EP4608912A1 - Thermoplastic polyolefin composition with reactive compatibilization - Google Patents
Thermoplastic polyolefin composition with reactive compatibilizationInfo
- Publication number
- EP4608912A1 EP4608912A1 EP23844220.6A EP23844220A EP4608912A1 EP 4608912 A1 EP4608912 A1 EP 4608912A1 EP 23844220 A EP23844220 A EP 23844220A EP 4608912 A1 EP4608912 A1 EP 4608912A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- based polymer
- ethylene
- propylene
- functionalized
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C08F8/00—Chemical modification by after-treatment
- C08F8/08—Epoxidation
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
- C08L23/0884—Epoxide-containing esters
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with monomers containing atoms other than carbon, hydrogen or oxygen
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C08L23/147—Copolymers of propene with monomers containing atoms other than carbon or hydrogen
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/08—Low density, i.e. < 0.91 g/cm3
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/27—Amount of comonomer in wt% or mol%
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/34—Melting point [Tm]
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Definitions
- Polyolefin elastomers including ethylene/a-olefin copolymers are commonly used as impact modifiers for thermoplastic polyolefin (TPO) compounds.
- TPO thermoplastic polyolefin
- POEs can be applied to provide a balance of stiffness, impact toughness, and flow properties to the TPO.
- the present disclosure provides a composition.
- the composition includes (A) a nonfunctionalized propylene-based polymer, (B) a functionalized propylene-based polymer, and (C) a functionalized ethylene-based polymer.
- the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) each has a different functional group, the functional group selected from the group consisting of maleic anhydride and an epoxide.
- the numerical ranges disclosed herein include all values from, and including, the lower and upper value.
- any subrange between any two explicit values is included e.g., the range 1-7 above includes subranges of 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).
- composition refers to a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
- compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
- the term “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step, or procedure, excepting those that are not essential to operability.
- the term “consisting of” excludes any component, step, or procedure not specifically delineated or listed.
- An "ethylene-based polymer” or “ethylene polymer” is a polymer that contains a majority amount of polymerized ethylene based on the weight of the polymer and, optionally, may comprise at least one comonomer. Ethylene-based polymers typically comprise at least 50 mole percent (mol%) units derived from ethylene (based on the total amount of polymerizable monomers).
- heteroatom is an atom other than carbon or hydrogen.
- the heteroatom can be a non-carbon atom from Groups IV, V, VI and VII of the Periodic Table.
- Nonlimiting examples of heteroatoms include: F, Cl, N, O, P, B, S, and Si.
- a “hydrocarbon” is a compound containing only hydrogen atoms and carbon atoms.
- a “hydrocarbyl group” is a hydrocarbon having a valence (typically univalent).
- An "interpolymer” is a polymer prepared by the polymerization of at least two different types of monomers.
- the generic term interpolymer thus includes copolymers (employed to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
- An "olefin-based polymer” or “polyolefin” is a polymer that contains a majority mole percent polymerized olefin monomer (based on total amount of polymerizable monomers), and optionally, may contain at least one comonomer.
- Nonlimiting examples of olefin-based polymer include ethylene-based polymer and propylene-based polymer.
- polystyrene resin examples include polyethylene, polypropylene, polybutene, polyisoprene and their various interpolymers.
- a "polymer” is a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
- the generic term polymer thus embraces the term “homopolymer” (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term “interpolymer,” as defined hereinafter. Trace amounts of impurities, for example, catalyst residues, may be incorporated into and/or within the polymer. It also embraces all forms of copolymer, e.g., random, block, etc.
- ethylene/a-olefin polymer and "propylene/a-olefin polymer” are indicative of copolymer as described above prepared from polymerizing ethylene or propylene respectively and one or more additional, polymerizable a- olefin monomer.
- a polymer is often referred to as being "made of” one or more specified monomers, "based on” a specified monomer or monomer type, "containing” a specified monomer content, or the like, in this context the term “monomer” is understood to be referring to the polymerized remnant of the specified monomer and not to the unpolymerized species.
- polymers herein are referred to as being based on “units” that are the polymerized form of a corresponding monomer.
- a "propylene-based polymer” is a polymer that contains a majority amount of polymerized propylene based on the weight of the polymer and, optionally, may comprise at least one comonomer. Propylene-based polymers typically comprise at least 50 mole percent (mol%) units derived from propylene (based on the total amount of polymerizable monomers).
- Density is measured in accordance with ASTM D792, Method B (g/cc or g/cm 3 ).
- DSC Differential Scanning Calorimetry
- RCS refrigerated cooling system
- autosampler was used to perform this analysis.
- a nitrogen purge gas flow of 50 ml/min was used.
- Each sample was melt pressed into a thin film at 190°C; the melted sample was then air-cooled to room temperature (25°C).
- a 3-10 mg, 6 mm diameter specimen was extracted from the cooled polymer, weighed, placed in a light aluminum pan (ca 50 mg), and crimped shut. Analysis was then performed to determine its thermal properties.
- T g Glass transition temperature
- DMS Dynamic Mechanical Spectroscopy
- a constant temperature dynamic frequency sweep in the range of 0.1 to 100 rad/s, was performed under nitrogen, at 230 °C.
- a sample of approximately "25 mm diameter x 3.3 mm thick” was cut from a compression molded disc (see below). The sample was placed on the lower plate, and allowed to melt for five minutes. The plates were then closed to a gap of "2.0 mm,” and the sample trimmed to "25 mm” in diameter.
- the sample was allowed to equilibrate at 230 °C for five minutes, before starting the test.
- the complex viscosity was measured at a constant strain amplitude of 10%.
- the stress response was analyzed in terms of amplitude and phase, from which the storage modulus (G'), loss modulus (G"), dynamic viscosity q*, and tan delta could be calculated.
- G' storage modulus
- G loss modulus
- q* dynamic viscosity q*
- tan delta tan delta
- the complex viscosity, iq*, measured at a frequency of 100 rad/s is reported as V100.
- the rheology ratio, RR was calculated as the ratio of V0.1/V100.
- the tan delta measured at a frequency of 0.1 rad/s is reported as tan 6.
- MFR Melt Flow Rate
- Melt index (Ml) for ethylene-based polymers was measured in accordance with ASTM D1238, Condition 190°C/2.16 kilogram (kg) weight, also known as L, and is reported in g/10 min.
- Notched Izod Notched Izod impact tests were conducted according to ASTM D256, Method A. Specimens (2.5 inch long by 0.5 inch wide by 0.125 inch thick) were cut from compression molded plaques. The samples were conditioned for at least 40 hours at 23 +/- 2 °C and 50 +/- 10 % relative humidity. Testing was conducted at 23°C. The impact strength reported in kilojoules per square meter (kJ/m 2 ) is the average of results for three specimens.
- Tensile testing was conducted in accordance with ASTM D1708 using 3.2 mm thick microtensile bars cut from compression molded plaques. Tensile modulus (2% secant modulus) (reported in MPa) and tensile strain-at-break (reported in percent, %) are reported as the average for five specimens.
- the present disclosure provides a composition.
- the composition includes (A) a nonfunctionalized propylene-based polymer, (B) a functionalized propylene- based polymer, and (C) a functionalized ethylene-based polymer.
- the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) each has a different functional group.
- the functional groups for each of the functionalized propylene- based polymer (B) and the functionalized ethylene-based polymer (C) are selected from groups capable of reacting with each other to form a covalent bond between the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C).
- the functional group for each of the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) is selected from the group consisting of an anhydride and an epoxide.
- Nonfunctionalized propylene-based polymer [0028] The composition contains a nonfunctionalized propylene-based polymer.
- a "nonfunctionalized propylene-based polymer,” as used herein, is a propylene-based polymer containing nonfunctional groups, such that the nonfunctionalized propylene-based polymer is a hydrocarbon and is void of a heteroatom.
- Nonlimiting examples of propylene-based polymer include propylene homopolymer, propylene/a-olefin terpolymer, propylene/a-olefin copolymer, propylene impact copolymer, and combinations thereof.
- the nonfunctionalized propylene-based polymer is a propylene homopolymer.
- the propylene homopolymer has one, some, or all of the following properties;
- a MFR from 0.1 g/10 min to 500 g/ 10 min, or from 1 g/10 min to 150 g/10 min, or from 10 g/10 min to 120 g/10 min, or from 10 g/10 min to 40 g/10 min.
- the propylene-based polymer is a propylene/a-olefin copolymer.
- suitable a-olefins include C2 and C4-C20 a-olefins, or C4- C10 a-olefins, or C4-C8 a-olefins.
- Representative a-olefins include ethylene, 1-butene, 1- pentene, 1-hexene, 1-heptene and 1-octene.
- the propylene-based polymer is a propylene impact copolymer.
- the propylene impact copolymer is a heterophasic polymer wherein a rubber phase (or a discontinuous phase) of discrete domains of ethylene/propylene copolymer is dispersed throughout a matrix phase (or a continuous phase) of propylene homopolymer.
- the propylene impact copolymer contains from 1 wt% to 40 wt%, or from 5 wt% to 25 wt%, or from 8 wt% to 15 wt% ethylene/propylene rubber phase, based on the total weight of the propylene impact copolymer.
- the propylene impact copolymer has one, some, or all of the following properties:
- a MFR from 0.1 g/10 min to 500 g/ 10 min, or from 1 g/10 min to 150 g/10 min, or from 10 g/lOmin to 40 g/10 min.
- the present composition includes (B) a functionalized propylene-based polymer and (C) a functionalized ethylene-based polymer.
- the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) each has a respective functional group selected from an anhydride and an epoxide.
- the functional group of the functionalized propylene-based polymer (B) is different than the functional group for the functionalized ethylene-based polymer (C).
- the functional group for each of the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) is selected from two functional groups, namely an anhydride and an epoxide.
- the functional group of the functionalized propylene-based polymer (B) is an anhydride
- the functional group of the functionalized ethylenebased polymer (C) is an epoxide
- the functional group of the functionalized propylene- based polymer (B) is an epoxide
- the functional group of the functionalized ethylene-based polymer (C) is an anhydride.
- the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) each has "a different" functional group wherein the functional group of the functionalized propylene-based polymer is capable of reacting with the functional group of the functionalized ethylene-based polymer to form a covalent bond between the functionalized propylene-based polymer and the functionalized ethylene-based polymer.
- the present composition includes an epoxide functionalized propylene-based polymer or an epoxide functionalized ethylene-based polymer (collectively referred to as "epoxide- functionalized olefin-based polymer").
- the epoxide functionalized olefin-based polymer is prepared by melt blending either an ethylene-SiH polymer or a propylene-SiH polymer (collectively interchangeably referred to as "olefin-SiH polymer”) with a monovinyl epoxide component in the presence of a hydrosilylation catalyst.
- the olefin-SiH polymer is an ethylene-SiH polymer (an ethylene-based polymer) or a propylene-SiH polymer (a propylene-based polymer).
- An "ethylene-SiH polymer,” as used herein is composed of (1) ethylene monomer, (2) from 0.1 wt% to 3.9 wt% of a SiH comonomer, and (3) optional C3 a-olefin (propylene) or optional C4-C8 a-olefin termonomer.
- a "propylene-SiH polymer,” as used herein is composed of (1) propylene monomer, (2) from 0.1 wt% to 3.9 wt% of a SiH comonomer, and (3) optional C2 a-olefin (ethylene) or optional C4-C8 a-olefin termonomer.
- SiH comonomer (interchangeably referred to as “SiH”) as used herein, is a silane monomer of Formula 1:
- A-(SiBC-O) x -Si-EFH wherein A is an alkenyl group, B is a hydrocarbyl group or hydrogen,
- C is a hydrocarbyl group or hydrogen, and wherein B and C may be the same or different, and further B is a hydrocarbyl group, C is a hydrocarbyl group, and further B and C are the same;
- H is hydrogen, and x > 0;
- E is a hydrocarbyl group or hydrogen
- F is a hydrocarbyl group or hydrogen, E and F may be the same or different, when E is a hydrocarbyl group F is a hydrocarbyl group, E and F may be the same hydrocarbyl group.
- Nonlimiting samples of suitable SiH comonomer of Formula 1 include compounds (with structures shown below) si) (allyldimethylsilane), s2) (propenyldimethylsilane), s3)
- the SiH comonomer is selected from allyldimethylsilane, hexenyldimethylsilane, octenyldimethylsilane, and hexenyltetramethyldisiloxane.
- the ethylene-SiH polymer is an ethylene/a-olefin/SiH terpolymer.
- the a-olefin in the ethylene/a-olefin/SiH comonomer terpolymer can be a C3-C12 a-olefin or a C4-C8 a-olefin.
- Nonlimiting examples of suitable a-olefin include propylene, butene, hexene, octene, and ethylidene norbornene for respective ethylene/propylene SiH terpolymer, ethylene/butene/SiH terpolymer, ethylene/hexene/SiH terpolymer, ethylene/octene/SiH terpolymer and ethylene/ethylidene norbornene/SiH terpolymer.
- the olefin-SiH polymer is an ethylene/a-olefin/SiH terpolymer and is an ethylene/octene/SiH terpolymer.
- suitable ethylene/octene/SiH terpolymer include ethylene/octene/hexenyldimethylsilane (HDMS) terpolymer, ethylene/octene/octenyldimethylsilane (ODMS) terpolymer, ethylene/octene/allyldimethylsilane (ADMS) and combinations thereof.
- the ethylene-SiH polymer is ethylene/octene/hexenyldimethylsilane (HDMS).
- the ethylene-SiH polymer is ethylene/octene/allyldimethylsilane (ADMS) terpolymer.
- the olefin-SiH polymer is a propylene/SiH polymer.
- the propylene/SiH polymer (a propylene-based polymer) is propylene/HDMS copolymer or propylene/allyldimethylsilane copolymer.
- the olefin-SiH polymer is a propylene/ethylene SiH polymer.
- the propylene/ethylene/SiH polymer (a propylene-based polymer) is propylene/ethylene/HDMS terpolymer.
- a monovinyl epoxide component is melt blended with the olefin-SiH polymer (the ethylene-SiH polymer or the propylene-SiH polymer). In an embodiment, the melt blending occurs in the presence of a catalyst.
- the monovinyl epoxide component has a single vinyl group and has the Structure (1)
- X of Structure (1) is (i) a C4-C20 heterohydrocarbyl group with one or more heteroatoms selected from O, N, and Si and an epoxide moiety or (ii) a C4-C20 hydrocarbyl group with an epoxide moiety.
- Structure (1) include allyl glycidyl ether (structure (a) below), glycidyl methacrylate (structure (b) below), 3,4-epoxy-l-butene (structure (c) below), l,2-epoxy-5-hexene (structure (d) below), l,2-epoxy-9-decene
- the olefin-SiH polymer is melt blended with (ii) the monovinyl epoxide component in the presence of a catalyst.
- the catalyst accelerates the hydrosilylation reaction between the SiH moiety of the olefin-SiH polymer and the vinyl group of the monovinyl epoxide component of Structure (1).
- the hydrosilylation catalyst can be a platinum group metalcontaining catalyst.
- platinum group includes ruthenium, rhodium, palladium, osmium, iridium and platinum and complexes thereof.
- the platinum group- containing catalyst can be platinum group metal, platinum group metal deposited on a carrier such as silica gel or powdered charcoal, or a compound or complex of a platinum group metal.
- Nonlimiting examples of suitable platinum-containing catalysts include chloroplatinic acid, either in hexahydrate form or anhydrous form, and/or a platinum-containing catalyst which is obtained by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organoalkene-platinum-silyl complexes such as (CODjPtfSiMeC h, where COD is 1,5-cyclooctadiene and Me is methyl.
- organoalkene-platinum-silyl complexes such as (CODjPtfSiMeC h, where COD is 1,5-cyclooctadiene and Me is methyl.
- These alkene-platinum-silyl complexes may be prepared, for example by mixing 0.015 mole (CODjPtCh with 0.045 mole COD and 0.0612 moles HMeSiCh. The appropriate amount of the catalyst will depend upon the particular catalyst used.
- the platinum catalyst is present in an amount sufficient to provide at least 2 parts per million (ppm), or from 4 to 200 ppm of platinum based on total weight percent solids (all non-solvent ingredients) in the composition. Typically, the platinum is present in an amount sufficient to provide from 4 weight ppm to 150 weight ppm of platinum on the same basis.
- the catalyst may be added as a single species or as a mixture of two or more different species.
- the hydrosilylation catalyst is selected from Speier's catalyst (chloroplatinic acid), Karstedt's catalyst, Wilkinson's catalyst, and combinations thereof.
- the olefin-SiH polymer (the ethylene-SiH polymer or the propylene-SiH polymer), the monovinyl epoxide component, and the catalyst are melt blended, or otherwise mixed, at a temperature and for a length of time sufficient to fully homogenize the mixture. Melt blending is conducted by way of batch mixing or continuous mixing at a temperature from 80°C to 160°C, or from 80°C to 120°C for 1 minute to 20 minutes, or from 2 minutes to 15 minutes, or from 3 minutes to 10 minutes.
- the melt blending in the presence of the catalyst, initiates a hydrosilylation reaction between the Si-H moiety of the olefin-SiH polymer (the ethylene-SiH polymer or the propylene-SiH polymer) and the vinyl group of the monovinyl epoxide component, thereby grafting the monovinyl epoxide component to the ethylene-SiH polymer (or propylene-SiH polymer) to form an epoxide-silane functionalization to the olefin- based polymer (an epoxide-silane functionalized ethylene-based polymer or an epoxidesilane functionalized propylene-based polymer).
- An "epoxide-silane functionalized ethylene-based polymer,” as used herein, is the reaction product between the ethylene-SiH polymer and the monovinyl epoxide component whereby the monovinyl epoxide component is grafted to, or otherwise covalently bonded to, the ethylene-SiH polymer at the silicon atom of the SiH moiety by way of a Si-C-C-Y bond, wherein "Y” is a C4-C20 heterohydrocarbyl group, or a Cg-Cis heterohydrocarbyl group with a one or more heteroatoms selected from O, N, and Si. In an embodiment, "Y” is a C4-C20 heterohydrocarbyl group and includes an epoxide moiety.
- An "epoxide-silane functionalized propylene-based polymer,” as used herein, is the reaction product between the propylene-SiH polymer and the monovinyl epoxide component whereby the monovinyl epoxide component is grafted to, or otherwise covalently bonded to, the propylene-SiH polymer at the silicon atom of the SiH moiety by way of a Si-C- C-Y bond, wherein "Y” is a C4-C20 heterohydrocarbyl group with an epoxide moeity, or a Ce- Cig heterohydrocarbyl group with an epoxide moiety and one or more heteroatoms selected from O, N, and Si. In an embodiment, "Y” is a C4-C20 heterohydrocarbyl group and includes an epoxide moiety.
- the epoxy-silane functionalized ethylene-based polymer has the Structure (2A) below: Structure (2A) wherein R is a hexyl group, a hydrogen atom, or any combination thereof,
- R' is selected from the group consisting of Cl- and -(CH2)4-,
- R" is CH3
- Y is a heterohydrocarbyl group with an epoxide moiety.
- a "epoxide-silane propylene-based polymer,” as used herein, is the reaction product between the propylene-SiH polymer and the monovinyl epoxide component whereby the monovinyl epoxide component is grafted to, or otherwise covalently bonded to, the propylene-SiH polymer at the silicon atom of the Si H moiety by way of a Si-C-C-Y bond, wherein "Y” is a C4-C20 heterohydrocarbyl group with an epoxide moiety, or a C5-C18 heterohydrocarbyl group with an epoxide moiety.
- the epoxy-silane functionalized propylene-based polymer has the Structure (2B) below:
- R is a methyl group, a hydrogen atom, or any combination thereof
- R' is selected from the group consisting of Cl- and -(Cl-hh-, R" is CH3
- Y is a heterohydrocarbonyl group with an epoxide moiety.
- the epoxide-silane functionalized ethylene-based polymer is the reaction product of ethylene/octene/HDMS terpolymer and allyl glycidyl ether (hereafter "AGE-SiPOE”), and the AGE-SiPOE has the Structure (3) below:
- the present epoxide-silane olefin-based polymer may comprise two or more embodiments disclosed herein.
- the present composition includes an anhydride functionalized propylene-based polymer or an anhydride functionalized ethylene-based polymer (collectively referred to as "anhydride functionalized olefin-based polymer").
- anhydride functionalized olefin-based polymer is prepared by grafting via a free radical mechanism, for example initiated thermally or by a peroxide, maleic anhydride to an olefin-based polymer (ethylene-based polymer or propylene-based polymer).
- an "anhydride functionalized ethylene-based polymer,” as used herein, is an ethylene-based polymer with anhydride functional groups, the anhydride functional groups being pendant to the polymer chain backbone.
- the functionalized ethylene-based polymer contains from 0.1 wt% to 10 wt%, or from 0.1 wt% to 5 wt%, or from 0.3 wt% to 1.2 wt% anhydride functional group based on the total weight of the anhydride functionalized ethylenebased polymer.
- the anhydride functionalized ethylene-based polymer has a Ml (2.16 kg, 190 °C) from 1 g/10 min to 2000 g/10 min, or from 10 g/10 min to 500 g/10 min, or from 40 g/10 min to 150 g/10 min.
- the anhydride functional group is maleic anhydride (or MAH).
- the anhydride functionalized ethylene-based polymer is a maleic anhydride-grafted ethylene-based polymer
- the maleic anhydride-grafted ethylenebased polymer has (i) a melt index (2.16 kg, 190 °C) from 0.1 g/10 min to 2000 g/10 min, or from 0.2 g/10 min to 50 g/10 min, or from 0.3 g/10 min to 25 g/10 min, or from 1 g/10 min to 5 g/lOmin,
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/a-olefin copolymer.
- Representative a-olefins include, but are not limited to, C3-C20 a-olefins, or C3-C10 a-olefins, or C4-C20 a-olefins, or C4-C10 a-olefins, or C4- Cs a-olefins.
- Representative a-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1- heptene and 1-octene.
- the anhydride functionalized ethylene-based polymer is made using an ethylene/Cs-Cs a-olefin copolymer ("base ethylene/Cs-Cs a-olefin copolymer") having a density from 0.850 g/cc to 0.920 g/cc, or from 0.850 g/cc to 0.910 g/cc, or from 0.855 g/cc to 0.905 g/cc, or from 0.855 g/cc to 0.890 g/cc.
- base ethylene/Cs-Cs a-olefin copolymer having a density from 0.850 g/cc to 0.920 g/cc, or from 0.850 g/cc to 0.910 g/cc, or from 0.855 g/cc to 0.905 g/cc, or from 0.855 g/cc to 0.890 g/cc.
- the anhydride functionalized ethylene-based polymer is made using an ethylene/octene copolymer having a density from 0.850 g/cc to 0.920 g/cc, or from 0.850 g/cc to 0.910 g/cc, or from 0.855 g/cc to 0.905 g/cc, or from 0.855 g/cc to 0.890 g/cc.
- the anhydride functionalized ethylene-based polymer is made using an ethylene/octene multi-block copolymer having a density from 0.850 g/cc to 0.920 g/cc, or from 0.850 g/cc to 0.910 g/cc, or from 0.855 g/cc to 0.890 g/cc.
- an "anhydride functionalized propylene-based polymer,” as used herein, is a propylene-based polymer with anhydride functional groups that are pendant to the polymer chain backbone.
- the anhydride functionalized propylene-based polymer contains from 0.1 wt% to 10 wt%, or from 0.1 wt% to 5 wt%, or from 0.3 wt% to 1.2 wt% anhydride functional group based on the total weight of the anhydride functionalized propylene-based polymer.
- the anhydride functionalized propylene-based polymer has a MFR (2.16 kg, 190 °C) from 1 g/10 min to 2000 g/10 min, or from 10 g/10 min to 500 g/10 min, or from 40 g/10 min to 150 g/10 min.
- the anhydride functional group is maleic anhydride.
- the anhydride functionalized propylene-based polymer is a maleic anhydride-grafted propylene homopolymer
- the maleic anhydride-grafted propylene homopolymer has: (i) a melt flow rate (2.16 kg, 190 °C) from 1 g/10 min to 2000 g/10 min, or from
- a maleic anhydride content from 0.1 wt% to 10 wt%, based on the total weight of the maleic anhydride functionalized propylene-based polymer.
- the composition contains a nonfunctionalized ethylene-based polymer.
- a "nonfunctionalized ethylene-based polymer,” as used herein, is an ethylene-based polymer containing no functional groups, such that the nonfunctionalized ethylene-based polymer is a hydrocarbon and is void of a heteroatom.
- Nonlimiting examples of nonfunctionalized ethylene-based polymer include ethylene homopolymer, ethylene/a-olefin terpolymer, ethylene/a-olefin copolymer, ethylene/octene multi-block copolymer, and combinations thereof.
- the nonfunctionalized ethylene-based polymer is a nonfunctionalized ethylene/a-olefin copolymer.
- Representative a-olefins include, but are not limited to, C3-C20 a-olefins, or C3-C10 a-olefins, or C4-C20 a-olefins, or C4-C10 a-olefins, or C4-C8 a- olefins.
- Representative a-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.
- the nonfunctionalized ethylene-based polymer is a nonfunctionalized random ethylene/octene copolymer having one, some, or all of the following properties:
- a Ml from 0.1 g/10 min to 2000 g/10 min, or from 0.2 g/10 min to 50 g/10 min, or from 0.5 g/10 min to 35 g/10 min, or from 0.5 g/lOmin to 8 g/lOmin.
- the nonfunctionalized ethylene-based polymer is a nonfunctionalized ethylene/octene multi-block copolymer (consisting only of ethylene and octene comonomer) and has one, some, or all of the following properties:
- Tm a melting point, from 115°C, or 118°C, or 119°C, or 120°C to 120°C, or
- a Ml from 0.1 g/10 min to 2000 g/ 10 min, orfrom 0.2 g/10 min to 50 g/10 min, or from 0.5 g/10 min to 8 g/10 min; and/or
- a nonlimiting example of a suitable nonfunctionalized ethylene/octene multi-block copolymer is INFUSE 9530 available from Dow Inc.
- the present nonfunctionalized ethylene-based polymer may comprise two or more embodiments disclosed herein.
- the present composition may include one or more fillers.
- suitable filler include talc, mica, calcium carbonate, nanoclay, carbon nanotube, carbon nanofiber, and combinations thereof.
- the present composition may include a catalyst or initiator to accelerate the reaction between the epoxide and anhydride.
- a catalyst or initiator to accelerate the reaction between the epoxide and anhydride.
- suitable catalysts include, a substituted or unsubstituted imidazole, benzimidazole, amines, imidazolium salts, aliphatic or aromatic alcohols, and aliphatic or aromatic carboxylic acids.
- a nonlimiting example of a suitable catalyst is 2-undecylimidazole.
- the present composition is produced in a batch mixer, a continuous mixer, and combinations thereof.
- the present composition is produced in a continuous mixer.
- suitable continuous mixers include co-rotating twin screw extruders, counter-rotating continuous mixers, tangential counter-rotating twin screw extruders, reciprocating kneaders, single screw extruders, multi-screw planetary extruders, and combinations thereof.
- the continuous mixer can be used as a single unit or as a combination of multiple continuous mixers, in tandem, for example.
- the composition includes:
- compositions includes:
- compositions includes:
- melt index from 0.1 g/10 min to 1.0 g/10 min, or from 0.1 g/10 min to 0.9 g/10 min, or from 0.2 g/10 min to 0.8 g/10 min (2.16 Kg, 190°C),
- melt index from 1.0 g/ 10 min to 10 g/10 min, or from 2 g/10 min to 8 g/ 10 min (2.16 Kg, 190C);
- composition 0 wt%, or from 0.05 wt% to 1.0 wt%, or from 0.1 wt% to 1.0 wt%, or from 0.1 wt% to 0.9 wt% additives (hereafter composition!). Weight percent is based on total weight of the composition.
- the composition (composition!) has one, some, or all, or the following properties:
- a molded article composed of composition! has one, some, or all, of the following molded article properties:
- the compositions includes: (A) from 20 wt% to 98 wt%, or from 30 wt% to 95 wt%, or from 50 wt% to 85 wt%, or from 55 wt% to 75 wt% of the nonfunctionalized propylene-based polymer;
- compositions includes:
- the present composition composed of (A) nonfunctionalized propylene-based polymer, (Bl) anhydride functionalized propylene-based polymer (or (B2) epoxide-silane functionalized propylene-based polymer), (Cl) epoxide-silane functionalized ethylene-based polymer (or (C2) anhydride functionalized ethylene-based polymer), and (D) nonfunctionalized ethylene-based polymer undergo a reaction during compounding, wherein the functional groups of the functionalized propylene-based polymer react with the functional groups of the functionalized ethylene-based polymer to form covalent bonds between the functionalized propylene-based polymer and the functionalized ethylene-based polymer.
- the anhydride functional groups and the epoxide-silane functional groups undergo a reaction to form an ester linkage between the two functionalized polymers. Depending on the number of functional groups on each polymer, multiple ester bonds form between the functionalized polymer chains.
- Blends of the propylene-based polymers and ethylene-based polymers are immiscible. The propylene-based polymers and the ethylene-based polymers form separate domains in the blend.
- In-situ reaction between the functionalized propylene- based polymer and the functionalized ethylene-based polymer can improve the compatibility of the propylene-based polymer domains and the ethylene-based polymer domains and/or improve the interfacial strength between the propylene-based polymer domains and the ethylene-based polymer domains.
- the reaction during compounding results in a TPO composition with more shear-thinning rheology (as indicated by higher melt viscosity at low shear rates with similar melt viscosity at high shear rates) and higher melt elasticity (as indicated by lower tan 6), and that has improved impact toughness when molded into an article.
- the present composition provides an improved balance of stiffness and impact toughness.
- the present composition can be molded into an article.
- Many types of molding operations can be used to form articles or parts from the present composition, including, but not limited to, injection molding, blow molding, compression molding, profile and sheet extrusion, and thermoforming.
- the article is injection molded.
- Nonlimiting examples of molded articles formed from the present composition include automotive interior and exterior components such as bumper fascia, airbag covers, door trim panels, instrument panels, seat backrests, exterior body panels (liftgate panels, door panels, fenders), rocker panels, cladding, wheel flares; household and personal articles such as freezer containers, storage containers, toys, electronics and computer parts, footwear components, and building materials.
- the interpolymer SiH-POE E was prepared in a one gallon polymerization reactor that was hydraulically full, and operated at steady state conditions.
- the solvent was ISOPAR- E, supplied by the ExxonMobil Chemical Company.
- 5-Hexenyldimethylsilane (HDMS) supplied by Gelest was used as a termonomer and was purified over AZ-300 alumina supplied by UOP Honeywell prior to use.
- HDMS was fed to the reactor as a 22 wt% solution in ISOPAR-E.
- the reactor temperature was measured at or near the exit of the reactor.
- the interpolymer was isolated and pelletized. Polymerization conditions are listed in Table 1C-1E, and catalysts are shown in Table IB.
- the polymer properties for ethylene/octene/silane interpolymer (SiH-POE E) are shown in Table IE.
- Ethylene/l-octene/HDMS terpolymer (SiH-POE E) was added to a preheated Haake mixer (Haake mixer equipped with a 50-cc mixing bowl) at the specified temperature of 100°C with a blend rate of 100 rpm. Mixing continued until the polymer became homogeneous. The monovinyl epoxide component, allyl glycidyl ether, was added, and mixing was allowed to continue for 1-5 minutes. Then, Speier's catalyst (50 ppm Pt with respect to the polymer) was added as a solution in isopropanol (2 mg catalyst/1 mL solvent) and the hydrosilylation reaction was allowed to proceed for 10 minutes.
- the epoxide-silane functionalized ethylene-based polymer AGE- SiPOE
- Purification is performed by precipitation from hot toluene into methanol.
- the resulting material is characterized by proton NMR spectroscopy in 1, 1,2,2- tetrachloroethane-c/2.
- Samples for NMR were prepared at 100 °C in sufficient solvent to allow full dissolution of the polymer.
- Proton NMR spectra were acquired on a Bruker Ascend NEO 500 MHz instrument with a Prodigy Cryoprobe at 383 K with a 60 s recycle delay. Properties of the resultant functionalized polymer are provided in Table IF below.
- the polymer pellets were melt blended with the antioxidant, and optionally the Ul catalyst, in the ratios described in Table 2A in an RSI RS5000, RHEOMIX 600 Haake mixer, at 200°C/50 RPM, for five minutes.
- the hot sample was cooled in a Carver press (cooled platens) at 20000 psi, for four minutes, to make a "pancake sample” for further testing.
- Samples (4.5 inch x 4.5 inch x 0.125 inch) were then compression molded according to ASTM D4703. Notched Izod impact strength was measured according to ASTM D256, and microtensile testing was conducted according to ASTM D1708.
- the DMS frequency sweep measurements were conducted on a DMS-ARES-G2 rheometer from TA Instruments, using a 25 mm diameter parallel plate setup, at 230°C from 0.1-100 rad/s.
- Table 2A Compositions wt% - based on total weight of composition
- Table 2B Molded article properties made from the compositions of Table 2A
- Table 2A includes formulations and properties of the blends as prepared by Haake blending.
- Table 2B includes properties of compression molded parts made from the compositions comparative sample ("CS").
- CS A is a formulation without either functionalized component.
- Inventive Example (IE) IE1 and IE2 contain both functionalized components.
- inventive examples IE1 and IE2 have impact toughness (higher notched Izod impact strength), while maintaining similar stiffness (tensile modulus).
- IE1 and IE2 have similar high-shear viscosity (viscosity at 100 rad/s) as CS A, indicating similar flow properties for processes such as injection molding.
- IE1 and IE2 provide an improved balance of stiffness, toughness, and flow versus CS A. Furthermore, IE1 and IE2 have higher low-shear viscosity (viscosity at 0.1 rad/s) and lower tan delta than CS A, indicating higher melt elasticity for the inventive compositions. Higher melt elasticity can be beneficial for reducing tiger stripping in injection molded parts or improving processability for thermoformed or foamed compounds.
- IE2 has the highest impact strength, highest viscosity at 0.1 rad/s, and lowest tan 6 at 0.1 rad/s, indicating the addition of the Ul catalyst resulted in a higher degree of reaction between the maleic anhydride-grafted polypropylene and epoxy-silane functionalized ethylene-based polymer.
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Abstract
The present disclosure provides a composition. In an embodiment, the composition includes (A) a nonfunctionalized propylene-based polymer, (B) a functionalized propylene- based polymer, and (C) a functionalized ethylene-based polymer. The functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) each has a different functional group, the functional group selected from the group consisting of maleic anhydride and an epoxide.
Description
THERMOPLASTIC POLYOLEFIN COMPOSITION WITH REACTIVE COMPATIBILIZATION
BACKGROUND
[0001] Polyolefin elastomers (POEs), including ethylene/a-olefin copolymers are commonly used as impact modifiers for thermoplastic polyolefin (TPO) compounds. When blended with polypropylene, other additives, and optionally reinforcing fillers (such as talc), POEs can be applied to provide a balance of stiffness, impact toughness, and flow properties to the TPO.
[0002] The art recognizes the on-going need for blends that achieve greater impact efficiency and improved stiffness-toughness-flow balance in TPO compounds containing polypropylene. Further, the art recognizes the on-going need for TPO compounds with improved stiffness-toughness-flow- balance.
SUMMARY
[0003] The present disclosure provides a composition. In an embodiment, the composition includes (A) a nonfunctionalized propylene-based polymer, (B) a functionalized propylene-based polymer, and (C) a functionalized ethylene-based polymer. The functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) each has a different functional group, the functional group selected from the group consisting of maleic anhydride and an epoxide.
DEFINITIONS
[0004] Any reference to the Periodic Table of Elements is that as published by CRC Press, Inc., 1990-1991. Reference to a group of elements in this table is by the new notation for numbering groups.
[0005] For purposes of United States patent practice, the contents of any referenced patent, patent application or publication are incorporated by reference in their entirety (or its equivalent US version is so incorporated by reference) especially with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.
[0006] The numerical ranges disclosed herein include all values from, and including, the lower and upper value. For ranges containing explicit values (e.g., 1 or 2, or 3 to 5, or 6, or 7), any
subrange between any two explicit values is included e.g., the range 1-7 above includes subranges of 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).
[0007] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight, and all test methods are current as of the filing date of this disclosure.
[0008] The term "composition" refers to a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
[0009] The terms "comprising," "including," "having" and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any succeeding recitation any other component, step, or procedure, excepting those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically delineated or listed. The term "or," unless stated otherwise, refers to the listed members individually as well as in any combination. Use of the singular includes use of the plural and vice versa.
[0010] An "ethylene-based polymer" or "ethylene polymer" is a polymer that contains a majority amount of polymerized ethylene based on the weight of the polymer and, optionally, may comprise at least one comonomer. Ethylene-based polymers typically comprise at least 50 mole percent (mol%) units derived from ethylene (based on the total amount of polymerizable monomers).
[0011] A "heteroatom" is an atom other than carbon or hydrogen. The heteroatom can be a non-carbon atom from Groups IV, V, VI and VII of the Periodic Table. Nonlimiting examples of heteroatoms include: F, Cl, N, O, P, B, S, and Si.
[0012] A "hydrocarbon" is a compound containing only hydrogen atoms and carbon atoms. A "hydrocarbyl group" is a hydrocarbon having a valence (typically univalent).
[0013] An "interpolymer" is a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers (employed to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
[0014] An "olefin-based polymer" or "polyolefin" is a polymer that contains a majority mole percent polymerized olefin monomer (based on total amount of polymerizable monomers), and optionally, may contain at least one comonomer. Nonlimiting examples of olefin-based polymer include ethylene-based polymer and propylene-based polymer. Representative polyolefins include polyethylene, polypropylene, polybutene, polyisoprene and their various interpolymers. [0015] A "polymer" is a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term "homopolymer" (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term "interpolymer," as defined hereinafter. Trace amounts of impurities, for example, catalyst residues, may be incorporated into and/or within the polymer. It also embraces all forms of copolymer, e.g., random, block, etc. The terms "ethylene/a-olefin polymer" and "propylene/a-olefin polymer" are indicative of copolymer as described above prepared from polymerizing ethylene or propylene respectively and one or more additional, polymerizable a- olefin monomer. It is noted that although a polymer is often referred to as being "made of" one or more specified monomers, "based on" a specified monomer or monomer type, "containing" a specified monomer content, or the like, in this context the term "monomer" is understood to be referring to the polymerized remnant of the specified monomer and not to the unpolymerized species. In general, polymers herein are referred to as being based on "units" that are the polymerized form of a corresponding monomer.
[0016] A "propylene-based polymer" is a polymer that contains a majority amount of polymerized propylene based on the weight of the polymer and, optionally, may comprise at least one comonomer. Propylene-based polymers typically comprise at least 50 mole percent (mol%) units derived from propylene (based on the total amount of polymerizable monomers).
TEST METHODS
[0017] Density is measured in accordance with ASTM D792, Method B (g/cc or g/cm3).
[0018] Differential Scanning Calorimetry (DSC) can be used to measure the melting, crystallization, and glass transition behavior of a polymer over a wide range of temperature. For example, the TA Instruments Discovery DSC, equipped with an RCS (refrigerated cooling system) and an autosampler was used to perform this analysis. During testing, a nitrogen purge gas flow of 50 ml/min was used. Each sample was melt pressed into a thin film at 190°C; the melted sample was then air-cooled to room temperature (25°C). A 3-10 mg, 6 mm diameter specimen
was extracted from the cooled polymer, weighed, placed in a light aluminum pan (ca 50 mg), and crimped shut. Analysis was then performed to determine its thermal properties.
[0019] The thermal behavior of the sample was determined by ramping the sample temperature up and down to create a heat flow versus temperature profile. First, the sample was rapidly heated to 180°C and held isothermal for 3 minutes in order to remove its thermal history. Next, the sample was cooled to -80°C at a 10°C/minute cooling rate and held isothermal at -80°C for 3 minutes. The sample was then heated to 180°C (this is the "second heat" ramp) at a 10°C/minute heating rate. The cooling and second heating curves were recorded. The values determined are peak melting temperature, Tm, and peak crystallization temperature, Tc. Heat of fusion (Hf) (in Joules per gram), and the calculated % crystallinity for polyethylene samples using the Equation: % Crystallinity = ((Hf)/292 J/g) x 100.
[0020] The heat of fusion (Hf) and the peak melting temperature were reported from the second heat curve. Peak crystallization temperature was determined from the cooling curve.
[0021] Glass transition temperature, Tg, was determined from the DSC heating curve where half the sample has gained the liquid heat capacity as described in Bernhard Wunderlich, The Basis of Thermal Analysis, in Thermal Characterization of Polymeric Materials 92, 278-279 (Edith A. Turi ed., 2d ed. 1997). Baselines were drawn from below and above the glass transition region and extrapolated through the Tg region. The temperature at which the sample heat capacity was half-way between these baselines is the Tg.
[0022] Dynamic Mechanical Spectroscopy (DMS). The rheology of each composition was analyzed by DMS, using an Advanced Rheometric Expansion System (ARES), equipped with "25 mm stainless steel parallel plates," under a nitrogen purge. A constant temperature dynamic frequency sweep, in the range of 0.1 to 100 rad/s, was performed under nitrogen, at 230 °C. A sample of approximately "25 mm diameter x 3.3 mm thick" was cut from a compression molded disc (see below). The sample was placed on the lower plate, and allowed to melt for five minutes. The plates were then closed to a gap of "2.0 mm," and the sample trimmed to "25 mm" in diameter. The sample was allowed to equilibrate at 230 °C for five minutes, before starting the test. The complex viscosity was measured at a constant strain amplitude of 10%. The stress response was analyzed in terms of amplitude and phase, from which the storage modulus (G'), loss modulus (G"), dynamic viscosity q*, and tan delta could be calculated. Each compression molded disc was formed at 230 °C, and 10 MPa molding
pressure, for five minutes, ambient atmosphere, and then quenched between chilled platens (15-20°C) for two minutes. The complex viscosity, r)*, measured at a frequency of 0.1 rad/s is reported as V0.1. The complex viscosity, iq*, measured at a frequency of 100 rad/s is reported as V100. The rheology ratio, RR, was calculated as the ratio of V0.1/V100. The tan delta measured at a frequency of 0.1 rad/s is reported as tan 6.
[0023] Melt Flow Rate (MFR) for propylene-based polymers was measured according to ASTM D1238, Condition 230°C/2.16 kilogram (kg) weight unless otherwise noted.
[0024] Melt index (Ml) for ethylene-based polymers was measured in accordance with ASTM D1238, Condition 190°C/2.16 kilogram (kg) weight, also known as L, and is reported in g/10 min. [0025] Notched Izod. Notched Izod impact tests were conducted according to ASTM D256, Method A. Specimens (2.5 inch long by 0.5 inch wide by 0.125 inch thick) were cut from compression molded plaques. The samples were conditioned for at least 40 hours at 23 +/- 2 °C and 50 +/- 10 % relative humidity. Testing was conducted at 23°C. The impact strength reported in kilojoules per square meter (kJ/m2) is the average of results for three specimens. [0026] Tensile testing. Tensile testing was conducted in accordance with ASTM D1708 using 3.2 mm thick microtensile bars cut from compression molded plaques. Tensile modulus (2% secant modulus) (reported in MPa) and tensile strain-at-break (reported in percent, %) are reported as the average for five specimens.
DETAILED DESCRIPTION
[0027] The present disclosure provides a composition. In an embodiment, the composition includes (A) a nonfunctionalized propylene-based polymer, (B) a functionalized propylene- based polymer, and (C) a functionalized ethylene-based polymer. The functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) each has a different functional group. The functional groups for each of the functionalized propylene- based polymer (B) and the functionalized ethylene-based polymer (C) are selected from groups capable of reacting with each other to form a covalent bond between the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C). The functional group for each of the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) is selected from the group consisting of an anhydride and an epoxide.
A. Nonfunctionalized propylene-based polymer
[0028] The composition contains a nonfunctionalized propylene-based polymer. A "nonfunctionalized propylene-based polymer," as used herein, is a propylene-based polymer containing nonfunctional groups, such that the nonfunctionalized propylene-based polymer is a hydrocarbon and is void of a heteroatom. Nonlimiting examples of propylene-based polymer include propylene homopolymer, propylene/a-olefin terpolymer, propylene/a-olefin copolymer, propylene impact copolymer, and combinations thereof.
[0029] In an embodiment, the nonfunctionalized propylene-based polymer is a propylene homopolymer. The propylene homopolymer has one, some, or all of the following properties;
(i) a density from 0.89 g/cc to 0.91 g/cc, or 0.90 g/cc; and/or
(ii) a MFR from 0.1 g/10 min to 500 g/ 10 min, or from 1 g/10 min to 150 g/10 min, or from 10 g/10 min to 120 g/10 min, or from 10 g/10 min to 40 g/10 min.
[0030] In an embodiment, the propylene-based polymer is a propylene/a-olefin copolymer. Nonlimiting examples of suitable a-olefins include C2 and C4-C20 a-olefins, or C4- C10 a-olefins, or C4-C8 a-olefins. Representative a-olefins include ethylene, 1-butene, 1- pentene, 1-hexene, 1-heptene and 1-octene.
[0031] In an embodiment, the propylene-based polymer is a propylene impact copolymer. The propylene impact copolymer is a heterophasic polymer wherein a rubber phase (or a discontinuous phase) of discrete domains of ethylene/propylene copolymer is dispersed throughout a matrix phase (or a continuous phase) of propylene homopolymer. The propylene impact copolymer contains from 1 wt% to 40 wt%, or from 5 wt% to 25 wt%, or from 8 wt% to 15 wt% ethylene/propylene rubber phase, based on the total weight of the propylene impact copolymer.
[0032] In an embodiment, the propylene impact copolymer has one, some, or all of the following properties:
(i) from 1 wt% to 40 wt%, or from 5 wt% to 25 wt%, or from 8 wt% to 15 wt% ethylene/propylene rubber phase; and/or
(ii) a density from 0.88 g/cc to 0.90 g/cc; and/or
(iii) a MFR from 0.1 g/10 min to 500 g/ 10 min, or from 1 g/10 min to 150 g/10 min, or from 10 g/lOmin to 40 g/10 min.
B. Epoxide functionalized polymer
[0033] The present composition includes (B) a functionalized propylene-based polymer and (C) a functionalized ethylene-based polymer. The functionalized propylene-based polymer (B)
and the functionalized ethylene-based polymer (C) each has a respective functional group selected from an anhydride and an epoxide. The functional group of the functionalized propylene-based polymer (B) is different than the functional group for the functionalized ethylene-based polymer (C). The functional group for each of the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) is selected from two functional groups, namely an anhydride and an epoxide. When the functional group of the functionalized propylene-based polymer (B) is an anhydride, the functional group of the functionalized ethylenebased polymer (C) is an epoxide. When the functional group of the functionalized propylene- based polymer (B) is an epoxide, the functional group of the functionalized ethylene-based polymer (C) is an anhydride. In this way, the functionalized propylene-based polymer (B) and the functionalized ethylene-based polymer (C) each has "a different" functional group wherein the functional group of the functionalized propylene-based polymer is capable of reacting with the functional group of the functionalized ethylene-based polymer to form a covalent bond between the functionalized propylene-based polymer and the functionalized ethylene-based polymer.
[0034] The present composition includes an epoxide functionalized propylene-based polymer or an epoxide functionalized ethylene-based polymer (collectively referred to as "epoxide- functionalized olefin-based polymer"). In an embodiment, the epoxide functionalized olefin-based polymer is prepared by melt blending either an ethylene-SiH polymer or a propylene-SiH polymer (collectively interchangeably referred to as "olefin-SiH polymer") with a monovinyl epoxide component in the presence of a hydrosilylation catalyst.
[0035] The olefin-SiH polymer is an ethylene-SiH polymer (an ethylene-based polymer) or a propylene-SiH polymer (a propylene-based polymer). An "ethylene-SiH polymer," as used herein is composed of (1) ethylene monomer, (2) from 0.1 wt% to 3.9 wt% of a SiH comonomer, and (3) optional C3 a-olefin (propylene) or optional C4-C8 a-olefin termonomer. A "propylene-SiH polymer," as used herein is composed of (1) propylene monomer, (2) from 0.1 wt% to 3.9 wt% of a SiH comonomer, and (3) optional C2 a-olefin (ethylene) or optional C4-C8 a-olefin termonomer.
[0036] An "SiH comonomer," (interchangeably referred to as "SiH") as used herein, is a silane monomer of Formula 1:
(Formula 1)
A-(SiBC-O)x-Si-EFH wherein A is an alkenyl group,
B is a hydrocarbyl group or hydrogen,
C is a hydrocarbyl group or hydrogen, and wherein B and C may be the same or different, and further B is a hydrocarbyl group, C is a hydrocarbyl group, and further B and C are the same;
H is hydrogen, and x > 0;
E is a hydrocarbyl group or hydrogen,
F is a hydrocarbyl group or hydrogen, E and F may be the same or different, when E is a hydrocarbyl group F is a hydrocarbyl group, E and F may be the same hydrocarbyl group.
Nonlimiting samples of suitable SiH comonomer of Formula 1 include compounds (with structures shown below) si) (allyldimethylsilane), s2) (propenyldimethylsilane), s3)
(butenyldimethylsilane), s4) (hexenyldimethylsilane), s5) (octenyldimethylsilane), s6),
(decenyldimethylsilane), s7) norbornylethyldimethylsilane, s8) octahydrodimethanonaphthalenylethyldimethysilane, s9) vinyltetramethyldisiloxane, slO) allyltetramethyldisiloxane, sll) _butenyltetramethyldisiloxane, sl2, hexenyltetra methyldisiloxane, sl3) octenyltetramethyldisiloxane, sl4) decenyltetra methyldisiloxane, sl5) norbornylethyltetramethyldisiloxane, sl6) octahydrodimethanonaphthalenylethyltetramethyldisiloxane below:
[0037] In an embodiment, the SiH comonomer is selected from allyldimethylsilane, hexenyldimethylsilane, octenyldimethylsilane, and hexenyltetramethyldisiloxane.
[0038] In an embodiment, the ethylene-SiH polymer is an ethylene/a-olefin/SiH terpolymer. The a-olefin in the ethylene/a-olefin/SiH comonomer terpolymer can be a C3-C12 a-olefin or a C4-C8 a-olefin. Nonlimiting examples of suitable a-olefin include propylene, butene, hexene, octene, and ethylidene norbornene for respective ethylene/propylene SiH terpolymer, ethylene/butene/SiH terpolymer, ethylene/hexene/SiH terpolymer, ethylene/octene/SiH terpolymer and ethylene/ethylidene norbornene/SiH terpolymer.
[0039] In an embodiment, the olefin-SiH polymer is an ethylene/a-olefin/SiH terpolymer and is an ethylene/octene/SiH terpolymer. Nonlimiting examples of suitable ethylene/octene/SiH terpolymer include ethylene/octene/hexenyldimethylsilane (HDMS) terpolymer, ethylene/octene/octenyldimethylsilane (ODMS) terpolymer, ethylene/octene/allyldimethylsilane (ADMS) and combinations thereof.
[0040] In an embodiment, the ethylene-SiH polymer is ethylene/octene/hexenyldimethylsilane (HDMS).
[0041] In an embodiment, the ethylene-SiH polymer is ethylene/octene/allyldimethylsilane (ADMS) terpolymer.
[0042] In an embodiment, the olefin-SiH polymer is a propylene/SiH polymer. In a further embodiment, the propylene/SiH polymer (a propylene-based polymer) is propylene/HDMS copolymer or propylene/allyldimethylsilane copolymer.
[0043] In an embodiment, the olefin-SiH polymer is a propylene/ethylene SiH polymer. In a further embodiment, the propylene/ethylene/SiH polymer (a propylene-based polymer) is propylene/ethylene/HDMS terpolymer.
[0044] A monovinyl epoxide component is melt blended with the olefin-SiH polymer (the ethylene-SiH polymer or the propylene-SiH polymer). In an embodiment, the melt blending occurs in the presence of a catalyst. The monovinyl epoxide component has a single vinyl group and has the Structure (1)
Structure (1)
H2C=CH2-X wherein X of Structure (1) is (i) a C4-C20 heterohydrocarbyl group with one or more heteroatoms selected from O, N, and Si and an epoxide moiety or (ii) a C4-C20 hydrocarbyl group with an epoxide moiety. Nonlimiting examples of Structure (1) include allyl glycidyl ether (structure (a) below), glycidyl methacrylate (structure (b) below), 3,4-epoxy-l-butene
(structure (c) below), l,2-epoxy-5-hexene (structure (d) below), l,2-epoxy-9-decene
(structure (e) below), and 4-vinyl-l-cyclohexene 1,2-epoxide (structure (f) below).
Structure (a) Structure (b) Structure (c)
Structure (d) Structure (e) Structure (f)
[0045] In an embodiment, (i) the olefin-SiH polymer is melt blended with (ii) the monovinyl epoxide component in the presence of a catalyst. The catalyst accelerates the hydrosilylation reaction between the SiH moiety of the olefin-SiH polymer and the vinyl group of the monovinyl epoxide component of Structure (1).
[0046] In an embodiment, the hydrosilylation catalyst can be a platinum group metalcontaining catalyst. The term "platinum group," as used herein, includes ruthenium, rhodium, palladium, osmium, iridium and platinum and complexes thereof. The platinum group- containing catalyst can be platinum group metal, platinum group metal deposited on a carrier such as silica gel or powdered charcoal, or a compound or complex of a platinum group metal. Nonlimiting examples of suitable platinum-containing catalysts include chloroplatinic acid, either in hexahydrate form or anhydrous form, and/or a platinum-containing catalyst which is obtained by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organoalkene-platinum-silyl complexes such as (CODjPtfSiMeC h, where COD is 1,5-cyclooctadiene and Me is methyl. These alkene-platinum-silyl complexes may be prepared, for example by mixing 0.015 mole (CODjPtCh with 0.045 mole COD and 0.0612 moles HMeSiCh. The appropriate amount of the catalyst will depend upon the particular catalyst used. In an further embodiment, the platinum catalyst is present in an amount sufficient to provide at least 2 parts per million (ppm), or from 4 to 200 ppm of platinum based on total weight percent solids (all non-solvent ingredients) in the composition. Typically, the platinum is present in an amount sufficient to provide from 4 weight ppm to 150 weight ppm of platinum on the same basis. The catalyst may be added as a single species or as a mixture of two or more different species.
[0047] In an embodiment, the hydrosilylation catalyst is selected from Speier's catalyst (chloroplatinic acid), Karstedt's catalyst, Wilkinson's catalyst, and combinations thereof.
[0048] The olefin-SiH polymer (the ethylene-SiH polymer or the propylene-SiH polymer), the monovinyl epoxide component, and the catalyst are melt blended, or otherwise mixed, at a temperature and for a length of time sufficient to fully homogenize the mixture. Melt blending is conducted by way of batch mixing or continuous mixing at a temperature from 80°C to 160°C, or from 80°C to 120°C for 1 minute to 20 minutes, or from 2 minutes to 15 minutes, or from 3 minutes to 10 minutes. The melt blending, in the presence of the catalyst, initiates a hydrosilylation reaction between the Si-H moiety of the olefin-SiH polymer (the ethylene-SiH polymer or the propylene-SiH polymer) and the vinyl group of the monovinyl epoxide component, thereby grafting the monovinyl epoxide component to the ethylene-SiH polymer (or propylene-SiH polymer) to form an epoxide-silane functionalization to the olefin- based polymer (an epoxide-silane functionalized ethylene-based polymer or an epoxidesilane functionalized propylene-based polymer).
[0049] An "epoxide-silane functionalized ethylene-based polymer," as used herein, is the reaction product between the ethylene-SiH polymer and the monovinyl epoxide component whereby the monovinyl epoxide component is grafted to, or otherwise covalently bonded to, the ethylene-SiH polymer at the silicon atom of the SiH moiety by way of a Si-C-C-Y bond, wherein "Y" is a C4-C20 heterohydrocarbyl group, or a Cg-Cis heterohydrocarbyl group with a one or more heteroatoms selected from O, N, and Si. In an embodiment, "Y" is a C4-C20 heterohydrocarbyl group and includes an epoxide moiety.
[0050] An "epoxide-silane functionalized propylene-based polymer," as used herein, is the reaction product between the propylene-SiH polymer and the monovinyl epoxide component whereby the monovinyl epoxide component is grafted to, or otherwise covalently bonded to, the propylene-SiH polymer at the silicon atom of the SiH moiety by way of a Si-C- C-Y bond, wherein "Y" is a C4-C20 heterohydrocarbyl group with an epoxide moeity, or a Ce- Cig heterohydrocarbyl group with an epoxide moiety and one or more heteroatoms selected from O, N, and Si. In an embodiment, "Y" is a C4-C20 heterohydrocarbyl group and includes an epoxide moiety.
[0051] In an embodiment, the epoxy-silane functionalized ethylene-based polymer has the Structure (2A) below:
Structure (2A)
wherein R is a hexyl group, a hydrogen atom, or any combination thereof,
R' is selected from the group consisting of Cl- and -(CH2)4-,
R" is CH3, and
Y is a heterohydrocarbyl group with an epoxide moiety.
[0052] A "epoxide-silane propylene-based polymer," as used herein, is the reaction product between the propylene-SiH polymer and the monovinyl epoxide component whereby the monovinyl epoxide component is grafted to, or otherwise covalently bonded to, the propylene-SiH polymer at the silicon atom of the Si H moiety by way of a Si-C-C-Y bond, wherein "Y" is a C4-C20 heterohydrocarbyl group with an epoxide moiety, or a C5-C18 heterohydrocarbyl group with an epoxide moiety.
[0053] In an embodiment, the epoxy-silane functionalized propylene-based polymer has the Structure (2B) below:
Structure (2B)
wherein R is a methyl group, a hydrogen atom, or any combination thereof, R' is selected from the group consisting of Cl- and -(Cl-hh-, R" is CH3, and
Y is a heterohydrocarbonyl group with an epoxide moiety.
[0054] In an embodiment, the epoxide-silane functionalized ethylene-based polymer is the reaction product of ethylene/octene/HDMS terpolymer and allyl glycidyl ether (hereafter "AGE-SiPOE"), and the AGE-SiPOE has the Structure (3) below:
Structure (3)
[0055] The present epoxide-silane olefin-based polymer may comprise two or more embodiments disclosed herein.
C. Anhydride functionalized polymer
[0056] The present composition includes an anhydride functionalized propylene-based polymer or an anhydride functionalized ethylene-based polymer (collectively referred to as "anhydride functionalized olefin-based polymer"). Nonlimiting examples of suitable anhydride- functionalized olefin-based polymers are prepared by grafting via a free radical mechanism, for example initiated thermally or by a peroxide, maleic anhydride to an olefin-based polymer (ethylene-based polymer or propylene-based polymer).
[0057] An "anhydride functionalized ethylene-based polymer," as used herein, is an ethylene-based polymer with anhydride functional groups, the anhydride functional groups being pendant to the polymer chain backbone. The functionalized ethylene-based polymer contains from 0.1 wt% to 10 wt%, or from 0.1 wt% to 5 wt%, or from 0.3 wt% to 1.2 wt% anhydride functional group based on the total weight of the anhydride functionalized ethylenebased polymer. The anhydride functionalized ethylene-based polymer has a Ml (2.16 kg, 190 °C) from 1 g/10 min to 2000 g/10 min, or from 10 g/10 min to 500 g/10 min, or from 40 g/10 min to 150 g/10 min. In an embodiment, the anhydride functional group is maleic anhydride (or MAH). [0058] In embodiment, the anhydride functionalized ethylene-based polymer is a maleic anhydride-grafted ethylene-based polymer, and the maleic anhydride-grafted ethylenebased polymer has
(i) a melt index (2.16 kg, 190 °C) from 0.1 g/10 min to 2000 g/10 min, or from 0.2 g/10 min to 50 g/10 min, or from 0.3 g/10 min to 25 g/10 min, or from 1 g/10 min to 5 g/lOmin,
(ii) a maleic anhydride content from 0.1 wt% to 10 wt%, based on the total weight of the functionalized ethylene-based polymer, and
(iii) a base ethylene/Cs-Cs a-olefin copolymer having a density from 0.850 g/cc to 0.920 g/cc, or from 0.860 g/cc to 0.900 g/cc.
[0059] In an embodiment, the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/a-olefin copolymer. Representative a-olefins include, but are not limited to, C3-C20 a-olefins, or C3-C10 a-olefins, or C4-C20 a-olefins, or C4-C10 a-olefins, or C4- Cs a-olefins. Representative a-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1- heptene and 1-octene.
[0060] In an embodiment, the anhydride functionalized ethylene-based polymer is made using an ethylene/Cs-Cs a-olefin copolymer ("base ethylene/Cs-Cs a-olefin copolymer") having a density from 0.850 g/cc to 0.920 g/cc, or from 0.850 g/cc to 0.910 g/cc, or from 0.855 g/cc to 0.905 g/cc, or from 0.855 g/cc to 0.890 g/cc.
[0061] In an embodiment, the anhydride functionalized ethylene-based polymer is made using an ethylene/octene copolymer having a density from 0.850 g/cc to 0.920 g/cc, or from 0.850 g/cc to 0.910 g/cc, or from 0.855 g/cc to 0.905 g/cc, or from 0.855 g/cc to 0.890 g/cc.
[0062] In an embodiment, the anhydride functionalized ethylene-based polymer is made using an ethylene/octene multi-block copolymer having a density from 0.850 g/cc to 0.920 g/cc, or from 0.850 g/cc to 0.910 g/cc, or from 0.855 g/cc to 0.890 g/cc.
[0063] An "anhydride functionalized propylene-based polymer," as used herein, is a propylene-based polymer with anhydride functional groups that are pendant to the polymer chain backbone. The anhydride functionalized propylene-based polymer contains from 0.1 wt% to 10 wt%, or from 0.1 wt% to 5 wt%, or from 0.3 wt% to 1.2 wt% anhydride functional group based on the total weight of the anhydride functionalized propylene-based polymer. The anhydride functionalized propylene-based polymer has a MFR (2.16 kg, 190 °C) from 1 g/10 min to 2000 g/10 min, or from 10 g/10 min to 500 g/10 min, or from 40 g/10 min to 150 g/10 min. In an embodiment, the anhydride functional group is maleic anhydride.
[0064] In an embodiment, the anhydride functionalized propylene-based polymer is a maleic anhydride-grafted propylene homopolymer, and the maleic anhydride-grafted propylene homopolymer has:
(i) a melt flow rate (2.16 kg, 190 °C) from 1 g/10 min to 2000 g/10 min, or from
10 g/10 min to 500 g/10 min, or from 40 g/10 min to 150 g/10 min, and
(ii) a maleic anhydride content from 0.1 wt% to 10 wt%, based on the total weight of the maleic anhydride functionalized propylene-based polymer.
D. Nonfunctionalized ethylene-based polymer
[0065] In an embodiment, the composition contains a nonfunctionalized ethylene-based polymer. A "nonfunctionalized ethylene-based polymer," as used herein, is an ethylene-based polymer containing no functional groups, such that the nonfunctionalized ethylene-based polymer is a hydrocarbon and is void of a heteroatom.
[0066] Nonlimiting examples of nonfunctionalized ethylene-based polymer include ethylene homopolymer, ethylene/a-olefin terpolymer, ethylene/a-olefin copolymer, ethylene/octene multi-block copolymer, and combinations thereof.
[0067] In an embodiment, the nonfunctionalized ethylene-based polymer is a nonfunctionalized ethylene/a-olefin copolymer. Representative a-olefins include, but are not limited to, C3-C20 a-olefins, or C3-C10 a-olefins, or C4-C20 a-olefins, or C4-C10 a-olefins, or C4-C8 a- olefins. Representative a-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.
[0068] In an embodiment, the nonfunctionalized ethylene-based polymer is a nonfunctionalized random ethylene/octene copolymer having one, some, or all of the following properties:
(i) a density from 0.850 g/cc to 0.920 g/cc, or from 0.850 g/cc to 0.910 g/cc, or from 0.860 g/cc to 0.905 g/cc, or from 0.860 g/cc to 0.890 g/cc; and/or
(ii) a Ml from 0.1 g/10 min to 2000 g/10 min, or from 0.2 g/10 min to 50 g/10 min, or from 0.5 g/10 min to 35 g/10 min, or from 0.5 g/lOmin to 8 g/lOmin.
[0069] In an embodiment, the nonfunctionalized ethylene-based polymer is a nonfunctionalized ethylene/octene multi-block copolymer (consisting only of ethylene and octene comonomer) and has one, some, or all of the following properties:
(i) a Mw/Mn from 1.7, or 1.8 to 2.2, or 2.5, or 3.5; and/or
(ii) a density from 0.850 g/cc to 0.920 g/cc, or from 0.850 g/cc to 0.910 g/cc, or from 0.860 g/cc to 0.890 g/cc ; and/or
(iii) a melting point, Tm, from 115°C, or 118°C, or 119°C, or 120°C to 120°C, or
123°C, or 125°C; and/or
(iv) a Ml from 0.1 g/10 min to 2000 g/ 10 min, orfrom 0.2 g/10 min to 50 g/10 min, or from 0.5 g/10 min to 8 g/10 min; and/or
(v) 50-93 wt% soft segment and 50-7 wt% hard segment; and/or
(vi) from 10 mol%, or 13 mol%, or 14 mol%, or 15 mol% to 16 mol%, or 17 mol%, or 18 mol%, or 19 mol%, or 20 mol% C4-C12 a-olefin in the soft segment; and/or
(vii) from 0.5 mol%, or 1.0 mol%, or 2.0 mol%, or 3.0 mol% to 4.0 mol%, or 5 mol%, or 6 mol%, or 7 mol%, or 9 mol% octene in the hard segment; and/or
(viii) an elastic recovery (Re) from 50%, or 60% to 70%, or 80%, or 90%, at 300%/min deformation rate at 21°C as measured in accordance with ASTM D 1708; and/or
(ix) a polydisperse distribution of blocks and a polydisperse distribution of block sizes. Ethylene/octene multi-block copolymer with properties (i)-(ix) is disclosed US Patent No. 7,608,668 the entire contents of which are incorporated by reference herein.
[0070] A nonlimiting example of a suitable nonfunctionalized ethylene/octene multi-block copolymer is INFUSE 9530 available from Dow Inc.
[0071] The present nonfunctionalized ethylene-based polymer may comprise two or more embodiments disclosed herein.
E. Filler
[0072] In an embodiment, the present composition may include one or more fillers. Nonlimiting examples of suitable filler include talc, mica, calcium carbonate, nanoclay, carbon nanotube, carbon nanofiber, and combinations thereof.
F. Catalyst
[0073] In an embodiment, the present composition may include a catalyst or initiator to accelerate the reaction between the epoxide and anhydride. Nonlimiting examples of suitable catalysts include, a substituted or unsubstituted imidazole, benzimidazole, amines, imidazolium salts, aliphatic or aromatic alcohols, and aliphatic or aromatic carboxylic acids. A nonlimiting example of a suitable catalyst is 2-undecylimidazole.
G. Composition
[0074] The present composition is produced in a batch mixer, a continuous mixer, and combinations thereof. In an embodiment, the present composition is produced in a continuous mixer. Nonlimiting examples of suitable continuous mixers include co-rotating twin screw extruders, counter-rotating continuous mixers, tangential counter-rotating twin screw extruders, reciprocating kneaders, single screw extruders, multi-screw planetary extruders, and
combinations thereof. The continuous mixer can be used as a single unit or as a combination of multiple continuous mixers, in tandem, for example.
[0075] In an embodiment, the composition includes:
(A) from 20 wt% to 98 wt%, or from 30 wt% to 95 wt%, or from 50 wt% to 85 wt%, or from 55 wt% to 75 wt% of the nonfunctionalized propylene-based polymer;
(B) from 1 wt% to 50 wt%, or from 1 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 7 wt% of the maleic anhydride-functionalized propylene-based polymer; and
(C) from 1 wt% to 50 wt%, or from 1 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 7 wt% of the epoxide-silane functionalized ethylene-based polymer. Weight percent is based on total weight of the composition.
[0076] In an embodiment, the compositions includes:
(A) from 20 wt% to 98 wt%, or from 30 wt% to 95 wt%, or from 50 wt% to 85 wt%, or from 55 wt% to 75 wt% of the nonfunctionalized propylene-based polymer;
(B) from 1 wt% to 50 wt%, or from 1 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 7 wt% of the maleic anhydride-functionalized propylene-based polymer; and
(C) from 1 wt% to 50 wt%, or from 1 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 7 wt% of the epoxide-silane functionalized ethylene-based polymer;
(D) from 10 wt% to 40 wt%, or from 15 wt% to 30 wt%, or from 20 wt% to 30 wt% of the nonfunctionalized ethylene-based polymer; and
(E) 0 wt%, or from 0.05 wt% to 1.0 wt%, or from 0.1 wt% to 1.0 wt%, or from 0.1 wt% to 0.9 wt% one or more additives. Weight percent is based on total weight of the composition.
[0077] In an embodiment, the compositions includes:
(A) from 20 wt% to 98 wt%, or from 30 wt% to 95 wt%, or from 50 wt% to 85 wt%, or from 55 wt% to 75 wt% of a nonfunctionalized propylene homopolymer having
(i) an MFR from 5.0 g/10 min to 15 g/10 min, or from 8.0 g/10 min to 13.0 g/10 min (2.16 kg, 230°C);
(B) from 1 wt% to 50 wt%, or from 1 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 7 wt% of the maleic anhydride-functionalized propylene homopolymer having
(i) from 0.1 wt% to 1.0 wt%, or 0.2 wt% to 0.8 wt% MAH (based on total weight of the maleic anhydride functionalized propylene homopolymer),
(ii) a MFR from 70 g/10 min to 150 g/10 min, or from 80 g/10 min to 140 g/10 min, or from 90 g/10 min to 135 g/10 min, or from 100 g/10 min to 130 g/10 min (2.16 Kg, 190°C);
(C) from 1 wt% to 50 wt%, or from 1 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 7 wt% of the epoxide-silane functionalized ethylene terpolymer having
(i) a density from 0.85 g/cc to 0.89 g/cc, or from 0.86 g/cc to 0.88 g/cc,
(ii) a melt index from 0.1 g/10 min to 1.0 g/10 min, or from 0.1 g/10 min to 0.9 g/10 min, or from 0.2 g/10 min to 0.8 g/10 min (2.16 Kg, 190°C),
(iii) a termonomer selected from HDMS or ODMS;
(D) from 10 wt% to 40 wt%, or from 15 wt% to 30 wt%, or from 20 wt% to 30 wt% of the nonfunctionalized ethylene-based polymer that is an ethylene/octene multi-block copolymer having
(i) a density from 0.86 g/cc to 0.89 g/cc, or from 0.87 g/cc to 0.89 g/cc,
(ii) a melt index from 1.0 g/ 10 min to 10 g/10 min, or from 2 g/10 min to 8 g/ 10 min (2.16 Kg, 190C); and
(E) 0 wt%, or from 0.05 wt% to 1.0 wt%, or from 0.1 wt% to 1.0 wt%, or from 0.1 wt% to 0.9 wt% additives (hereafter composition!). Weight percent is based on total weight of the composition. The composition (composition!) has one, some, or all, or the following properties:
(i) a viscosity at 0.1 rad/s (230 °C) from 1600 Pa.s to 2,600 Pa.s, or from 1700 Pa.s to 2,500 Pa.s, and/or
(ii) a viscosity at 100 rad/s (230 °C) from 300 Pa.s to 500 Pa.s, or from 330 Pa.s to 400 Pa.s; and/or
(iii) a tan 6 at 0.1 rad/s from 1.0 to 5.0, or from 1.5 to 3.0. In an embodiment, a molded article composed of composition! has one, some, or all, of the following molded article properties:
(iv) a tensile strain at break value from 50% to 100%, or from 51% to 90%, and/or
(v) a notched Izod impact strength at 23 °C from 5.0 kJ/m2 to 20.0 kJ/m2 or from 7.0 kJ/m2 to 18.0 kJ/m2, and/or
(vi) a tensile modulus (2% secant) from 500 MPa to 700 MPa, or from 550 MPa to 650
MPa.
[0078] In an embodiment, the compositions includes:
(A) from 20 wt% to 98 wt%, or from 30 wt% to 95 wt%, or from 50 wt% to 85 wt%, or from 55 wt% to 75 wt% of the nonfunctionalized propylene-based polymer;
(B) from 1 wt% to 50 wt%, or from 1 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 7 wt% of the epoxide-silane functionalized propylene-based polymer; and
(C) from 1 wt% to 50 wt%, or from 1 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 7 wt% of the maleic anhydride functionalized ethylene-based polymer. Weight percent is based on total weight of the composition.
[0079] In an embodiment, the compositions includes:
(A) from 20 wt% to 98 wt%, or from 30 wt% to 95 wt%, or from 50 wt% to 85 wt%, or from 55 wt% to 75 wt% of the nonfunctionalized propylene-based polymer;
(B) from 1 wt% to 50 wt%, or from 1 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 7 wt% of the epoxide-silane functionalized propylene-based polymer;
(C) from 1 wt% to 50 wt%, or from 1 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 7 wt% of the epoxide-silane functionalized ethylene-based polymer;
(D) from 10 wt% to 40 wt%, or from 15 wt% to 30 wt%, or from 20 wt% to 25 wt% of the nonfunctionalized ethylene-based polymer; and
(E) 0 wt%, or from 0.05 wt% to 1.0 wt%, or from 0.1 wt% to 1.0 wt%, or from 0.1 wt% to 0.9 wt% additives Weight percent is based on total weight of the composition.
[0080] The present composition composed of (A) nonfunctionalized propylene-based polymer, (Bl) anhydride functionalized propylene-based polymer (or (B2) epoxide-silane functionalized propylene-based polymer), (Cl) epoxide-silane functionalized ethylene-based polymer (or (C2) anhydride functionalized ethylene-based polymer), and (D) nonfunctionalized ethylene-based polymer undergo a reaction during compounding, wherein the functional groups of the functionalized propylene-based polymer react with the functional groups of the functionalized ethylene-based polymer to form covalent bonds between the functionalized propylene-based polymer and the functionalized ethylene-based polymer. The anhydride functional groups and the epoxide-silane functional groups undergo a reaction to form an ester linkage between the two functionalized polymers. Depending on the number of functional groups on each polymer, multiple ester bonds form between the functionalized polymer chains. Blends of the propylene-based polymers and ethylene-based polymers are immiscible. The propylene-based polymers and the ethylene-based polymers form separate domains in the blend. In-situ reaction between the functionalized propylene-
based polymer and the functionalized ethylene-based polymer can improve the compatibility of the propylene-based polymer domains and the ethylene-based polymer domains and/or improve the interfacial strength between the propylene-based polymer domains and the ethylene-based polymer domains. The reaction during compounding results in a TPO composition with more shear-thinning rheology (as indicated by higher melt viscosity at low shear rates with similar melt viscosity at high shear rates) and higher melt elasticity (as indicated by lower tan 6), and that has improved impact toughness when molded into an article. The present composition provides an improved balance of stiffness and impact toughness.
G. Article
[0081] The present composition can be molded into an article. Many types of molding operations can be used to form articles or parts from the present composition, including, but not limited to, injection molding, blow molding, compression molding, profile and sheet extrusion, and thermoforming. In an embodiment, the article is injection molded. Nonlimiting examples of molded articles formed from the present composition include automotive interior and exterior components such as bumper fascia, airbag covers, door trim panels, instrument panels, seat backrests, exterior body panels (liftgate panels, door panels, fenders), rocker panels, cladding, wheel flares; household and personal articles such as freezer containers, storage containers, toys, electronics and computer parts, footwear components, and building materials.
[0082] By way of example, and not limitation, examples of the present disclosure are provided.
EXAMPLES
[0083] The materials used in comparatives samples (CS) and inventive examples (IE) are provided in Table A below.
Table A: Materials
1. Preparation of SiH POE
[0001] The interpolymer SiH-POE E , was prepared in a one gallon polymerization reactor that was hydraulically full, and operated at steady state conditions. The solvent was ISOPAR- E, supplied by the ExxonMobil Chemical Company. 5-Hexenyldimethylsilane (HDMS) supplied by Gelest was used as a termonomer and was purified over AZ-300 alumina supplied by UOP Honeywell prior to use. HDMS was fed to the reactor as a 22 wt% solution in ISOPAR-E. The reactor temperature was measured at or near the exit of the reactor. The interpolymer was isolated and pelletized. Polymerization conditions are listed in Table 1C-1E, and catalysts are shown in Table IB. The polymer properties for ethylene/octene/silane interpolymer (SiH-POE E) are shown in Table IE.
21
SUBSTITUTE SHEET (RULE 26)
Table IB: Catalysts and co-catalysts
SUBSTITUTE SHEET (RULE 26)
Table 1C: Polymerization Conditions to produce SiH-POE E
Table ID: Catalyst Feed Flows and Efficiency
*The "ppm" amount based on the weight of the respective catalyst feed solution. **The "ppm" amount based on the weight of the co-catalyst feed solution.
***The "ppm" amount of Al based on the weight of the co-catalyst feed solution.
Table IE: Polymer Properties
*Mol% silane based on total moles of monomers in polymer, and determined by 13C NMR.
1. Preparation of AGE-SiPOE
[0085] Ethylene/l-octene/HDMS terpolymer (SiH-POE E) was added to a preheated Haake mixer (Haake mixer equipped with a 50-cc mixing bowl) at the specified temperature of 100°C with a blend rate of 100 rpm. Mixing continued until the polymer became homogeneous. The monovinyl epoxide component, allyl glycidyl ether, was added, and mixing was allowed to continue for 1-5 minutes. Then, Speier's catalyst (50 ppm Pt with respect to the polymer) was added as a solution in isopropanol (2 mg catalyst/1 mL solvent) and the hydrosilylation reaction was allowed to proceed for 10 minutes. At the conclusion of the hydrosilylation reaction, the epoxide-silane functionalized ethylene-based polymer, AGE- SiPOE, was collected. Purification is performed by precipitation from hot toluene into methanol. The resulting material is characterized by proton NMR spectroscopy in 1, 1,2,2- tetrachloroethane-c/2. Samples for NMR were prepared at 100 °C in sufficient solvent to allow full dissolution of the polymer. Proton NMR spectra were acquired on a Bruker Ascend NEO
500 MHz instrument with a Prodigy Cryoprobe at 383 K with a 60 s recycle delay. Properties of the resultant functionalized polymer are provided in Table IF below.
Table IF
2. Preparation of composition
[0086] For each composition, the polymer pellets were melt blended with the antioxidant, and optionally the Ul catalyst, in the ratios described in Table 2A in an RSI RS5000, RHEOMIX 600 Haake mixer, at 200°C/50 RPM, for five minutes. The hot sample was cooled in a Carver press (cooled platens) at 20000 psi, for four minutes, to make a "pancake sample" for further testing. Samples (4.5 inch x 4.5 inch x 0.125 inch) were then compression molded according to ASTM D4703. Notched Izod impact strength was measured according to ASTM D256, and microtensile testing was conducted according to ASTM D1708. The DMS frequency sweep measurements were conducted on a DMS-ARES-G2 rheometer from TA Instruments, using a 25 mm diameter parallel plate setup, at 230°C from 0.1-100 rad/s.
Table 2A: Compositions
wt% - based on total weight of composition
Table 2B: Molded article properties made from the compositions of Table 2A
[0087] Table 2A includes formulations and properties of the blends as prepared by Haake blending. Table 2B includes properties of compression molded parts made from the compositions comparative sample ("CS"). CS A is a formulation without either functionalized component. Inventive Example (IE) IE1 and IE2 contain both functionalized components. As compared to comparative example CS A, inventive examples IE1 and IE2 have impact toughness (higher notched Izod impact strength), while maintaining similar stiffness (tensile modulus). Meanwhile, IE1 and IE2 have similar high-shear viscosity (viscosity at 100 rad/s) as CS A, indicating similar flow properties for processes such as injection molding. Therefore, IE1 and IE2 provide an improved balance of stiffness, toughness, and flow versus CS A. Furthermore, IE1 and IE2 have higher low-shear viscosity (viscosity at 0.1 rad/s) and lower tan delta than CS A, indicating higher melt elasticity for the inventive compositions. Higher melt elasticity can be beneficial for reducing tiger stripping in injection molded parts or improving processability for thermoformed or foamed compounds. IE2 has the highest impact strength, highest viscosity at 0.1 rad/s, and lowest tan 6 at 0.1 rad/s, indicating the addition of the Ul catalyst resulted in a higher degree of reaction between the maleic anhydride-grafted polypropylene and epoxy-silane functionalized ethylene-based polymer.
[0088] It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.
Claims
1. A composition comprising:
(A) a nonfunctionalized propylene-based polymer;
(B) a functionalized propylene-based polymer, and
(C) a functionalized ethylene-based polymer, the functionalized propylene-based polymer (B) and the functionalized ethylenebased polymer (C) each having a different functional group, the functional group selected from the group consisting of maleic anhydride and an epoxide.
2. The composition of claim 1 comprising
(A) from 20 wt% to 98 wt% nonfunctionalized propylene-based polymer;
(B) from 1 wt% to 50 wt% maleic anhydride-grafted propylene-based polymer; and
(C) from 1 wt% to 50 wt% epoxy functionalized ethylene-based polymer.
3. The composition of claim 2 wherein the maleic anhydride-grafted propylene-based polymer is a maleic anhydride-grafted propylene homopolymer having
(i) a melt flow rate (2.16 kg, 190 °C) from 1 g/10 min to 2000 g/10 min, and
(ii) a maleic anhydride content from 0.1 wt% to 10 wt%, based on the total weight of the functionalized propylene-based polymer.
4. The composition of any of claims 2-3 wherein the epoxy functionalized ethylenebased polymer has
(i) a density from 0.85 g/cc to 0.89 g/cc,
(ii) a melt index from 0.1 g 10 min to 1.0 g/ 10 min, and
(iii) a termonomer selected from the group consisting of allyldimethylsilane, hexenyldimethylsilane and octenyldimethylsilane.
5. The composition of claim 4 wherein the epoxy functionalized ethylene-based polymer is an epoxy-silane functionalized ethylene-based polymer having a Structure (2A) below
Structure (2A)
wherein R is a hexyl group, a hydrogen atom, or any combination thereof, R' is selected from the group consisting of Cl- and -(Cl- h-, R" is CH3, and
Y is a heterohydrocarbyl group with an epoxide.
6. The composition of claim 5 wherein the epoxy-silane functionalized ethylene-based polymer has a Structure 3 below
7. The composition of any of claims 1-6 comprising
(D) a nonfunctionalized ethylene-based polymer.
8. The composition of claim 7 wherein the nonfunctionalized ethylene-based polymer is an ethylene/C3-C8 a-olefin copolymer having
(i) a density from 0.850 g/cc to 0.920 g/cc, and
(ii) a melt index (2.16 kg, 190 °C) from 0.1 g/10 min to 2000 g/10 min.
9. The composition of any of claims 7-8 comprising:
(A) from 50 wt% to 85 wt% of a nonfunctionalized propylene homopolymer;
(B) from 1 wt% to 10 wt% of a maleic anhydride-functionalized propylene homopolymer;
(C) from 1 wt% to 10 wt% of an epoxide-silane functionalized ethylene terpolymer;
(D) from 15 wt% to 30 wt%, of the nonfunctionalized ethylene-based polymer; and
(E) from 0 wt% to 1.0 wt% additives.
10. The composition of claim 9 wherein the composition has a property selected from the group consisting of
(i) a viscosity at 0.1 rad/s (230 °C) from 1600 Pa.s to 2,600 Pa.s,
(ii) a viscosity at 100 rad/s (230 °C) from 300 Pa.s to 500 Pa.s,
(iii) a tan 5 at 0.1 rad/s from 1.0 to 5.0, and
(iv) combinations thereof.
11. A molded article composed of the composition of claim 10, the molded article having a molded article property selected from the group consisting of
(i) a tensile strain at break value from 50% to 100%,
(ii) a notched Izod impact strength at 23 °C from 5.0 kJ/m2 to 20.0 kJ/m2,
(iii) a tensile modulus (2% secant) from 500 MPa to 700 MPa , and
(iv) combinations thereof.
12. The composition of claim 1 comprising:
(A) from 20 wt% to 98 wt% nonfunctionalized propylene-based polymer;
(B) from 1 wt% to 50 wt% epoxy-silane functionalized propylene-based polymer; and
(C) from 1 wt% to 50 wt% maleic anhydride-grafted ethylene-based polymer.
13. The composition of claim 12 comprising:
(D) a nonfunctionalized ethylene-based polymer.
14. The composition of claim 13 wherein the nonfunctionalized ethylene-based polymer is an ethylene/Cs-Cg a-olefin copolymer having
(i) a density from 0.850 g/cc to 0.920 g/cc, and
(ii) a melt index (2.16 kg, 190 °C) from 0.1 g/10 min to 2000 g/10 min.
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| US202263387444P | 2022-12-14 | 2022-12-14 | |
| PCT/US2023/082325 WO2024129419A1 (en) | 2022-12-14 | 2023-12-04 | Thermoplastic polyolefin composition with reactive compatibilization |
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| EP (1) | EP4608912A1 (en) |
| JP (1) | JP2025542583A (en) |
| KR (1) | KR20250121322A (en) |
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| US5721314A (en) * | 1993-12-07 | 1998-02-24 | E. I. Du Pont De Nemours And Company | Thermoformable thermoplastic polymer alloy compositions |
| US5395881A (en) * | 1994-03-04 | 1995-03-07 | E. I. Du Pont De Nemours And Company | Flexible polar thermoplastic polyolefin compositions |
| US7608668B2 (en) | 2004-03-17 | 2009-10-27 | Dow Global Technologies Inc. | Ethylene/α-olefins block interpolymers |
| JP2009221349A (en) * | 2008-03-17 | 2009-10-01 | Sumitomo Chemical Co Ltd | Propylene based resin composition and its molded article |
| US20150104597A1 (en) * | 2013-10-16 | 2015-04-16 | E. I. Du Pont De Nemours And Company | Double component system for polyolefin compatibilization |
| WO2020169548A1 (en) * | 2019-02-18 | 2020-08-27 | Total Research & Technology Feluy | Polyolefin compositions and process to produce such compositions by the addition of coupling agents |
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