30% by weight, more preferably 5% by weight to 25% by weight. The composition can comprise more than one olefin block copolymer. The olefin block copolymer can also be present in an amount of 1% by weight to 20% by weight. All weight percentages are based on the total weight of the composition.
[0050] Olefin block copolymers are produced through a chain transport process as described in U.S. Patent No. 7,858,706, which is incorporated herein by reference. In particular, suitable chain transport agents and related information are listed in Col. 16, line 39 to Col. 19, line 44. Suitable catalysts are described in Col. 19, line 45 to Col. 46, line 19 and suitable cocatalysts in Col. 46, line 20 to Col. 51, line 28. The process is described throughout the document, but particularly in Col. 51, line 29 to Col. 54, line 56. The process is also described, for example, in the following: US Patent Nos. 7,608,668; U.S. 7,893,166; and U.S. 7.947,793.
[0051] Olefin block copolymers can be produced through a chain transport process as described in U.S. Patent No. 7,858,706, which is incorporated herein by reference. In particular, suitable chain transport agents and related information are listed in Col. 16, line 39 to Col. 19, line 44. Suitable catalysts are described in Col. 19, line 45 to Col. 46, line 19 and suitable cocatalysts in Col. 46, line 20 to Col. 51, line 28. The process is described throughout the document, but particularly in Col. 51, line 29 to Col. 54, line 56. The process is also described, for example, in the following: US Patent Nos. 7,608,668; U.S. 7,893,166; and U.S. 7.947,793. Polypropylene Based Elastomer
[0052] The propylene-alpha-olefin interpolymer is characterized as having substantially isotactic propylene sequences. Propylene-alpha-olefin interpolymers include propylene-based elastomers (PBE). "Substantially isotactic propylene sequences" means that the sequences have an isotactic triad (mm) measured by 13C NMR of greater than about 0.85; alternatively, more than about 0.90; in another alternative, more than about 0.92; and in another alternative, more than about 0.93. Isotactic triads are known in the art and are described in, for example, USP 5,504,172 and International Publication No. WO 00/01745, which refers to isotactic sequence in terms of a triad unit in the copolymer molecular chain determined by 13C spectrum NMR.
[0053] Propylene/alpha-olefin interpolymer can have a melt flow rate in the range of 0.1 to 500 g for 10 minutes (g/10min), measured in accordance with ASTM D-1238 (at 230°C /2.16 kg). All individual values and subranges from 0.1 to 500 g/10min are included here and disclosed here; for example, the melt flow rate can be from a lower limit of 0.1g/10min, 0.2g/10min, or 0.5g/10min to an upper limit of 500g/10min, 200g /10min, 100g/10min, or 25g/10min. For example, the propylene/alpha-olefin copolymer can have a melt rate index in the range of 0.1 to 200 g/10min; or, alternatively, the propylene/alpha-olefin copolymer may have a melt flow rate in the range of 0.2 to 100 g/10min; or alternatively, the propylene/alpha-olefin copolymer may have a melt flow rate in the range of 0.2 to 50 g/10min; or alternatively, the propylene/alpha-olefin copolymer can have a melt flow rate in the range of 0.5 to 50 g/10min; or alternatively, the propylene/alpha-olefin copolymer may have a melt flow rate in the range of 1 to 50 g/10min; or alternatively, the propylene/alpha-olefin copolymer can have a melt flow rate in the range of 1 to 40 g/10min; or, alternatively, the propylene/alpha-olefin interpolymer can have a melt flow rate in the range of 1 to 30 g/10min.
[0054] Propylene/alpha-olefin interpolymer has crystallinity in the range of at least 1 percent by weight (a heat of fusion (Hf) of at least 2 joules/gram (J/g)) to 30 percent by weight (an Hf of less than 50 J/g). All individual values and subranges from 1 percent by weight (an Hf of at least 2 J/g) to 30 percent by weight (an Hf of less than 50 J/g) are included herein and disclosed herein; for example, crystallinity can be a lower limit of 1 percent by weight (an Hf of at least 2 J/g), 2.5 percent (an Hf of at least 4 J/g), or 3 percent ( an Hf of at least 5 J/g) to an upper limit of 30 percent by weight (an Hf of less than 50 J/g), 24 percent by weight (an Hf of less than 40 J/g), 15 percent by weight (an Hf of less than 24.8 J/g) or 7 percent by weight (an Hf of less than 11 J/g). For example, the propylene/alpha-olefin copolymer can have a crystallinity in the range of at least 1 percent by weight (an Hf of at least 2 J/g) to 24 percent by weight (an Hf of less than 40 J /g); or alternatively, the propylene/alpha-olefin copolymer may have a crystallinity in the range of at least 1 percent by weight (an Hf of at least 2 J/g to 15 percent by weight (an Hf of less than 24.8 J/g); or, alternatively, the propylene/alpha-olefin copolymer may have a crystallinity in the range of at least 1 percent by weight (an Hf at least 2 J/g) to 7 percent by weight (a Hf of less than 11 J/g); or alternatively, the propylene/alpha-olefin copolymer may have a crystallinity in the Hf range of less than 8.3 J/g). Crystallinity is measured by differential scanning calorimetry (DSC) as described in USP 7,199,203. The propylene/alpha-olefin copolymer comprises units derived from propylene and polymeric units derived from one or more alpha-olefin comonomers. Exemplary comonomers used to make the propylene/alpha-olefin copolymer are C2, and C4 to C10 alpha-olefins; for example, C2, C4, C6 and C8 alpha-olefins.
[0055] The propylene/alpha-olefin interpolymer comprises from 1 to 40 percent by weight of one or more alpha-olefin comonomers. All individual values and sub-ranges from 1 to 40 percent by weight are included here and disclosed here; for example, the comonomer content can be a lower limit of 1 percent by weight, 3 percent by weight, 4 percent by weight, 5 percent by weight, 7 percent by weight, or 9 percent by weight. of an upper limit of 40 percent by weight, 35 percent by weight, 30 percent by weight, 27 percent by weight, 20 percent by weight, 15 percent by weight, 12 percent by weight, or 9 percent by weight. hundred by weight. For example, the propylene/alpha-olefin copolymer comprises from 1 to 35 percent by weight of one or more alpha-olefin comonomers; or alternatively, the propylene/alpha-olefin copolymer comprises from 1 to 30 percent by weight of one or more alpha-olefin comonomers; or alternatively, the propylene/alpha-olefin copolymer comprises from 3 to 27 percent by weight of one or more alpha-olefin comonomers; or alternatively, the propylene/alpha-olefin copolymer comprises from 3 to 20 percent by weight of one or more alpha-olefin comonomers; or, alternatively, the propylene/alpha-olefin copolymer comprises from 3 to 15 percent by weight of one or more alpha-olefin comonomers.
[0056] The propylene/alpha-olefin interpolymer has a density of typically less than 0.895 g/cm3; or, alternatively, less than 0.890 g/cm3; or, alternatively, less than 0.880 g/cm3; or alternatively less than 0.870 g/cm3. The propylene/alpha-olefin interpolymer has a density typically greater than 0.855 g/cm3; or, alternatively, greater than 0.860 g/cm3; or, alternatively, greater than 0.865 g/cm3.
[0057] Propylene/alpha-olefin interpolymer has a melting temperature (Tm) typically less than 120°C; or, alternatively, < 100 °C; or, alternatively, < 90 °C; or, alternatively, < 80 °C; or, alternatively, < 70°C; and a heat of fusion (Hf) typically of less than 70 Joules per gram (J/g) as measured by differential scanning calorie (DSC) as described in USP 7,199,203.
[0058] Propylene-alpha-olefin interpolymer has a molecular weight distribution (MWD), defined as weight average molecular weight divided by number average molecular weight (Mw/Mn) of 3.5 or less; in 3.0 or less; or from 1.8 to 3.0.
[0059] Such propylene/alpha-olefin interpolymers are further described in USP 6,960,635 and 6,525,157. Such propylene/alpha-olefin interpolymers are commercially available from The Dow Chemical Company under the trade name VERSIFY or from ExxonMobil Chemical Company under the trade name VISTAMAXX.
[0060] In one embodiment, the propylene/alpha-olefin interpolymers are further characterized as comprising (A) between 60 and less than 100, preferably between 80 and 99 and more preferably between 85 and 99, weight percent units derived from propylene , and (B) between more than zero and 40, preferably between 1 and 20, more preferably between 4 and 16 and even more preferably between 4 and 15, weight percent units derived from at least one of ethylene and/or a C4- 10 α-olefin; and containing an average of at least 0.001, preferably an average of at least 0.005 and more preferably an average of at least 0.01, long chain branches/1000 total carbons. The maximum number of long chain branches in the propylene/alpha-olefin copolymer is not critical, but normally should not exceed 3 long chain branches/1000 total carbons. The term long chain branch, as used herein in connection with propylene/alpha-olefin copolymers, refers to a chain length of at least one (1) carbon more than one short chain branch, and chain branch short, as used herein in connection with propylene/alpha-olefin copolymers, refers to a chain length of two (2) carbons less than the number of carbons in the comonomer. For example, a propylene/1-octene interpolymer has structures with long chain branches of at least seven (7) carbons in length, but these structures also have short chain branches of only six (6) carbons in length. Such propylene/alpha-olefin copolymers are further described in detail in U.S. Patent Application No. 20100285253 and International Patent Publication No. WO 2009/067337. Additions
[0061] Compositions including thermoplastic mixtures according to the invention may also contain antiozonants or antioxidants which are known to a rubber chemist skilled in the art. Antiozonants can be physical protectants such as waxy materials that come to the surface and protect the oxygen or ozone part or they can be chemical protectants that react with oxygen or ozone. Suitable chemical protectants include styrenated phenols, octylated butylated phenol, di(dimethylbenzyl) butylated phenol, p-phenylenediamines, butylated p-cresol and dicyclopentadiene (DCPD) reaction products, polyphenolic antioxidants, hydroquinone derivatives, quinoline, diphenylene antioxidants, thioester antioxidants , and mixtures thereof. Some representative trade names for these 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 Antioxidant ™ SN-1, and Irganox™ antioxidants. In some applications, the antioxidants and antiozonants used will preferably be non-staining and non-migratory.
[0062] To provide additional stability against UV radiation, hindered amine light stabilizers (HALS) and UV absorbers can also be used. Suitable examples include Tinuvin™ 123, Tinuvin™ 144, Tinuvin™ 622, Tinuvin™ 765, Tinuvin™ 770, and Tinuvin™ 780, available from Ciba Specialty Chemicals, and Chemisorb™ T944, available from Cytex Plastics, Houston TX, USA. A Lewis acid can be additionally included with a HALS compound to achieve superior surface quality, as disclosed in USP 6,051,681.
[0063] For some compositions, additional mixing process may be employed to pre-disperse antioxidants, antiozonants, carbon black, UV absorbers, and/or light stabilizers to form a masterbatch, and later to form polymer blends of those. anti-deformation agents
[0064] Polar functional polyolefins can be added to compositions to mitigate warping of rotational molded parts. Such polyolefins can include copolymers of ethylene with suitable comonomers such as maleic anhydride, vinyl acetate, α,β-ethylenically unsaturated mono- or dicarboxylic acids, and combinations thereof, glycidyl methacrylate, ethyl acrylate, or butyl acrylate. LDPE copolymers containing α,β-ethylenically unsaturated mono- or dicarboxylic acids can be neutralized in a post-polymerization process with metal ions and compounds of alkali metals, alkaline earth metals, and transition metals; and combinations thereof. Particular cation sources include, but are not limited to, metal ions and compounds of lithium, sodium, potassium, magnesium, cesium, calcium, barium, manganese, copper, zinc, tin, rare earth metals, and combinations thereof. Polar functional polyolefins also include polyolefins derived from grafting copolymers such as polyethylene or maleic anhydride grafted polypropylene.
[0065] Nucleating or clarifying agents can also be added to the compositions to reduce warping or increase cycle time. Such nucleating agents may include Bis(4-propylbenzylidene) propyl sorbitol such as MILLAD® NX8000, 1,3:2,4-Bis(3,4-Dimethylbenzylidene) Sorbitol such as MILLAD® 3988i, Bicyclo[2.2.1]Heptane Acid 2,3-Dicarboxylic acid (disodium salt) as Hyperform® HPN-68L, 1,2-Cyclohexanedicarboxylic acid, Calcium Salt/Zinc Stearate 66/34 as Hyperform® HPN-20E. Compositions
[0066] In embodiments of the invention, polyethylene has a density of 0.935 - 0.965 g/cm3; I2 (> 190°C) 0.5 - 30 g/10min; and can be heterogeneous PE or homogeneous PE and is present in an amount of 20 - 90% by weight based on the total weight of the composition; polypropylene has an MFR (@ 230°C) 2 - 50 g/10min, can be homo-PP, RCP and ICP and can be homogeneous or heterogeneous PP and is present in an amount of 10 to 80% by weight based on total weight of the composition; the polyolefin elastomer may have MI (<190°C) 0.2 - 30 and Density <0.880 g/cm3 preferably <=0.870 g/cm3 and is present in an amount of 2-20% by weight based on the total weight of the composition; and the crystalline block composite has an MFR (@ 230°C) 3 - 60 g/10min; density 0.900 - 0.920 g/cm3, the crystalline alpha olefin copolymer and corresponding block are C3 + a-olefin (0 - 10% by weight; preferably C2), the crystalline ethylene based polymer and corresponding block preferably have propylene as the monomer with >85% by weight derived from ethylene monomer and has a 50% by weight split between CAOP and CEB, based on the weight of the block composite, preferably CBC is present in the composition in an amount of 2-10% by weight based on the total weight of the composition.
[0067] In another description of exemplary embodiments, the one or more polyethylene may represent 25% by weight to 70% by weight (for example, 30% by weight to 55% by weight, 30% by weight to 45% by weight, 35% by weight to 40% by weight, etc.) of a total weight of the composition. The one or more polypropylene may represent 35% by weight to 70% by weight (40% by weight to 65% by weight, 45% by weight to 60% by weight, 50% by weight to 55% by weight, etc.) of the total weight of the composition. The crystalline block composite may represent 0.5% by weight to 20.0% by weight (1% by weight to 15% by weight, 1% by weight to 10% by weight, 3% by weight to 8% by weight , etc.) of the total weight of the composition. The one or more polyolefin elastomer may represent 0.5% by weight to 20.0% by weight (1% by weight to 15% by weight, 1% by weight to 10% by weight, 3% by weight to 8% by weight, etc.) of the total weight of the composition. This composition is useful for applications including molding, and in particular rotational molding or rotational molding. Rotationally molded articles
[0068] Rotational molding or rotational molding involves adding an amount of material to a mold, heating and rotating the mold so that the material lines the mold walls, cooling the mold to produce a formed article, and releasing the article. One-piece hollow items can be prepared through rotational molding. Examples of rotational molded items include, but are not limited to, toys, furniture, containers, for example, tanks and watering cans, and sporting goods, for example, canoes and kayaks. TEST METHODS Differential Scanning Calorimetry (DSC)
[0069] Differential Scan Calorimetry is performed on a TA Instruments Q1000 DSC equipped with an RCS refrigeration accessory and an autosampler. 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 air cooled to room temperature (25°C). About 3-10 mg of material is then cut, accurately weighed, and placed in a lightweight aluminum pan (ca 50 mg) which is later crimped. The thermal behavior of the sample is investigated with the following temperature profile: the sample is rapidly heated to 190°C and kept isothermal for 3 minutes in order to remove any 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/minute. Cooling and second heating curves are recorded. 13C Nuclear Magnetic Resonance (NMR) Sample Preparation
[0070] Samples are prepared by adding approximately 2.7 g of a 50/50 mixture of tetrachloroethane-d2/orthodichlorobenzene which is 0.025 M in chromium acetylacetonate (relaxing agent) to 0.21 g of sample in an NMR tube 10mm. The samples are dissolved and homogenized by heating the tube and its contents to 150°C. Data Acquisition Parameters
[0071] Data is collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high temperature CryoProbe. Data is acquired using 320 transients per data file, a 7.3 sec pulse repetition delay (6 sec delay + 1.3 sec water time), 90 degree flip angles, and inverse closed decoupling with a sample temperature of 125°C. All measurements are taken on samples without rotating in locked mode. Samples are homogenized immediately prior to insertion into the heated (130°C) NMR Sample Changer, and are allowed to thermally equilibrate in the probe for 15 minutes prior to data acquisition. Gel Permeation Chromatography (GPC)
The gel permeation chromatography system consists of a Polymer Laboratories Model PL210 instrument or a Polymer Laboratories Model PL-220 instrument. Column and carousel compartments are operated at 140°C. Three Polymer Laboratories 10-micron Mixed-B columns are used. The solvent is 1,2,4-trichlorobenzene. Samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm butylated hydroxytoluene (BHT). Samples are prepared by gentle shaking for 2 hours at 160°C. The injection volume used is 100 microliters and the flow rate is 1.0 ml/minute.
[0073] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in 6 "cocktail" mixtures with at least a decade of separation between individual molecular weights. Standards were purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared in 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of 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 were run first, and in descending order of higher molecular weight component, to minimize degradation. Polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)). Mpolypropylene = 0.645(Mpolystyrene).
[0074] Polypropylene equivalent molecular weight calculations are performed using Viscotek TriSEC software Version 3.0. Fast Temperature Rise Elution Fractionation (F-TREF)
[0075] In TREF-F analysis, the composition to be analyzed is dissolved in ortho-dichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel dose), slowly reducing the temperature to 30°C (to one preferred rate of 0.4 °C/min). The column is equipped with an infrared detector. An F-TREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (o-dichlorobenzene) from 30 to 140°C (at a preferential rate of 1.5°C/min ). High Temperature Liquid Chromatography (HTLC)
[0076] HTLC is performed in accordance with the methods disclosed in U.S. Patent Application Publication No. 2010-0093964 and U.S. Patent Application No. 2011—152499, both of which are incorporated herein by reference. Samples are analyzed by the method described below.
[0077] A Waters GPCV2000 SEC high temperature chromatograph was reconfigured to build the HT-2DLC instrumentation. Two Shimadzu LC-20AD pumps were connected to the injector valve on GPCV2000 via a binary mixer. The first dimension HPLC column (D1) was connected between the injector and a 10-port exchange valve (Valco Inc). The second dimension SEC column (D2) was connected between the 10-port valve and LS (Varian Inc.), IR (concentration and composition), RI (refractive index), and IV (intrinsic viscosity) detectors. RI and IV were built-in detectors in GPCV2000. The IR5 detector was provided by PolymerChar, Valencia, Spain.
Columns: Column D1 was a high temperature Hypercarb graphite column (2.1 x 100 mm) purchased from Thermo Scientific. Column D2 was a PLRapid-H column purchased from Varian (10 x 100 mm).
Reagents: HPLC grade trichlorobenzene (TCB) was purchased from Fisher Scientific. 1-Decanol and Dean were from Aldrich. 2,6-Di-tert-butyl-4-methyphenol (Ionol) was also purchased from Aldrich.
[0080] Sample Preparation: 0.01 - 0.15 g of polyolefin sample was placed in a 10 mL Waters autosampler bottle. 7 ml of 1-decanol or decane with 200 ppm Ionol was added later to the vial. After spraying helium to the sample vial for about 1 min, the sample vial was placed on a heated stirrer with a set temperature at 160 °C. Dissolution was carried out by shaking the flask at temperature for 2 hr. The vial was transferred to the autosampler for injection. Please note that the actual volume of the solution was more than 7 mL due to thermal expansion of the solvent.
[0081] 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 min of the run. The composition was then increased to 60% strong eluent (TCB) in 489 min. Data were collected for 489 min as the duration of the raw chromatogram. The 10-port valve switched every three minutes generating 489/3 = 163 SEC chromatograms. A post-run gradient was used after data acquisition time of 489 min to clean and balance the column for the next run: Clean step: 1.490 min: flow = 0.01 min; // Keep the flow rate constant from 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 = 100; // Wash column using 2 mL TCB Equilibration step: 5. 503 min: %B = 0; // Change mobile phase composition to 100% 1-decanol or 6-decane. 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; // Increase flow rate to 0.01 mL/min.
[0082] After step 8, the flow rate and composition of the mobile phase were equal to the initial conditions of the running gradient.
[0083] The D2 flow rate was 2.51 ml/min. Two 60 µL handles were installed on the 10-port exchange valve. 30 µL of eluent from column D1 was loaded onto the SEC column with each valve change.
[0084] The IR, LS15 (15° light scattering signal), LS90 (90° light scattering signal) and IR (intrinsic viscosity) signals were collected by EZChrom through an analog-to-conversion box. SS420X digital. The chromatograms were exported in ASCII format and imported into an in-house written MATLAB software for data reduction. Using an appropriate calibration curve of polymer composition and retention volume, of polymers that are similar in nature to the hard block and soft block contained in the block composite being analyzed. Calibration polymers must be narrow in composition (molecular weight and chemical composition) and cover a reasonable molecular weight range to cover the composition of interest during analysis. Analysis of the raw data was calculated as follows, the first dimensional HPLC chromatogram was reconstructed by plotting the IR signal of each slice (from the total SEC IR chromatogram of the slice) as a function of the elution volume. The elution volume IR vs D1 was normalized by the total IR signal to obtain a graph of weight fractions vs. elution volume D1. The methyl/measurement IR ratio was obtained from the reconstructed IR measurement and methyl IR chromatograms. The ratio was converted to composition using a PP % by weight (by NMR) vs methyl/measure calibration curve obtained from SEC experiments. MW was obtained from reconstructed IR measurement and LS chromatograms. The ratio was converted to MW after calibrating the IR and LS detectors using a PE standard.
The % by weight of isolated PP is measured as the area corresponding to the hard block composition based on the isolated peak and the retention volume as determined by a composition calibration curve. Estimating the Crystalline Block Composite Index (CBCI)
[0086] Crystalline block composites having a CAOP and CAOB composed of crystalline polypropylene and a CEP and CEB composed of crystalline polyethylene cannot be fractionated by conventional means. Techniques based on solvent or temperature fractionation, for example using xylene fractionation, solvent/non-solvent separation, temperature rise elution fractionation, or crystallization elution fractionation are not able to resolve the block copolymer once that CEB and CAOB co-crystallize with CEP and CAOP, respectively. However, using a method such as high temperature liquid chromatography that separates the polymer chains using a combination of a mixed solvent/non-solvent and a graphitic column, crystalline polymer species such as polypropylene and polyethylene can be separated from each other and of the block copolymer.
[0087] For crystalline block composites, the amount of isolated PP is smaller than if the polymer was a simple mixture of iPP homopolymer (in this example, the CAOP) and polyethylene (in this case, the CEP). Consequently, the polyethylene fraction contains an appreciable amount of propylene that would otherwise not be present if the polymer were simply a mixture of iPP and polyethylene. To account for this "extra propylene", a mass balance calculation can be performed to estimate a crystalline block composite index by the amount of polypropylene and polyethylene fractions and the % by weight of propylene present in each of the fractions that are separated by HTC. Polymers contained in the crystalline block composite include diblock iPP-PE, unbound iPP, and unbound PE where the individual PP or PE components may contain a small amount of ethylene or propylene, respectively. Composition of Crystalline Block Composite
[0088] A summation of % by weight propylene of each component in the polymer according to equation 1 results in the % by weight of propylene (of the entire polymer). This mass balance equation can be used to quantify the amount of iPP and PE present in the diblock copolymer. This mass balance equation can also be used to quantify the amount of iPP and PE in a binary mixture or augmented for a ternary, or n-component, mixture. For the crystalline block composite, the total amount of iPP or PE is contained within the blocks present in the diblock and the unbound iPP and PE polymers.
Eq. 1 where wpp = weight fraction of PP in the polymer wPE = weight fraction of PE in the polymer %wpC3PP = weight percentage of propylene in the PP component or block %wPEC3PE = weight percentage of propylene in the PE component or block
[0089] Note that the % total weight of propylene (C3) is preferably measured from C13 NMR or some other compositional measurement that represents the total amount of C3 present in the entire polymer. The weight % of propylene in the iPP block (wt%C3PP) is set to 100 or if otherwise known from your DSC melting point, NMR measurement or other compositional estimate, this value can be put in its place. Likewise, the % weight of propylene in the PE block (%w/wC3PE) is set to 100 or if otherwise known from your DSC melting point, NMR measurement, or other compositional estimate, this value can be set to your place. Calculating the Ratio of PP to PE in Crystalline Block Composite
[0090] Based on equation 1, the overall weight fraction of PP present in the polymer can be calculated using Equation 2 of the mass balance of the total C3 measured in the polymer. Alternatively, it can also be estimated from a mass balance of monomer and comonomer consumption during polymerization. In general, this represents the amount of PP and PE present in the polymer regardless of whether it is present in the unbound components or in the diblock copolymer. For a conventional blend, the weight fraction of the PP fraction and the weight of PE corresponds to the individual amount of PP and PE polymer present. For the crystalline block composite, it is assumed that the weight fraction ratio of PP to PE also corresponds to the average block ratio between PP and PE present in this statistical block copolymer.
Eq. 2 where wPP = weight fraction of PP present in the entire polymer %empesoC3PP = weight percentage of propylene in the PP component or block %empesoC3PE = weight percentage of propylene in the PE component or block Estimating the amount of Diblock in the Block Composite Crystalline
[0091] Applying equations 3 to 5, the amount of isolated PP that is measured by HTLC analysis is used to determine the amount of polypropylene present in the diblock copolymer. The amount isolated or separated first in the HTLC analysis represents the 'unbound PP' and its composition is representative of the hard PP block present in the diblock copolymer. Substituting the C3 total weight % of the entire polymer on the left side of equation 3, and the PP weight fraction (HTLC isolate) and PE weight fraction (HTLC separated) on the right side of equation 3, the % by weight of C3 in the PE fraction can be calculated using equations 4 and 5. The PE fraction is described as the fraction separated from unbound PP and contains the diblock and unbound PE. The composition of the isolated PP is assumed to be equal to the % by weight of propylene in the iPP block as described above.
Eq. 3
where wPPisolated = weight fraction of PP isolated from HTLC wPE-fraction = weight fraction of PE separated from HTLC, containing the diblock and unbound PE wt%C3PP = wt% propylene in the PP; which is also the same amount of propylene present in the PP block and in the unalloyed PP %wwtC3PE-fraction = %wt propylene in the HTLC-fraction that was separated by HTLC %wtwC3Total = %wt total propylene in the entire polymer
[0092] The amount of % by weight of C3 in the polyethylene fraction of HTLC represents the amount of propylene present in the block copolymer fraction that is above the amount present in the ‘unalloyed polyethylene.
[0093] To consider the 'additional' propylene present in the polyethylene fraction, the only way to have PP present in this fraction is that the PP polymer chain must be linked to a PE polymer chain (or else it would have been isolated with the PP fraction separated by HTLC). Thus, the PP block remains adsorbed with the PE block until the PE fraction is separated.
[0094] The amount of PP present in the diblock is calculated using Equation 6.
Eq. 6 where %wt/C3PE-fraction = % by weight of propylene in the PE-fraction that has been separated by HTLC (Equation 4) %wt.% of propylene in the PP component or block (defined above) %wt. of propylene in the PE component or block (defined above) wPP-diblock = weight fraction of PP in the diblock separated with PE- fraction by HTLC
[0095] The amount of diblock present in this PE fraction can be estimated by assuming that the ratio of PP block to PE block is the same as the overall PP to PE ratio present in the entire polymer. For example, if the overall ratio of PP to PE is 1:1 in the entire polymer, then it is assumed that the ratio of PP to PE in the diblock is also 1:1. Thus, the diblock weight fraction present in the PE fraction would be the PP weight fraction in the diblock (wPP-diblock) multiplied by two. Another way to calculate this is by dividing the weight fraction of PP in the diblock (wPP-diblock) by the weight fraction of PP in the entire polymer (equation 2).
[0096] To further estimate the amount of diblock present in the entire polymer, the estimated amount of diblock in the PE fraction is multiplied by the weight fraction of the measured PE fraction of HTLC.
[0097] To estimate the crystalline block composite index, the amount of block copolymer is determined by equation 7. To estimate the CBCI, the diblock weight fraction in the PE fraction calculated through equation 6 is divided by the fraction of total PP weight (as calculated in equation 2) and then multiplied by the weight fraction of the PE fraction. The CBCI value can range from 0 to 1, where 1 would equal 100% diblock and zero would be a material such as a traditional blend or random copolymer.
Eq. 7 where wPP-diblock = weight fraction of PP in the diblock separated with PE- fraction by HTLC (Equation 6) wPP = weight fraction of PP in the polymer wPE-fraction = weight fraction of PE separated from HTLC, containing the diblock and unbound PE (Equation 5)
[0098] For example, if an iPP-PE polymer contains a total of 62.5% by weight of C3 and is prepared under the conditions to produce a PE polymer with 10% by weight of C3 and an iPP polymer containing 97 .5% by weight of C3, the weight fractions of PE and PP are 0.400 and 0.600, respectively (as calculated using Equation 2). Since the percentage of PE is 40.0% by weight and of iPP is 60.0% by weight, the relative ratio of the PE:PP blocks is expressed as 1:1.5.
[0099] Therefore, if a person skilled in the art performs an HTLC separation of the polymer and isolates 28% by weight of PP and 72% by weight of the PE fraction, this would be an unexpected result and this would lead to the conclusion that a fraction of block copolymer was present. If the PE fraction content (% by weight C3PE-fraction) is further calculated to be 48.9% by weight of C3 from equations 4 and 5, the PE fraction containing the additional propylene has 0.556 PE polymer weight fraction and 0.444 polymer weight fraction PP (wPP-diblock, calculated using Equation 6).
[00100] Since the PE fraction contains 0.444 weight fraction of PP, it should be linked to an additional 0.293 weight fraction of PE polymer based on the iPP:PE block ratio of 1.5:1. Thus, the weight fraction of diblock present in the PE fraction is 0.741; further calculation of the weight fraction of diblock present in the entire polymer is 0.533. For the whole polymer, the composition is described as 53.3% by weight iPP-PE diblock, 28% by weight PP polymer, and 18.7% by weight PE polymer. The crystalline block composite index (CBCI) is the estimated weight fraction of diblock present in the entire polymer. For the example described above, the CBCI for the crystalline block composite is 0.533.
[00101] The Crystalline Block Composite Index (CBCI) provides an estimate of the amount of block copolymer within the crystalline block composite under the assumption that the ratio of CEB to CAOB within the diblock is the same as the ratio of crystalline ethylene for crystalline alpha-olefin in the total crystalline block composite. This assumption is valid for these statistical olefin block copolymers based on an understanding of individual catalyst kinetics and the polymerization mechanism for the formation of diblocks through chain transport catalysis as described in the specification.
[00102] The calculation of CBCI is based on the analytical observation that the amount of free CAOP is less than the total amount of CAOP that was produced in the polymerization. The remainder of the CAOP is bound to CEB to form the diblock copolymer. Due to the fact that the PE fraction separated by HTLC contains CEP and the diblock polymer, the observed amount of propylene for this fraction is greater than that of CEP. This difference can be used to calculate the CBCI.
[00103] Based solely on analytical observations without prior knowledge of polymerization statistics, the minimum and maximum amounts of block copolymer present in a polymer can be calculated, distinguishing a crystalline block composite from a simple copolymer or copolymer mixture.
[00104] The upper limit on the amount of block copolymer present within a crystalline block composite, wDBMax, is obtained by subtracting the fraction of unbound PP measured by HPLC from one as in Equation 8. This maximum assumes the fraction HTLC PE is entirely diblock and all crystalline ethylene is bonded to crystalline PP without unbound PE. The only material in CBC that is not diblock is the PP portion separated by HTLC.
[1] The lower limit on the amount of block copolymer present within a crystalline block composite, wDBMtn, corresponds to the situation where little or no PE is bound to PP. This lower limit is obtained by subtracting the amount of unbound PP as measured by HTLC from the total amount of PP in the sample as shown in Equation 9. [2]
[3] In addition, the crystalline block composite index will fall between these two values:
[4] Based on the polymerization mechanism for producing crystalline block composites, the CBCI represents the best estimate of the actual fraction of diblock copolymer in the composite. For unknown polymer samples, it can be used to determine if a material is a crystalline block composite. Consider applying this analysis to homopolymers, copolymers or blends. For a physical mixture of PE and PP, the total weight fraction of PP must equal the % by weight of PP of HTLC and the lower limit on the diblock content, Equation 9, is zero. If this analysis is applied to a PP sample that does not contain PE, the fraction of PP weight and amount of PP obtained from HTLC are 100% and again the lower limit on the diblock content, Equation 9, is zero. Finally, if this analysis is applied to a PE sample that does not contain PP then the weight fraction of PP and the weight fraction of PP recovered by HTLC are zero and the lower limit in the diblock, Equation 9, is zero. Since the lower limit for diblock content is not greater than zero in any of these three cases, these materials are not crystalline block composites. compression molding
[00105] Unless otherwise mentioned, plates were used for microtensile testing that were prepared by compression molding using a Tetrahedron press. The polymer was pre-melted at 190°C for 1 minute at 5 klb and then pressed for 5 minutes at 30 klb and then stopped by an ice-water bath. Some were cooled to 5°C min-1 between chilled rolls using circulating water below 30 klb. The nominal plate thickness was 2.9 mm. Compression molded plates were used for microtensile and Izod impact testing. Traction test
[00106] The stress-strain behavior in uniaxial stress was measured using ASTM D1708 microtensile samples. Sample gauge length is 22 mm and samples were stretched with an Instron to 554% min-1 at 23°C. Tensile strength and elongation at break were reported for an average of 5 samples. Additional stress-strain behavior in uniaxial stress was measured using ASTM Compression Molded D638 at 2/min. Izod impact
[00107] Notched Izod impact tests were performed on molded compression specimens. The samples were cut from the same tensile test plates to have dimensions 63.5mm x 12.7mm x 2.9mm. The samples were notched using a chisel to produce a 2.54 +/- 0.05 mm notch depth in accordance with ASTM D256. Five samples from each sample were tested at 23°C and 0°C. Flexion Module
[00108] Secant modulus of 1 or 2% percent bending were measured in accordance with ASTM D-790. Samples are prepared by injection molding of drawbars (approx. 165mm x 19mm x 3mm) and conditioned for at least 40 hours at room temperature. Dart
[00109] Instrumented dart impact was measured using a 6 cm X 6 cm X 2 mm specimen in a CEAST drop dart impact tester. The attack speed was set at 4.3 m/s with a load of 25 kg. Charpy
[00110] Notched Charpy impact test was done in accordance with ISO 294-1 type B. Environmental Stress Crack Resistance (ESCR)
[00111] ESCR was measured according to ASTM D 1693 at 10% and 100% Igepal™ at 50°C. Polymer plates were prepared by compression molding in accordance with ASTM D 4703 using a Tetrahedron press. The compression molding temperature is 190°C and nominal plate thickness is 0.075 in. Results are presented in hours for the 5th, or 50th percentile, failure, f50, on 10 samples. Transmission Electron Microscopy (TEM)
[00112] The injection molded and compression molded samples were examined with TEM. The samples were trimmed so that sections could be collected near the core of the pieces. Trimmed samples were freeze-polished prior to staining by removing sections from the blocks at -60°C to avoid staining of the elastomer phases. The cryopolished blocks were stained with the vapor phase of a 2% aqueous ruthenium tetroxide solution for 3 hours at room temperature. The staining solution was prepared by weighing 0.2 g of ruthenium(III) chloride hydrate (RuCl3 x H2O) into a glass bottle with a screw cap and adding 10 mL of 5.25% sodium hypochlorite water into the jar. The samples were placed in the glass jar using a glass slide having double-sided tape. The slide was placed in the bottle to suspend the blocks about 1 inch above the staining solution. Sections approximately 90 nanometers thick were collected at room temperature using a diamond knife on a Leica EM UC6 microtome and placed virgin 600-mesh TEM grids for observation. For image collection, TEM images were collected on a JEOL JEM-1230 operated at an accelerating voltage of 100 kV and collected on a Gatan-791 and 794 digital cameras. Scanning Electron Microscopy (SEM)
[00113] For high resolution SEM study, small pieces were cut out of the plates. The samples were mounted on a sample holder and trimmed at -100°C using a diamond cutting knife with a Leica EM FC7. Afterwards, the samples were stained in RuO4 steam overnight. After washing and drying, the block samples were further polished using the microtome with a diamond knife at room temperature. SEM images of the block samples were obtained with a NOVA nanoSEM 600 (FEI, Eindhoven, The Netherlands) operated in high vacuum mode at 3 kV and point 4. Images were acquired using a vCD backscatter electron detector in reversed contrast . Contrast on a RuO4-stained sample was created by different degrees of absorption of the heavy metal stain into the material. Optical Microscopy (OM)
[00114] The rotational molded plates were sectioned using a wood plane in the thickness direction. The cut section was unrolled and adhered to microscope slides with the aid of double-sided tape. A cross-sectional region of interest (ROI) measuring approximately 2 inches was coated with iridium for 30 seconds using an “Emitech K575X” turbo plasma applicator to make the samples reflective under illuminated light. The coated mold cross section was illuminated with reflected light and a Leica MZ-16 stereo microscope was used at low magnification (2mm scale) to capture digital images of the bubble defects using a Nikon DMX digital camera and “ACT1” software. Density is measured in accordance with ASTM D 792.
[00115] The melt flow rate or I2 of the samples is measured using ASTM D 1238, Condition 230 °C, 2.16 kg. Melt Index is measured using ASTM D 190, Condition 190 °C, 2.16 kg. The melt or I10 flow rate of the samples is measured using ASTM D 1238, Condition 230°C, 10 kg. Melt Index is measured using ASTM D 1238, Condition 190°C, 10 kg. EXAMPLES Crystalline Block Composites
[00116] The crystalline block composite of the present Example is designated CBC1 and CBC2. They are prepared using two continuous stirred tank reactors (CSTR) connected in series. The first reactor was approximately 12 gallons in volume, while the second reactor was approximately 26 gallons. Each reactor is hydraulically complete and tuned to operate under steady-state conditions. Monomers, solvent, hydrogen, catalyst-1, cocatalyst-1, cocatalyst-2 and CSA-1 are fed to the first reactor according to the process conditions described in Table A. The first reactor contents as described in Table A flow for a second reactor in series. Additional monomers, solvent, hydrogen, catalyst-1, cocatalyst-1 and optionally cocatalyst-2 are added to the second reactor.
[00117] Catalyst-1 ([[rel-2',2'''-[(1R,2R)-1,2-cylcohexanediylbis(methyleneoxy-KO)] bis[3-(9H-carbazol-9-yl) - 5-methyl[1,1'-biphenyl]-2-olate-KO]](2-)]dimethyl-hafnium) and cocatalyst-1, a mixture of methyldi(C14-18 alkyl)ammonium salts of tetrakis( pentafluorophenyl)borate, prepared by reacting a long-chain trialkylamine (Armeen™ M2HT, available from Akzo-Nobel, Inc.), HCl and Li[B(C6F5)4], substantially as disclosed in USP 5,919,983, Ex. 2. are purchased from Boulder Scientific and used without further purification.
[00118] CSA-1 (diethylzinc or DEZ) and cocatalyst-2 (modified methylalumoxane (MMAO)) were purchased from Akzo Nobel and used without further purification. The solvent for the polymerization reactions is a mixture of hydrocarbons (ISOPAR® E) purchased from ExxonMobil Chemical Company and purified through beds of 13-X molecular sieves prior to use. Table A. Reactor Process Conditions for Producing Crystalline Block Composites



Examples 1-4, Comparative AF Methods
[00119] The blending formulations were blended using a Haake Rheomix mixer rotating at 50 RPM, in accordance with compositions shown in Table 2. The mixer is preheated to 190°C. The mixture is held for 5 min after the run is held down. Table 2
Results
[00120] The dataset to study the effect of cooling rate on mechanical properties is tabulated in Table 3 and shown in Figure 2. Examples 1 to 4 give better impact strength/modulus balance vs comparative examples A to F. For example, each of Examples 1 to 4 provide, good elongation at break (such as at least 12%), good tensile modulus (such as at least 130000 psi possibly with an upper limit of 1000000 psi), good hardness ( such as at least 6.0 in* lbf possibly with an upper limit of 100 in* lbf), a good voltage in yd (such as at least 3800 psi possibly with an upper limit of 10000 psi), a good Izod impact @ 23 °C (as at least 10 KJ/m2 possibly with an upper limit of 1000 KJ/m2), and a good Izod impact @ 0 °C (as at least 10 KJ/m2 possibly with an upper limit of 1000 KJ/m2). Figure 3 shows Ex 1 morphology stability after slow cooling to 5°C/min, while the dispersed phase significantly coalesced after slow cooling to Ex B. Table 3 Virgin PP/HDPE blends results (5°C/min)
Examples 5 and 6, Comparatives G and H Experimental
[00121] The formulations in Table 5 were prepared in a BUSS composer, granulated and then sent to be cryogenically ground. In addition, a sample of DOWLEX™ 2432 (Ex. G) was included to also be cryogenically ground for this sample to be used as a reference. Blend formulations are blended using a BUSS composer (MDK/B 46-15LD), granulated with an underwater cutter. The pellets are cryogenically ground to a typical powder specification as shown in Table 6. The powders were then compression molded in accordance with ISO 2932004 where the powders were loaded into a frame, placed in the mold (180°C) and the rollers closed. to a low pressure setting (6-12 bar) for 10 minutes preheat time. The mold was then closed under high pressure (80 bar) for 2 minutes. The material is then allowed to cool at a cooling rate of 15C +/- 5C/min until the samples are cool enough to be removed from the mold. Table 5 Rotational Molding Compounds
Table 6 Powder Milling Parameters
Table 7 Physical Properties
Results
[00122] As can be seen in Table 7 when CBC is added to HDPE/PP/OBC systems, it results in an increase in impact performance while at the same time the rigidity of the formulations is maintained which generates a formulation that shows enhanced impact on non-compatibilized specimens and enhanced stiffness and impact on DOWLEX™ specimens. The effect of CBC is seen in the micrographs obtained from the samples where a finer morphology is observed when CBC is added to the system.
[00123] In addition, it is possible to see great improvement in the ESCR of samples when PP is included. This is a useful property in applications such as rotational molding where materials are used for chemical storage. These compounds would overcome the problem of having to try and use very high molecular weight PE to get enough ESCR, but at the same time sacrifice processability. These materials shown here have the potential to combine ESCR and processability. Examples 7-10 Experimental
[00124] The blend formulations are blended using a W&P ZSK25 twin screw extruder according to the formulations shown in Table 8. For the formulations in Table 8, A02 can be added in place of or in addition to A01. The extruder has 8 heating zones, which have been set at 140, 190, 190, 190, 190, 190, 190 and 190°C respectively. Screw speed runs at 400 rpm, with torque at 50-60% and a feed rate of 40 lbs hr-1. The polymer melting temperature is measured to be 218°C. Pellets are pelletized with a wire cutter. The pellets are all cryogenically ground using a 35 / 500 micron mesh screen. The powders are rotational molded with Rotoline DC 2.50 XT with a Major Shaft at 6 rpm and Minor Shaft at 1.5 rpm. The mold dimension is (13x13x4 inches). Typical molding condition is shown in Table 9. Table 8
Table 9

[00125] The properties of rotational molded parts are shown in Table 16. Ex. 7 shows the formation of bubbles inside the plate. Eg 8 to 10 are virtually bubble free. Ex. 9 has some surface bubbles on the mold side, but no internal bubbles. The addition of alkyl hydroxylamine (AO2) helps to melt the powders and remove internal bubbles. Accordingly, in exemplary embodiments, the rotational molded parts are substantially free of internal bubbles and/or substantially free of total bubbles (which includes surface bubbles and internal bubbles). Table 10
Examples 11 and 12, Experimental JL Comparatives
[00126] Blend formulations are blended using a W&P ZSK25 twin screw extruder. The formulations are shown in Table 11. For the formulations in Table 11, A02 can be added in place of or in addition to A01. Only the percentage of the added modifier is shown in the tables, the balance being the matrix materials. Samples are compression molded and cooled to 5°C min-1 between chilled rollers using circulating water. Table 11 Formulations

[00127] The properties of compression molded parts are shown in Table 12. Ex. J (MDPE) has good Izod hardness but low modulus. Eg K has good modulus and hardness but low ESCR (expected). Ex. L, being a non-compatibilized mixture, shows low impact strength. Ex 11 and 12 show a balanced property of good modulus (like at least 95 ksi, possibly with an upper limit of 1000 ksi), good impact strength, and good ESCR (expected). For example, the Izod impact @ 23 °C might be at least 10 KJ/m2, possibly with an upper limit of 1000 KJ/m2, the Izod impact @ 0 °C might be like at least 10 KJ/m2, possibly with a upper limit of 1000 KJ/m2, and the Izod impact @ -18 °C can be at least 9 KJ/m2 possibly with an upper limit of 1000 KJ/m2. Table 12 Physical Properties

权利要求:
Claims (8)
[0001]
1. Composition, characterized in that it comprises: a) one or more polyethylene; b) one or more polypropylene; c) one or more polyolefin elastomers; and d) a crystalline block composite comprising three components: i) a polymer based on crystalline ethylene, j)) a polymer based on crystalline propylene, and k) i) a block copolymer having a block based on crystalline ethylene and a block on propylene crystalline, wherein the composition of component i) is the same as the crystalline ethylene-based block of the block copolymer and the composition of component ii) is the same as the crystalline propylene block of the block copolymer; wherein the one or more polyolefin elastomers includes an olefin block copolymer having an ethylene/α-olefin copolymer.
[0002]
2. Composition according to claim 1, characterized in that the copolymer comprises from 5% by weight to 95% by weight of blocks based on crystalline ethylene and from 95% by weight to 5% by weight of crystalline propylene blocks .
[0003]
3. Composition according to any one of claims 1 or 2, characterized in that the block copolymer comprises from 30 to 70% by weight of blocks based on crystalline ethylene and 70 to 30% by weight of crystalline propylene blocks.
[0004]
4. Composition according to any one of claims 1 to 3, characterized in that the amount of one or more polyolefin elastomers is from 1% by weight to 45% by weight, based on the total weight of the composition.
[0005]
5. Composition according to any one of claims 1 to 4, characterized in that the block based on crystalline ethylene includes at least 85% by weight of ethylene and the polymer based on propylene is isotactic polypropylene.
[0006]
6. Composition according to any one of claims 1 to 5, characterized in that the block copolymers include 40% by weight to 60% by weight of crystalline propylene blocks, and a remainder of blocks based on crystalline ethylene based on the total weight of the block copolymers.
[0007]
7. Article, characterized in that it is prepared using the composition defined in any one of claims 1 to 6.
[0008]
8. Rotomolded article, characterized in that it is prepared using the composition defined in any one of claims 1 to 6.

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公开号 | 公开日 | 专利标题

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BR112016007421B1|2021-09-14|COMPOSITION, ARTICLE AND ROTOMOLDED ARTICLE

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KR101826210B1|2018-02-06|Crystalline block composites as compatibilizers

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CN107922686B|2021-01-08|Polyolefin blends including compatibilizers

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US8785554B2|2014-07-22|Crystalline block composites as compatibilizers

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JP5792294B2|2015-10-07|Crystalline block composites as compatibilizers

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BR112014014469B1|2020-09-08|COMPOSITION

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JP5595733B2|2014-09-24|Polyolefin composition

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KR101820183B1|2018-01-18|Crystalline block composites as compatibilizers

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WO2018049300A1|2018-03-15|Impact modified compositions for low temperature use containers

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TW201809107A|2018-03-16|Thermoplastic polyolefin blends having improved low temperature impact performance

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WO2011076555A1|2011-06-30|Impact-resistant polyolefin compositions

同族专利:

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公开号 | 公开日

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KR20160072128A|2016-06-22|

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ES2750647T3|2020-03-26|

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TW201527382A|2015-07-16|

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WO2015057423A1|2015-04-23|

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CN105593286B|2018-10-09|

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EP3058027A1|2016-08-24|

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JP2016537449A|2016-12-01|

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BR112016007421A2|2017-08-01|

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EP3058027B1|2019-08-14|

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JP2019116638A|2019-07-18|

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US9752024B2|2017-09-05|

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JP6853293B2|2021-03-31|

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TWI640562B|2018-11-11|

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US20160264765A1|2016-09-15|

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CN105593286A|2016-05-18|

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-03-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-03-16| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-06-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-09-14| 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 07/10/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361891245P| true| 2013-10-15|2013-10-15|

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US61/891,245|2013-10-15|

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PCT/US2014/059450|WO2015057423A1|2013-10-15|2014-10-07|Compatibilized polyolefin blends|

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