Patent Description:
Thermoplastics polymers have become ubiquitous in everyday life. For example, thermoplastic polymers are used in a variety of durable goods (e.g., home appliances, consumer electronics, furniture, and automobiles), consumable goods, and packaging materials for such goods. The ubiquity of thermoplastic polymers combined with an increase in recycling rates has enabled resin producers to introduce resin grades containing a significant amount of recycled material, such as post-consumer recycled (PCR) material (e.g., <NUM>-<NUM>% PCR content). While these recycled resins are beneficial from a sustainability standpoint, the resins frequently exhibit diminished physical properties relative to <NUM>% virgin resins. For example, the recycled resins typically exhibit lower impact strength and stiffness. Further, many recycled resins typically exhibit a relatively low melt flow rate (MFR), which can necessitate the use of a peroxide to increase the MFR into a desirable range for processing. However, increasing the MFR with a peroxide typically leads to further reductions in the impact resistance and stiffness of the recycled resin. Accordingly, when extant technologies are used in conjunction with recycled resins, one must strike a compromise between increasing the PCR content and undesirably decreasing the impact resistance and stiffness of the resulting polymer composition.

<CIT> discloses a thermoplastic heterophasic polymer composition comprises a propylene polymer phase, an ethylene polymer phase, and a specified compatibilizing agent comprising a fulvene moiety or a fulvene-derived moiety.

<CIT> relates to a method of creating a modified heterophasic polyolefin composition, whereby a polyolefin composition having at least two phases is melt-mixed with a free radical generator, such as a peroxide, and a compatibilizing agent characterized by at least one nitroxide radical and at least one unsaturated bond capable of undergoing a radical addition reaction.

A need therefore remains for additives and processes that can produce polymer compositions having high recycled polymer content while maintaining, or even improving, the impact resistance of the polymer composition relative to compositions having lower recycled polymer content.

In a first embodiment, the invention provides a method for producing a polymer composition, the method comprising the steps of:.

The following definitions are provided to define several of the terms used throughout this application.

The term "recycled polymer" refers to post-consumer recycled polymer, post-industrial recycled polymer, and mixtures thereof.

The term "post-consumer recycled" (PCR) refers to material (e.g., a polymer or polymers) that has reached the intended end user or consumer, is no longer being used for its intended purpose, and which has been collected or reclaimed after it is discarded by the end user or consumer. Thus, for example, it is understood that the term refers to material that would have otherwise been disposed of as waste, but has instead been collected and recovered (reclaimed) as a material input, in lieu of new virgin material, for a recycling or manufacturing process. The term is inclusive of such collected or reclaimed materials which have been further treated or processed to facilitate re-use of the material. Thus, for example, the term is inclusive of material that has been reprocessed from collected or reclaimed material by means of a manufacturing process and made into a product or into a component for incorporation into a product.

The term "post-industrial recycled" (PIR) refers to material (e.g., a polymer or polymers) that has never reached the end user and has been collected or reclaimed from a waste stream produced in a manufacturing process. The term "post-industrial recycled" does not include materials that are generated in a manufacturing process and then are reused as a substitute for a raw material in the same manufacturing process, such as regrind polymer that is collected from the waste stream of a manufacturing process (e.g., a thermoforming process), ground to reduce its size, and then reused as a substituted for virgin polymer in the same manufacturing process (e.g., the same thermoforming process). The term is inclusive of such collected or reclaimed materials which have been further treated or processed to facilitate re-use of the material in another manufacturing process.

The term "hydrocarbyl groups" refers to univalent functional groups derived from hydrocarbons by removal of a hydrogen atom from a carbon atom of the hydrocarbon.

The term "substituted hydrocarbyl groups" refers to univalent functional groups derived from substituted hydrocarbons by removal of a hydrogen atom from a carbon atom of the substituted hydrocarbon. In this definition, the term "substituted hydrocarbon" refers to compounds derived from acyclic, monocyclic, and polycyclic, unbranched and branched hydrocarbons in which (<NUM>) one or more of the hydrogen atoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., a halogen atom) or a non-hydrocarbyl functional group (e.g., a hydroxy group or heteroaryl group) and/or (<NUM>) the carbon-carbon chain of the hydrocarbon is interrupted by an oxygen atom (e.g., as in an ether), a nitrogen atom (e.g., as in an amine), or a sulfur atom (e.g., as in a sulfide).

The term "substituted alkyl groups" refers to univalent functional groups derived from substituted alkanes by removal of a hydrogen atom from a carbon atom of the alkane. In this definition, the term "substituted alkanes" refers to compounds derived from acyclic unbranched and branched hydrocarbons in which (<NUM>) one or more of the hydrogen atoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., a halogen atom) or a non-alkyl functional group (e.g., hydroxy, aryl, or heteroaryl) and/or (<NUM>) the carbon-carbon chain of the hydrocarbon is interrupted by an oxygen atom (as in an ether), a nitrogen atom (as in an amine), or a sulfur atom (as in a sulfide).

The term "substituted cycloalkyl groups" refers to univalent functional groups derived from substituted cycloalkanes by removal of a hydrogen atom from a carbon atom of the cycloalkane. In this definition, the term "substituted cycloalkanes" refers to compounds derived from saturated monocyclic and polycyclic hydrocarbons (with or without side chains) in which (<NUM>) one or more of the hydrogen atoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., halogen) or a non-alkyl functional group (e.g., hydroxy, aryl, or heteroaryl) and/or (<NUM>) the carbon-carbon chain of the hydrocarbon is interrupted by an oxygen atom, a nitrogen atom, or a sulfur atom.

The term "alkenyl groups" refers to univalent functional groups derived from acyclic, unbranched and branched olefins (i.e., hydrocarbons having one or more carbon-carbon double bonds) by removal of a hydrogen atom from a carbon atom of the olefin.

The term "substituted alkenyl groups" refers to univalent functional groups derived from acyclic, substituted olefins by removal of a hydrogen atom from a carbon atom of the olefin. In this definition, the term "substituted olefins" refers to compounds derived from acyclic, unbranched and branched hydrocarbons having one or more carbon-carbon double bonds in which (<NUM>) one or more of the hydrogen atoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., halogen) or a non-alkyl functional group (e.g., hydroxy, aryl, heteroaryl) and/or (<NUM>) the carbon-carbon chain of the hydrocarbon is interrupted by an oxygen atom (as in an ether) or a sulfur atom (as in a sulfide).

The term "substituted cycloalkenyl groups" refers to univalent functional groups derived from substituted cycloalkenes by removal of a hydrogen atom from a carbon atom of the cycloalkene. In this definition, the term "substituted cycloalkenes" refers to compounds derived from monocyclic and polycyclic olefins (i.e., hydrocarbons having one or more carbon-carbon double bonds) in which one or more of the hydrogen atoms of the olefin is replaced with a non-hydrogen atom (e.g., halogen) or a non-alkyl functional group (e.g., hydroxy, aryl, or heteroaryl).

The term "substituted aryl groups" refers to univalent functional groups derived from substituted arenes by removal of a hydrogen atom from a ring carbon atom. In this definition, the term "substituted arenes" refers to compounds derived from monocyclic and polycyclic aromatic hydrocarbons in which one or more of the hydrogen atoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., halogen) or a non-alkyl functional group (e.g., hydroxy).

The term "substituted heteroaryl groups" refers to univalent functional groups derived from substituted heteroarenes by removal of a hydrogen atom from a ring atom. In this definition, the term "substituted heteroarenes" refers to compounds derived from monocyclic and polycyclic aromatic hydrocarbons in which (<NUM>) one or more of the hydrogen atoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., halogen) or a non-alkyl functional group (e.g., hydroxy) and (<NUM>) at least one methine group (-C=) of the hydrocarbon is replaced by a trivalent heteroatom and/or at least one vinylidene group (-CH=CH-) of the hydrocarbon is replaced by a divalent heteroatom.

The term "alkanediyl groups" refers to divalent functional groups derived from alkanes by removal of two hydrogen atoms from the alkane. These hydrogen atoms can be removed from the same carbon atom on the alkane (as in ethane-<NUM>,<NUM>-diyl) or from different carbon atoms (as in ethane-<NUM>,<NUM>-diyl).

The term "substituted alkanediyl groups" refers to divalent functional groups derived from substituted alkanes by removal of two hydrogen atoms from the alkane. These hydrogen atoms can be removed from the same carbon atom on the substituted alkane (as in <NUM>-fluoroethane-<NUM>,<NUM>-diyl) or from different carbon atoms (as in <NUM>-fluoroethane-<NUM>,<NUM>-diyl). In this definition, the term "substituted alkanes" has the same meaning as set forth above in the definition of substituted alkyl groups.

The term "cycloalkanediyl groups" refers to divalent functional groups derived from cycloalkanes (monocyclic and polycyclic) by removal of two hydrogen atoms from the cycloalkane. These hydrogen atoms can be removed from the same carbon atom on the cycloalkane or from different carbon atoms.

The term "substituted cycloalkanediyl groups" refers to divalent functional groups derived from substituted cycloalkanes by removal of two hydrogen atoms from the cycloalkane. In this definition, the term "substituted cycloalkanes" has the same meaning as set forth above in the definition of substituted cycloalkyl groups.

The term "cycloalkenediyl groups" refers to divalent functional groups derived from cycloalkenes (monocyclic and polycyclic) by removal of two hydrogen atoms from the cycloalkene. These hydrogen atoms can be removed from the same carbon atom on the cycloalkene or from different carbon atoms.

The term "substituted cycloalkenediyl groups" refers to divalent functional groups derived from substituted cycloalkenes by removal of two hydrogen atoms from the cycloalkene. These hydrogen atoms can be removed from the same carbon atom on the cycloalkene or from different carbon atoms. In this definition, the term "substituted cycloalkenes" has the same meaning as set forth above in the definition of substituted cycloalkene groups.

The term "arenediyl groups" refers to divalent functional groups derived from arenes (monocyclic and polycyclic aromatic hydrocarbons) by removal of two hydrogen atoms from ring carbon atoms.

The term "substituted arenediyl groups" refers to divalent functional groups derived from substituted arenes by removal of two hydrogen atoms from ring carbon atoms. In this definition, the term "substituted arenes" refers to compounds derived from monocyclic and polycyclic aromatic hydrocarbons in which one or more of the hydrogen atoms of the hydrocarbon is replaced with a non-hydrogen atom (e.g., a halogen atom) or a non-alkyl functional group (e.g., hydroxy).

The term "heteroarenediyl groups" refers to divalent functional groups derived from heteroarenes by removal of two hydrogen atoms from ring atoms. In this definition, the term "heteroarenes" refers to compounds derived from monocyclic and polycyclic aromatic hydrocarbons in which at least one methine group (-C=) of the hydrocarbon is replaced by a trivalent heteroatom and/or at least one vinylidene group (-CH=CH-) of the hydrocarbon is replaced by a divalent heteroatom.

The term "substituted heteroarenediyl groups" refers to divalent functional groups derived from substituted heteroarenes by removal of two hydrogen atoms from ring atoms. In this definition, the term "substituted heteroarenes" has the same meaning as set forth above in the definition of substituted heteroaryl groups.

Unless otherwise indicated, conditions are <NUM>, <NUM> atmosphere of pressure and <NUM>% relative humidity, concentrations are by weight, and molecular weight is based on weight average molecular weight. The term "polymer" as used in the present application denotes a material having a weight average molecular weight (Mw) of ≥ <NUM>,<NUM>. The term "copolymer" is used in its broad sense to include polymers containing two or more different monomer units, such as terpolymers, and unless otherwise indicated, includes random, block, and statistical copolymers. The concentration of ethylene or propylene in a particular phase or in the heterophasic composition is based on the weight of reacted ethylene units or propylene units relative to the total weight of polyolefin polymer in the phase or heterophasic composition, respectively, excluding any fillers or other non-polyolefin additives. The concentration of each phase in the overall heterogeneous polymer composition is based on the total weight of polyolefin polymers in the heterophasic composition, excluding any fillers or other non-polyolefin additives or polymers. In the structures of functional groups set forth below, the truncated bonds (i.e., the bonds truncated by the wavy lines) represent bonds to other portions of the compound containing the illustrated group.

In a first embodiment, the invention provides a method for producing a polymer composition. The method comprising the steps of (a) providing a compatibilizing agent, (b) providing a heterophasic polymer composition, (c) providing a second polymer composition, (d) mixing the compatibilizing agent, the heterophasic polymer composition, and the second polymer composition, and (e) generating free radicals in the heterophasic polymer composition and in the polymer of the second polymer composition. The compatibilizing agent preferably comprises two or more functional groups capable of reacting with a free radical in a radical addition reaction and is a compound of the formula (EX) described in more detail below. The heterophasic polymer composition preferably comprises a propylene polymer phase and an ethylene polymer phase. The second polymer composition preferably comprises recycled polymer.

The compatibilizing agent is a compound comprising two or more functional groups capable of reacting with a free radical in a radical addition reaction (each such functional group can be hereinafter referred to as a "reactive functional group"). Examples of suitable reactive functional groups for the compatibilizing agent include groups containing carbon-carbon multiple bonds (e.g., cyclic and acyclic carbon-carbon double bonds and carbon-carbon triple bonds), nitroxide radicals (including functional groups or moieties that form nitroxide radicals in situ during processing of the polymer), nitrones, and groups containing at least one tertiary carbon-hydrogen bond (e.g., a one tertiary carbon-hydrogen bond having a bond-dissociation energy of ≤ <NUM> kJ/mol). Suitable examples of groups containing carbon-carbon multiple bonds include vinyl groups, allyl groups, acrylate groups, and methacrylate groups. The compatibilizing agent can contain two or more of the same reactive functional group or more than one type of reactive functional group can be present on the compatibilizing agent. Suitable examples of compatibilizing agents include butadiene, butadiene oligomers, isoprene, isoprene oligomers, and mixtures thereof.

In another preferred embodiment, the compatibilizing agent comprises (i) at least one tertiary carbon-hydrogen bond and (ii) at least one acyclic carbon-carbon double bond. The tertiary carbon-hydrogen bond in the compatibilizing agent preferably is relatively weak or labile, which is believed to allow the hydrogen atom to dissociate from the compatibilizing agent by homolysis and yield a radical form of the compatibilizing agent bearing an unpaired electron on the tertiary carbon atom. While not wishing to be bound to any particular theory, it is believed that the tertiary nature of this carbon atom results in a radical that exhibits sufficient stability to react with polymer radicals formed in the heterophasic polymer composition. The relative strength or lability of the tertiary carbon-hydrogen bond can be characterized by the bond-dissociation energy. The bond-dissociation energy of the tertiary carbon-hydrogen bond is the enthalpy (per mole) required to break the tertiary carbon-hydrogen bond by homolysis. The tertiary carbon-hydrogen bond in the compatibilizing agent can therefore have any bond-dissociation energy that is low enough for the compatibilizing agent to be stable under storage and yet form radicals in the heterophasic polymer composition as described above. Preferably, the tertiary carbon-hydrogen bond has a bond-dissociation energy of ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol) at <NUM>. More preferably, the tertiary carbon-hydrogen bond has a bond-dissociation energy of ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol), ≤ <NUM> KJ/mol (≤ <NUM> kcal/mol), ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol), ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol), ≤ <NUM> kJ/mol (<NUM> kcal/mol), ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol), ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol), or ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol). While not wishing to be bound to any particular theory, the inventors believe that an acceptable bond-dissociation energy for the tertiary carbon-hydrogen bond can depend, at least in part, on the number of acyclic carbon-carbon double bonds present in the compatibilizing agent. For example, if the compatibilizing agent comprises two or more acyclic carbon-carbon double bonds, the compatibilizing agent can exhibit satisfactory performance when the bond-dissociation energy of the tertiary carbon-hydrogen bond lies higher in the ranges listed above. On the other hand, if the compatibilizing agent comprises only one acyclic carbon-carbon double bond, the bond dissociation energy of the tertiary carbon-hydrogen bond preferably lies lower in the ranges listed above. For example, if the compatibilizing agent comprises only one acyclic carbon-carbon double bond, the bond dissociation energy of the tertiary carbon-hydrogen bond preferably is ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol), more preferably ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol), more preferably ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol), and most preferably ≤ <NUM> kJ/mol (≤ <NUM> kcal/mol). All of the bond-dissociation energies listed above are for the homolytic cleavage of the tertiary carbon-hydrogen bond at a temperature of <NUM>.

The bond-dissociation energy of the tertiary carbon-hydrogen bond can be determined by any suitable means. Given the difficulties inherent in directly measuring the bond-dissociation energy of the bonds within a molecule, the bond-dissociation energy typically is calculated from a molecular model of the compatibilizing agent using commercially available molecular modeling software. For example, the bond-dissociation energy can be computed using density functional theory with the B3LYP functional. The bond-dissociation energy of the tertiary carbon-hydrogen bond (ΔH° (C-H)) in the molecule M is defined in Equation <NUM> below <MAT> In Equation <NUM>, H°(M) , H°(M•) and H°(H•) are the absolute enthalpies at <NUM> of the molecule M, M• radical and H• radical, respectively. The absolute enthalpies can be calculated, for example, with the Dmol3 program in the Materials Studio (version <NUM>) software tool from Biovia. When using the Dmol3 program, the input parameters for the calculations are shown in Table A for molecule M and in Table B for radicals M• and H•. The value of H°(H•) is calculated at -<NUM> Hartrees (<NUM> Hartree (Ha) = <NUM> kcal/mol).

The bond-dissociation energies for the tertiary carbon-hydrogen bond in the compatibilizing agent preferably are calculated using the procedure described above.

As utilized in describing the compatibilizing agent, the term "acyclic carbon-carbon double bond" refers to a carbon-carbon double bond that is not contained within a cyclic system, such as an aromatic ring. Thus, for example, the carbon-carbon double bonds in the vinylidene groups (-CH=CH-) contained within a phenyl ring are not acyclic carbon-carbon double bonds. However, the carbon-carbon double bond contained within the vinyl group of the compound styrene (i.e., phenylethene) is an acyclic carbon-carbon double bond. Further, carbon-carbon double bonds that are pendant to a cyclic system (e.g., the carbon-carbon bond is formed between a first carbon atom that is part of a cyclic system and a second carbon atom that is not part of a cyclic system) are also acyclic carbon-carbon double bonds. In a preferred embodiment, the acyclic carbon-carbon double bond in the compatibilizing agent has at least two hydrogen atoms bonded to the carbon atoms in the acyclic carbon-carbon double bond. These hydrogen atoms can be bonded to the same carbon atom in the acyclic carbon-carbon double bond, such as in a vinyl group, or these hydrogen atoms can be bonded to each of the carbon atoms in the acyclic carbon-carbon double bond, such as in a <NUM>-phenylethenyl group. In a preferred embodiment, the acyclic carbon-carbon double bond comprises two hydrogen atoms bonded to one of the carbon atoms in the acyclic carbon-carbon double bond.

The compatibilizing agent is a compound of Formula (EX) below
<CHM>
In Formula (EX), R<NUM>-R<NUM> are each independently selected from H, halogen, hydrocarbyl groups, and substituted hydrocarbyl groups, provided adjacent hydrocarbyl groups or substituted hydrocarbyl groups can be combined to form a secondary ring fused to the ring of the moiety. Further, at least one of R<NUM>-R<NUM> is H; preferably, at least two of R<NUM>-R<NUM> are H. The truncated bonds (i.e., the bonds truncated by the wavy lines) attached to the terminal vinylic carbon atom (in both Formulae (EI) and (EIII)) and the adjacent carbon atoms in the ring (in Formula (EIII)) represent bonds to other portions of the compatibilizing agent. In Formula (EV), R<NUM>-R<NUM> are each independently selected from halogen.

In a preferred embodiment, R<NUM>-R<NUM> are each independently selected from H, halogen, and alkyl, aryl, and heteroaryl, each optionally substituted. Examples of suitable alkyl groups include linear and branched C<NUM>-<NUM>-alkyl. Examples of suitable substituted alkyl groups include linear and branched C<NUM>-<NUM>-alkyl substituted with one or more non-hydrogen groups selected from halogen, hydroxy, aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Examples of suitable aryl groups include phenyl and naphthyl. Examples of suitable substituted aryl groups include monocyclic and polycyclic aryl groups substituted with one or more non-hydrogen groups selected from halogen, hydroxy, alkyl, and substituted alkyl. Examples of suitable heteroaryl groups include furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, pyridinyl, pyrazinyl, pyrimidinyl and benzannulated analogs of such groups, such as benzimidazolyl. Examples of suitable substituted heteroaryl groups include the heteroaryl groups described immediately above substituted with one or more non-hydrogen groups selected from halogen, hydroxy, alkyl, and substituted alkyl. In another preferred embodiment, R<NUM>, R<NUM>, R<NUM>, and R<NUM> are each H.

R<NUM> and R<NUM> are individual substituents independently selected from H, and alkyl, alkenyl, amine, aryl and heteroaryl, each optionally substituted , or R<NUM> and R<NUM> together form a single substituent selected from aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Preferably, no more than one of R<NUM> and R<NUM> can be H.

In a preferred embodiment, the compatibilizing agent is selected from compounds of Formula (EV)
<CHM>
wherein R<NUM>, R<NUM>, R<NUM>, and R<NUM> are independently selected from the group consisting of halogens.

In a preferred embodiment, R<NUM> and R<NUM> are independently groups of any of the Formulae (F), (FX) and (FXV)
<CHM>
<CHM>
<CHM>
In Formula (F), R<NUM>, R<NUM>, and R<NUM> are independently selected from C(H), C(R<NUM>), and a nitrogen atom. The variable f is an integer of <NUM>-<NUM>, but does not exceed a value equal to <NUM>-z, where z is the number of nitrogen atoms in the ring. Each R<NUM> is independently selected from alkyl (e.g., C<NUM>-<NUM>-alkyl), substituted alkyl (e.g., substituted C<NUM>-<NUM>-alkyl), aryl (e.g., C<NUM>-<NUM>-aryl), substituted aryl (e.g., substituted C<NUM>-<NUM>-aryl), heteroaryl (e.g., C<NUM>-<NUM>-heteroaryl), substituted heteroaryl (e.g., substituted C<NUM>-<NUM>-heteroaryl), halogen, nitro, cyano, amine, hydroxy, alkoxy (e.g., C<NUM>-<NUM>-alkoxy), aryloxy (e.g., C<NUM>-<NUM>-aryloxy), alkenyl (e.g., C<NUM>-<NUM>-alkenyl), alkynyl (e.g., C<NUM>-<NUM>-alkynyl), alkyl ester (e.g., C<NUM>-<NUM>-alkyl ester), and aryl ester (e.g., C<NUM>-<NUM>-aryl ester). Further, two adjacent R<NUM> groups can be linked to form a fused ring structure, such as a polycyclic aryl group. In Formula (FX), R<NUM> is selected from an oxygen atom, a sulfur atom, and N(R<NUM>). R<NUM> is selected from H, alkyl (e.g., C<NUM>-<NUM>-alkyl), substituted alkyl (e.g., substituted C<NUM>-<NUM>-alkyl), aryl (e.g., C<NUM>-<NUM>-aryl), and substituted aryl (e. g substituted C<NUM>-<NUM>-aryl). R<NUM> is selected from C(H), C(R<NUM>), and a nitrogen atom. R<NUM> is selected from alkyl (e.g., C<NUM>-<NUM>-alkyl), substituted alkyl (e.g., substituted C<NUM>-<NUM>-alkyl), aryl (e.g., C<NUM>-<NUM>-aryl), substituted aryl (e.g., substituted C<NUM>-<NUM>-aryl), heteroaryl (e.g., C<NUM>-<NUM>-heteroaryl), substituted heteroaryl (e.g., substituted C<NUM>-<NUM>-heteroaryl), halogen, nitro, cyano, amine, hydroxy, alkoxy (e.g., C<NUM>-<NUM>-alkoxy), aryloxy (e.g., C<NUM>-<NUM>-aryloxy), alkenyl (e.g., C<NUM>-<NUM>-alkenyl), alkynyl (e.g., C<NUM>-<NUM>-alkynyl), alkyl ester (e.g., C<NUM>-<NUM>-alkyl ester), and aryl ester (e.g., C<NUM>-<NUM>-aryl ester). Further, two adjacent R<NUM> groups can be linked to form a fused ring structure, such as a polycyclic aryl group. The variable g is an integer of <NUM>-<NUM>. In Formula (FXV), R<NUM> and R<NUM> are selected from the same groups described above for Formula (FX), and the variable h is an integer of <NUM>-<NUM>.

In a preferred embodiment, R<NUM>-R<NUM> are each H, and R<NUM> and R<NUM> are each phenyl. In another preferred embodiment, R<NUM>-R<NUM> are each H, and R<NUM> and R<NUM> are each <NUM>-chlorophenyl. In another preferred embodiment, R<NUM>-R<NUM> are each H, and R<NUM> and R<NUM> are each <NUM>-fluorophenyl. In another preferred embodiment, R<NUM>-R<NUM> are each H, R<NUM> is methyl, and R<NUM> is phenyl. In another preferred embodiment, R<NUM>-R<NUM> are each H, R<NUM> is H, and R<NUM> is <NUM>-thienyl. In another preferred embodiment, R<NUM>-R<NUM> are each H, R<NUM> is H, and R<NUM> is <NUM>-thienyl. In another preferred embodiment, R<NUM>-R<NUM> are each H, R<NUM> is methyl, and R<NUM> is <NUM>-furyl. In another preferred embodiment, R<NUM>-R<NUM> are each H, R<NUM> is H, and R<NUM> is dimethylamino. In another preferred embodiment, R<NUM>-R<NUM> are each H, and R<NUM> and R<NUM> are each C<NUM>-<NUM>-alkyl, preferably propyl. In another preferred embodiment, R<NUM>-R<NUM> are each H, R<NUM> is H, and R<NUM> is <NUM>-phenylethenyl.

The compatibilizing agent can comprise multiple fulvene moieties. For example, the compatibilizing agent can comprise two fulvene moieties and is of Formula (EXX) below:
<CHM>
In Formula (EXX), R<NUM>-R<NUM> is each independently selected from the groups recited above for Formula (EX), each R<NUM> is independently selected from the group recited above in Formula (EX), and R<NUM> is selected from alkanediyl, arenediyl and heteroarenediyl, each optionally substituted. In a preferred embodiment, R<NUM>-R<NUM> is each H, each R<NUM> is an aromatic group, and R<NUM> is an arenediyl group. More specifically, in such a preferred embodiment, R<NUM>-R<NUM> each is H, each R<NUM> is phenyl, and R<NUM> is phen-<NUM>,<NUM>-diyl. In another preferred embodiment, R<NUM>-R<NUM>, and R<NUM> each is H, and R<NUM> is arenediyl, preferably phen-<NUM>,<NUM>-diyl.

In certain instances, the compatibilizing agent can undergo a dimerization or oligomerization via an auto-Diels-Alder reaction. In such an auto-Diels-Alder reaction, the cyclopentadienyl moiety in one molecule of the compatibilizing agent acts as the diene, and a double bond in the cyclopentadienyl moiety of another molecule of the compatibilizing agent acts as the dienophile.

The dimer resulting from the auto-Diels-Alder reaction of a compatibilizing agent of Formula (EX) above will conform to the structure of Formula (EXA) below
<CHM>
In Formula (EXA), R<NUM>-R<NUM>, R<NUM>, and R<NUM> are selected from the groups disclosed above for the compound of Formula (EX). The dimer can be either the endo or exo isomer. Further, a dimer possessing the structure of Formula (EXA) can serve as the dienophile in subsequent Diels-Alder reactions with a diene, with such subsequent reactions yielding a variety of oligomeric species. While not wishing to be bound to any particular theory, it is believed that the dimeric and oligomeric species described above can undergo a retro-Diels-Alder reaction to yield the fulvene-containing compounds from which the dimeric and oligomeric species were originally derived. It is believed that this retro-Diels-Alder reaction can occur when a polymer composition containing the dimeric or oligomeric species is heated during processing, such as the heating that occurs when the polymer composition is extruded.

The compatibilizing agent can have any suitable molar mass. As will be understood by those of ordinary skill in the art, the molar mass of a compound, in combination with other factors, influences the melting point and boiling point of a compound. Thus, compounds with higher molar masses generally have higher melting points and boiling points. While not wishing to be bound to any particular theory, it is believed that the melting point and boiling point of the compatibilizing agent may influence the efficacy of the compatibilizing agent in the compositions of the invention. For example, it is believed that a compatibilizing agent having a relatively low molar mass and low boiling point (e.g., a boiling point that is significantly lower than the temperature at which the polymer composition is extruded) may volatilize to a significant degree during the extrusion process, thereby leaving less compatibilizing agent to modify the properties of the polymer composition. Thus, the compatibilizing agent preferably has a molar mass that is high enough that the compatibilizing agent exhibits a boiling point that is greater than the temperature at which the polymer composition is extruded. In a series of preferred embodiments, the compatibilizing agent preferably has a molar mass of ≥ <NUM>/mol, ≥ <NUM>/mol, ≥ <NUM>/mol, or ≥ <NUM>/mol. Also, it is believed that a compatibilizing agent having a relatively high melting point (e.g., a melting point that is higher than the temperature at which the polymer composition is extruded) may not disperse well in the molten polymer during the extrusion process, or at least not disperse as well as a compatibilizing agent having a melting point below the extrusion temperature. And poor dispersion of the compatibilizing agent will negatively impact the physical property improvements that can be achieved as compared to a well-dispersed compatibilizing agent. Thus, in a series of preferred embodiments, the compatibilizing has a melting point of ≤ <NUM>, ≤ <NUM>, ≤ <NUM>, or ≤ <NUM>.

The concentration of the compatibilizing agent in the composition can be varied to meet the objectives of the end user. For example, the concentration can be varied in order to achieve a desired increase in the MFR of the polymer composition with a minimal decrease (or potentially even an increase) in the strength of the polymer, in particular the impact strength. In a preferred embodiment, the compatibilizing agent can be present in an amount of ≥ <NUM> ppm, ≥ <NUM> ppm, ≥ <NUM> ppm, ≥ <NUM> ppm, or ≥ <NUM> ppm, based on the total weight of the polymer composition. In another preferred embodiment, the compatibilizing agent can be present in an amount of ≤ <NUM> wt. % (<NUM>,<NUM> ppm), ≤ <NUM> wt. % (<NUM>,<NUM> ppm), ≤ <NUM> wt. % (<NUM>,<NUM> ppm), ≤ <NUM> wt. % (<NUM>,<NUM> ppm), ≤ <NUM> wt. % (<NUM>,<NUM> ppm), or ≤ <NUM> wt. % (<NUM>,<NUM> ppm), based on the total weight of the polymer composition. Thus, in certain preferred embodiments, the compatibilizing agent can be present in an amount of <NUM> to <NUM>,<NUM> ppm, <NUM> to <NUM>,<NUM> ppm, or <NUM> to <NUM>,<NUM> ppm, based on the total weight of the polymer composition.

When a chemical free radical generator is employed (as discussed below), the concentration of the compatibilizing agent in the polymer composition can additionally or alternatively be expressed in terms of a ratio between the amount of the compatibilizing agent and the amount of the chemical free radical generator. In order to normalize this ratio for differences in the molecular weight of compatibilizing agents and number of peroxide bonds in the chemical free radical generators, the ratio is usual expressed as a ratio of the number of moles of compatibilizing agent present in the composition to the molar equivalents of peroxide bonds (O-O bonds) present from the addition of the chemical free radical generator. Preferably, the ratio (i.e., ratio of moles of compatibilizing agent to molar equivalents of peroxide bonds) is ≥ (<NUM>:<NUM>), ≥ (<NUM>:<NUM>), ≥ (<NUM>:<NUM>), ≥ (<NUM>:<NUM>), ≥ (<NUM>:<NUM>), ≥ (<NUM>:<NUM>), ≥ (<NUM>:<NUM>), ≥ (<NUM>:<NUM>), ≥ (<NUM>:<NUM>), or ≥ (<NUM>:<NUM>). In another preferred embodiment, the ratio is ≤ (<NUM>:<NUM>), ≤ (<NUM>:<NUM>), ≤ (<NUM>:<NUM>), ≤ (<NUM>:<NUM>), ≤ (<NUM>:<NUM>), ≤ (<NUM>:<NUM>), ≤ (<NUM>:<NUM>), ≤ (<NUM>:<NUM>), ≤ (<NUM>:<NUM>), or ≤ (<NUM>:<NUM>). Thus, in a series of preferred embodiments, the compatibilizing agent can be present in the composition in a ratio of moles of compatibilizing agent to molar equivalents of peroxide bonds of (<NUM>:<NUM>)-(<NUM>:<NUM>), (<NUM>:<NUM>)-(<NUM>:<NUM>), (<NUM>:<NUM>)-(<NUM>:<NUM>), (<NUM>:<NUM>)-(<NUM>:<NUM>), (<NUM>:<NUM>)-(<NUM>:<NUM>), or (<NUM>:<NUM>)-(<NUM>:<NUM>).

The second step of the method of the invention entails providing a heterophasic polymer composition. The heterophasic polymer composition preferably is a heterophasic polyolefin polymer composition. The subject heterophasic polyolefin polymers that can be advantageously modified according to the method of the invention are characterized by at least two distinct phases: a propylene polymer phase; and an ethylene polymer phase. The propylene polymer phase preferably comprises propylene polymers selected from polypropylene homopolymers and copolymers of propylene and up to <NUM> wt. % of ethylene and/or C<NUM>-C<NUM> α-olefins. The ethylene polymer phase preferably comprises ethylene polymers selected from ethylene homopolymers and copolymers of ethylene and C<NUM>-C<NUM> α-olefins. The ethylene content of the ethylene polymer phase preferably is at least <NUM> wt. When the ethylene phase is a copolymer of ethylene and C<NUM>-C<NUM> α-olefins, the ethylene content of the ethylene phase can be <NUM>-<NUM> wt. In one embodiment, the ethylene content of the ethylene phase preferably is at least <NUM> wt. Either the propylene polymer phase or the ethylene polymer phase can form the continuous phase of the composition and the other will form the discrete or dispersed phase of the composition. For example, the ethylene polymer phase can be the discontinuous phase and the polypropylene polymer phase can be the continuous phase. In one embodiment of the invention, the propylene content of the propylene polymer phase preferably is greater than the propylene content of the ethylene polymer phase.

The relative concentrations of the propylene polymer phase and the ethylene polymer phase in the heterophasic polymer composition can vary over a wide range. By way of example, the ethylene polymer phase can comprise <NUM>-<NUM> wt. % of the total weight of propylene polymers and ethylene polymers in the composition, and the propylene polymer phase can comprise <NUM>-<NUM> wt. % of the total weight of propylene polymers and ethylene polymers in the composition.

In various embodiments of the invention, (i) the ethylene content can be <NUM>-<NUM> wt. %, or even <NUM>-<NUM> wt. %, based on the total propylene polymer and ethylene polymer content in the heterophasic composition, (ii) the ethylene polymer phase can be an ethylene-propylene or ethylene-octene elastomer, and/or (iii) the propylene content of the propylene polymer phase can be ≥ <NUM> wt.

The method of the invention is particularly useful for modifying polypropylene impact copolymers. Suitable impact copolymers can be characterized by (i) a continuous phase comprising polypropylene polymers selected from polypropylene homopolymers and copolymers of propylene and up to <NUM> wt. % of ethylene and/or C<NUM>-C<NUM> α-olefins and (ii) a discontinuous phase comprising elastomeric ethylene polymers selected from copolymers of ethylene and C<NUM>-C<NUM> α-olefin monomers. Preferably, the ethylene polymers have an ethylene content of <NUM>-<NUM> wt.

In various embodiments of the invention directed to propylene impact copolymers, (i) the ethylene content of the discontinuous phase can be <NUM>-<NUM> wt. %, (ii) the ethylene content of the heterophasic composition can be <NUM>-<NUM> wt. %, based on the total propylene polymers and ethylene polymers in the composition; (iii) the propylene content of the continuous phase can be ≥ <NUM> wt. % and/or (iv) the discontinuous phase can be from <NUM> to <NUM> wt. % of the total propylene polymers and ethylene polymers in the composition.

Examples of heterophasic polyolefin polymers that can be modified are impact copolymers characterized by a relatively rigid, polypropylene homopolymer matrix (continuous phase) and a finely dispersed phase of ethylene-propylene rubber (EPR) particles. Such polypropylene impact copolymers can be made in a two-stage process, where the polypropylene homopolymer is polymerized first and the ethylene-propylene rubber is polymerized in a second stage. Alternatively, the impact copolymer can be made in three or more stages, as is known in the art. Suitable processes can be found <CIT> and <CIT>. Examples of suitable processes to make polypropylene impact copolymers are known in the industry by the commercial names Spheripol®, Unipol®, Mitsui process, Novolen process, Spherizone®, Catalloy®, Chisso process, Innovene®, Borstar®, and Sinopec process. These processes could use heterogeneous or homogeneous Ziegler-Natta or metallocene catalysts to accomplish the polymerization.

The heterophasic polymer composition can be formed by melt mixing two or more polymer compositions, which form at least two distinct phases in the solid state. By way of example, the heterophasic composition can comprise three distinct phases. The heterophasic polymer composition can result from melt mixing two or more types of recycled polymer compositions (e.g., polyolefin polymer compositions). Accordingly, the phrase "providing a heterophasic polymer composition" as used herein includes employing a polymer composition in the process that is already heterophasic, as well as melt mixing two or more polymer compositions during the process, wherein the two or more polymer compositions form a heterophasic system. For example, the heterophasic polymer composition can be made by melt mixing a polypropylene homopolymer and an ethylene /α-olefin copolymer, such as an ethylene / butene elastomer. Examples of suitable ethylene/α-olefin copolymers are commercially available under the names Engage™, Exact®, Vistamaxx®, Versify™, INFUSE™, Nordel™, Vistalon®, Exxelor™, and Affinity™. Furthermore, it can be understood that the miscibility of the polymer components that form the heterophasic polymer composition can vary when the composition is heated above the melting point of the continuous phase in the system, yet the system will form two or more phases when it cools and solidifies. Examples of heterophasic polymer compositions can be found in <CIT> and <CIT>.

Certain characteristics of the bulk heterophasic polymer composition (as measured prior to treatment with the compatibilizing agent) have been found to influence the physical property improvements (e.g., increase in impact strength) realized through the incorporation of the compatibilizing agent. In particular, with respect to the bulk characteristics of the heterophasic polymer composition, the ethylene preferably comprises ≥ <NUM> wt. %, ≥ <NUM> wt. %, ≥ <NUM> wt. %, or ≥ <NUM> wt. % of the total weight of the heterophasic polymer composition. The heterophasic polymer composition preferably contains ≥ <NUM> wt. %, ≥ <NUM> wt. %, ≥ <NUM> wt. %, or ≥ <NUM> wt. % xylene solubles or amorphous content. Further, ≥ <NUM> mol. %, ≥ <NUM> mol. %, ≥ <NUM> mol. %, or ≥ <NUM> mol. % of the ethylene present in the heterophasic polymer composition preferably is present in ethylene triads (i.e., a group of three ethylene monomer units bonded in sequence). Lastly, the number-average sequence length of ethylene runs (ethylene monomer units bonded in sequence) in the heterophasic polymer composition preferably is ≥ <NUM>, ≥ <NUM>, ≥ <NUM>, ≥ <NUM>, or ≥ <NUM>. % of ethylene in ethylene triads and the number-average sequence length of ethylene runs can both be measured using <NUM>C nuclear magnetic resonance (NMR) techniques known in the art. The heterophasic polymer composition can exhibit any one of the characteristics described in this paragraph. Preferably, the heterophasic polymer composition exhibits two or more of the characteristics described in this paragraph. Most preferably, the heterophasic polymer composition exhibits all of the characteristics described in this paragraph.

Certain characteristics of the ethylene phase of the heterophasic polymer composition (as measured prior to treatment with the compatibilizing agent) have also been found to influence the physical property improvements (e.g., increase in impact strength) realized through the incorporation of the compatibilizing agent. The characteristics of the ethylene phase of the composition can be measured using any suitable technique, such as temperature rising elution fractionation (TREF) and <NUM>C NMR analysis of the fractions obtained. In a preferred embodiment, ≥ <NUM> mol. %, ≥ <NUM> mol. %, or ≥ <NUM> mol. % of the ethylene present in a <NUM> TREF fraction of the heterophasic polymer composition is present in ethylene triads. In another preferred embodiment, ≥ <NUM> mol. %, ≥ <NUM> mol. %, or ≥ <NUM> mol. % of the ethylene present in an <NUM> TREF fraction of the heterophasic polymer composition is present in ethylene triads. In another preferred embodiment, ≥ <NUM> mol. %, ≥ <NUM> mol. %, ≥ <NUM> mol. %, or ≥ <NUM> mol. % of the ethylene present in a <NUM> TREF fraction of the heterophasic polymer composition is present in ethylene triads. The number-average sequence length of ethylene runs present in a <NUM> TREF fraction of the heterophasic polymer composition preferably is ≥ <NUM>, ≥ <NUM>, ≥ <NUM>, or ≥ <NUM>. The number-average sequence length of ethylene runs present in an <NUM> TREF fraction of the heterophasic polymer composition preferably is ≥ <NUM>, <NUM>, ≥ <NUM>, or ≥ <NUM>. The number-average sequence length of ethylene runs present in a <NUM> TREF fraction of the heterophasic polymer composition preferably is ≥ <NUM>, ≥ <NUM>, ≥ <NUM>, or ≥ <NUM>. The heterophasic polymer composition can exhibit any one of the TREF fraction characteristics described above or any suitable combination of the TREF fraction characteristics described above. In a preferred embodiment, the heterophasic polymer composition exhibits all of the TREF fraction characteristics described above (i.e., the ethylene triad and number-average sequence length characteristics for the <NUM>, <NUM>, and <NUM> TREF fractions described above).

Heterophasic polymer compositions exhibiting the characteristics described in the two preceding paragraphs have been observed to respond more favorably to the addition of the compatibilizing agent than heterophasic polymer compositions that do not exhibit these characteristics. In particular, heterophasic polymer compositions exhibiting these characteristics show significant improvements in impact strength when processed according to the method of the invention, whereas heterophasic polymer compositions that do not exhibit these characteristics do not show such marked improvements when processed under the same conditions. This differential response and performance has been observed even when the different polymer compositions have approximately the same total ethylene content (i.e., the percent ethylene in each polymer composition is approximately the same). This result is surprising and was not anticipated.

In one embodiment of the invention, the heterophasic polymer composition does not have any polyolefin constituents with unsaturated bonds. In particular, both the propylene polymers in the propylene phase and the ethylene polymers in the ethylene phase are free of unsaturated bonds.

In another embodiment of the invention, in addition to the propylene polymer and ethylene polymer components, the heterophasic polymer composition can further comprise an elastomer, such as elastomeric ethylene copolymers, elastomeric propylene copolymers, styrene block copolymers, such as styrenebutadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene (SEPS) and styrene-isoprene-styrene (SIS), plastomers, ethylene-propylene-diene terpolymers, LLDPE, LDPE, VLDPE, polybutadiene, polyisoprene, natural rubber, and amorphous polyolefins. The rubbers can be virgin or recycled.

The method of the invention preferably utilizes a second polymer composition in addition to the heterophasic polymer composition described above. The second polymer composition preferably contains recycled polymer. Preferably, the second polymer composition contains ≥ <NUM> wt. % recycled polymer. More preferably, the second polymer composition contains ≥ <NUM> wt. %, ≥ <NUM> wt. %, ≥ <NUM> wt. %, ≥ <NUM> wt. %, or ≥ <NUM> wt. % recycled polymer. The recycled polymer present in the second polymer composition can be any suitable polymer or combination of polymers. Typically, the recycled polymer present in the second polymer composition is selected from polyolefins (e.g., polypropylene, polyethylene), polyesters (e.g., polyethylene terephthalate), polystyrene, poly(vinyl chloride), and mixtures thereof. Preferably, the recycled polymer content of the second polymer composition is mainly derived from a polyolefin polymer or combination of polyolefin polymers. In other words, recycled polyolefins preferably account for ≥ <NUM> wt. % (e.g., ≥ <NUM> wt. %, ≥ <NUM> wt. %, ≥ <NUM> wt. %, or <NUM> wt. %) of the recycled polymer content of the second polymer composition. In a preferred embodiment, the recycled content of the second polymer composition is principally derived from PCR polymer (e.g., > <NUM> wt. %, ≥ <NUM> wt. %, ≥ <NUM> wt. %, ≥ <NUM> wt. %, ≥ <NUM> wt. %, ≥ <NUM> wt. %, ≥ <NUM> wt. %, or ≥ <NUM> wt. % of the recycled polymer content is PCR polymer).

In addition to the recycled polymer, the second polymer composition can comprise virgin polymer (i.e., polymer that has not been used by a consumer/end user and then recycled). When present in the second polymer composition, this virgin polymer can be any suitable polymer or combination of polymers. Preferably, the virgin polymer is a polyolefin, such as a polypropylene polymer.

In certain embodiments, the second polymer composition can further comprise one or more fillers. For example, the second polymer composition can comprise talc, calcium carbonate, and mixtures thereof.

As noted above, the method entails the step of mixing the compatibilizing agent, the heterophasic polymer composition, and the second polymer composition. The compatibilizing agent, the heterophasic polymer composition, and the second polymer composition can be mixed using any suitable technique or apparatus. In one embodiment of the invention, the polymer composition is produced by melt mixing the heterophasic polymer composition and second polymer composition with a compatibilizing agent in the presence of free radicals, which have been generated in the composition. The melt mixing step is conducted under conditions such that the composition is heated to above the melting temperature of the major polyolefin component of the mixture (i.e., the mixture of the heterophasic polymer composition and second polymer composition) and mixed while in the molten state. Examples of suitable melt mixing processes include melt compounding, such as in an extruder, injection molding, and mixing in a Banbury mixer or kneader. By way of example, the mixture can be melt mixed at a temperature of <NUM>-<NUM>. In particular, propylene impact copolymers can be melt mixed at a temperature of <NUM>-<NUM>. The heterophasic polymer composition (propylene polymer phase and ethylene polymer phase), second polymer composition, compatibilizing agent and an organic peroxide can be melt compounded in an extruder at a temperature above the melting temperature of all of the polyolefin polymers in the composition (i.e., the mixture of the heterophasic polymer composition and second polymer composition).

In another embodiment of the invention, the heterophasic polymer composition and second polymer composition can be dissolved in a solvent, the compatibilizing agent can be added to the resulting polymer solution, and the free radicals can be generated in the solution. In another embodiment of the invention, the compatibilizing agent can be combined with the heterophasic polymer composition and the second polymer composition in the solid state and free radicals can be generated during solid-state shear pulverization as described in <NPL>).

Conventional processing equipment may be used to mix the heterophasic polymer composition (e.g., propylene polymers and ethylene polymers) and compatibilizing agent together in a single step, in the presence of free radicals that are either added to the mixture, such as an organic peroxide, or generated in-situ, such as by shear, UV light, etc. Nevertheless, it is also possible to mix various combinations of the components in multiple steps and in various sequences, and subsequently subject the mixture to conditions whereby the compatibilizing agent reacts with the polyolefin polymers, as described herein.

For example, the compatibilizing agent and/or the free radical generator (when a chemical compound is used) can be added to the polymer in the form of one or masterbatch compositions. Suitable masterbatch compositions can comprise the compatibilizing agent and/or the free radical generator in a carrier resin. The compatibilizing agent and/or the free radical generator can be present in the masterbatch composition in an amount of <NUM>-<NUM> wt. % based on the total weight of the composition. Any suitable carrier resin can be used in the masterbatch compositions, such as any suitable thermoplastic polymer. For example, the carrier resin for the masterbatch compositions can be a polyolefin polymer, such as a polypropylene impact copolymer, a polyolefin copolymer, an ethylene/α-olefin copolymer, a polyethylene homopolymer, a linear low density polyethylene polymer, a polyolefin wax, or mixtures of such polymers. The carrier resin can also be a propylene polymer or an ethylene polymer that is the same as or similar to the propylene polymer or ethylene polymer present in the heterophasic polyolefin polymer composition. Such a masterbatch composition would allow the end user to manipulate the ratio of propylene polymer(s) to ethylene polymer(s) present in the heterophasic polymer composition. This may be preferred when the end user needs to modify the propylene to ethylene ratio of a commercial resin grade in order to achieve the desired set of properties (e.g., balance of impact and stiffness).

The method further comprises the step of generating free radicals in the resulting mixture of the compatibilizing agent, the heterophasic polymer composition, and the second polymer composition. More specifically, this step involves generating free radicals in the propylene polymer phase and the ethylene polymer phase of the heterophasic polymer composition and in the polymer of the second polymer composition. The free radicals can be generated in the heterophasic polymer composition and the second polymer composition by any suitable means.

A free radical generator is employed in the present invention to cause polymer chain scission and thereby positively affect (i.e., increase) the MFR of the polymer composition, while generating sufficient free radicals to foster the reaction of the compatibilizing agent with the free radicals generated in the polymers (e.g., the propylene and ethylene polymers in the heterophasic polymer composition and the polymers in the second polymer composition). The free radical generator can be a chemical compound, such as an organic peroxide or a bis-azo compound, or free radicals may be generated by subjecting the mixture of compatibilizing agent, heterophasic polymer composition, and second polymer composition to ultrasound, shear, an electron beam (for example β-rays), light (for example UV light), heat and radiation (for example γ-rays and X-rays), or combinations of the foregoing.

Organic peroxides having one or more O-O functionalities are of particular utility as the free radical generator in the method of the present invention. Examples of such organic peroxides include: <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-di(t-butylperoxy)hexane, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-di(t-butyl peroxy)hexyne-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentamethyl-<NUM>-(ethyl acetate)-<NUM>,<NUM>,<NUM>,<NUM>-tetraoxy cyclononane, t-butyl hydroperoxide, hydrogen peroxide, dicumyl peroxide, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxide, p-chlorobenzoyl peroxide, dibenzoyl diperoxide, t-butyl cumyl peroxide; t-butyl hydroxyethyl peroxide, di-t-amyl peroxide and <NUM>,<NUM>-dimethylhexene-<NUM>,<NUM>-diperisononanoate, acetylcyclohexanesulphonyl peroxide, diisopropyl peroxydicarbonate, tert-amyl perneodecanoate, tert-butyl-perneodecanoate, tert-butylperpivalate, tert-amylperpivalate, bis(<NUM>,<NUM>-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(<NUM>-methylbenzoyl)peroxide, disuccinoyl peroxide, diacetyl peroxide, dibenzoyl peroxide, tert-butyl per-<NUM>-ethylhexanoate, bis(<NUM>-chlorobenzoyl)peroxide, tert-butyl perisobutyrate, tert-butyl permaleate, <NUM>,<NUM>-bis(tert-butylperoxy)-<NUM>,<NUM>,<NUM>-trimethylcyclo-hexane, <NUM>,<NUM>-bis(tert-butylperoxy)cyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl perisononaoate, <NUM>,<NUM>-dimethylhexane <NUM>,<NUM>-dibenzoate, tert-butyl peracetate, tert-amyl perbenzoate, tert-butyl perbenzoate, <NUM>,<NUM>-bis(tert-butylperoxy)butane, <NUM>,<NUM>-bis(tert-butylperoxy)propane, dicumyl peroxide, <NUM>,<NUM>-dimethylhexane <NUM>,<NUM>-di-tert-butylperoxid, <NUM>-tert-butylperoxy-<NUM>-phenyl phthalide, di-tert-amyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, <NUM>,<NUM>-bis(tert-butylperoxy)-<NUM>,<NUM>-dimethyl-<NUM>,<NUM>-dioxolane, di-tert-butyl peroxide, <NUM>,<NUM>-dimethylhexyne <NUM>,<NUM>-di-tert-butyl peroxide, <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexamethyl-<NUM>,<NUM>,<NUM>,<NUM>-tetraoxacyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-α-hydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide.

The organic peroxide can be present in the composition (i.e., the mixture of the compatibilizing agent, the heterophasic polymer composition, and the second polymer composition) in any suitable amount. The suitable amount of organic peroxide will depend upon several factors, such as the particular polymers that are used in the composition, the starting MFR of the heterophasic polymer composition and/or the second polymer composition, and the desired MFR of the final polymer composition. In a preferred embodiment, the organic peroxide can be present in the polymer composition in an amount of ≥ <NUM> ppm, ≥ <NUM> ppm, or ≥ <NUM> ppm, based on the total weight of the polymer composition. In another preferred embodiment, the organic peroxide can be present in the polymer composition in an amount of ≤ <NUM> wt. % (<NUM>,<NUM> ppm), ≥ <NUM> wt. % (<NUM>,<NUM> ppm), ≥ <NUM> wt. % (<NUM>,<NUM> ppm), ≥ <NUM> wt. % (<NUM>,<NUM> ppm), ≥ <NUM> wt. % (<NUM>,<NUM> ppm), ≥ <NUM> wt. % (<NUM>,<NUM> ppm), or ≥ <NUM> wt. % (<NUM>,<NUM> ppm), based on the total weight of the polymer composition. Thus, in a series of preferred embodiments, the organic peroxide can be present in the polymer composition in an amount of <NUM>-<NUM>,<NUM> ppm, <NUM>-<NUM>,<NUM> ppm, <NUM>-<NUM>,<NUM> ppm, or <NUM>-<NUM>,<NUM> ppm, based on the total weight of the polymer composition. The amount of organic peroxide can also be expressed in terms of a molar ratio of the compatibilizing agent and peroxide bonds, as is described above. It will be understood that the amounts of peroxide provided above and elsewhere in the application refer to the initial amount of peroxide present in the composition (i.e., the mixture of the compatibilizing agent, the heterophasic polymer composition, and the second polymer composition) prior to the generation of free radicalsAs will be understood by those familiar with the art, peroxide is consumed to produce the free radicals and, therefore, the final polymer composition (after free radicals are produced) contains very little, if any, residual peroxide.

Suitable bis azo compounds may also be employed as a source of free radicals. Such azo compounds include, for example, <NUM>,<NUM>'-azobisisobutyronitrile, <NUM>,<NUM>'-azobis(<NUM>-methylbutyronitrile), <NUM>,<NUM>'-azobis(<NUM>,<NUM>-dimethylvaleronitrile), <NUM>,<NUM>'-azobis(<NUM>-methoxy-<NUM>,<NUM>-dimethylvaleronitrile), <NUM>,<NUM>'-azobis(<NUM>-cyclohexanecarbonitrile), <NUM>,<NUM>'-azobis(isobutyramide)dihydrate, <NUM>-phenylazo-<NUM>,<NUM>-dimethyl-<NUM>-methoxyvaleronitrile, dimethyl <NUM>,<NUM>'-azobisisobutyrate, <NUM>-(carbamoylazo)isobutyronitrile, <NUM>,<NUM>'-azobis(<NUM>,<NUM>,<NUM>-trimethylpentane), <NUM>,<NUM>'-azobis(<NUM>-methyl-propane), <NUM>,<NUM>'-azobis(N,N'-dimethyleneisobutyramidine) as free base or hydrochloride, <NUM>,<NUM>'-azobis(<NUM>-amidinopropane) as free base or hydrochloride, <NUM>,<NUM>'-azobis{<NUM>-methyl-N-[<NUM>,<NUM>-bis(hydroxymethyl)ethyl]propionamide}, and <NUM>,<NUM>'-azobis{<NUM>-methyl-N-[<NUM>,<NUM>-bis(hydroxymethyl)-<NUM>-hydroxyethyl]propionamide}.

Other chemical compounds useful as free radical generators include <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-diphenylbutane and sterically hindered hydroxylamine ester. The various free radical generators described above may be employed alone or in combination.

As is generally described above, at least a portion of the free radicals generated in the polymers (the propylene polymer phase and the ethylene polymer phase of the heterophasic polymer composition and the polymers in the second polymer composition) react with the reactive functional groups present on the compatibilizing agent. Specifically, the free radicals and the reactive functional groups react in a radical addition reaction thereby bonding the compatibilizing agent to the polymer. For example, when the compatibilizing agent reacts with a free radical in the propylene polymer phase and a free radical in the ethylene polymer phase, the compatibilizing agent then provides a link or bridge between the two phases. Further, when the compatibilizing agent reacts with a free radical in the heterophasic polymer composition (in the ethylene polymer phase or the propylene polymer phase) and a free radical in a polymer of the second polymer composition, the compatibilizing agent provides a link or bridge between these two polymers. While not wishing to be bound to any particular theory, it is believed that such links or bridges between the polymers of the composition are responsible for the increase in strength observed in polymer compositions that have been modified according to the method of the invention.

The polymer composition of the present invention is compatible with various types of additives conventionally used in thermoplastic compositions, including stabilizers, UV absorbers, hindered-amine light stabilizers (HALS), antioxidants, flame retardants, acid neutralizers, slip agents, antiblocking agents, antistatic agents, antiscratch agents, processing aids, blowing agents, colorants, opacifiers, carbon fibers, clarifiers, and/or nucleating agents. By way of further example, the composition can comprise fillers, such as calcium carbonate, talc, glass fibers, glass spheres, magnesium oxysulfate whiskers, calcium sulfate whiskers, calcium carbonate whiskers, mica, wollastonite, clays, such as montmorillonite, and bio-sourced or natural filler. The additives can comprise up to <NUM> wt. % of the total components in the modified heterophasic polymer composition.

The polymer composition of the present invention can be used in conventional polymer processing applications, including e.g. injection molding, thin-wall injection molding, single-screw compounding, twin-screw compounding, Banbury mixing, co-kneader mixing, two-roll milling, sheet extrusion, fiber extrusion, film extrusion, pipe extrusion, profile extrusion, extrusion coating, extrusion blow molding, injection blow molding, injection stretch blow molding, compression molding, extrusion compression molding, compression blow forming, compression stretch blow forming, thermoforming, and rotomolding. Articles made using the heterophasic polymer composition of the invention can be comprised of multiple layers, with one or any suitable number of the multiple layers containing a heterophasic polymer composition of the invention. By way of example, typical end-use products include containers, packaging, automotive parts, bottles, expanded or foamed articles, appliance parts, closures, cups, furniture, housewares, battery cases, crates, pallets, films, sheet, fibers, pipe, and rotationally molded parts.

The following examples further illustrate the subject matter described above but, of course, should not be construed as in any way limiting the scope thereof. The following methods, unless noted, were used to determine the properties described in the following examples.

Each of the compositions was compounded by blending the components in a closed container for approximately one minute. The compositions were then melt compounded on a Prism TSE-<NUM>-TC co-rotating, fully intermeshing, parallel, twin-screw extruder with a <NUM> screw diameter and a length/diameter ratio of <NUM>:<NUM>. The barrel temperature of the extruder was ramped from <NUM> to <NUM>, and the screw speed was set at <NUM> rpm. The extrudate (in the form of a strand) for each polypropylene copolymer composition was cooled in a water bath and subsequently pelletized.

The pelletized compositions were then used to form bars by injection molding the compositions on a Nissei HM7 <NUM> ton injection molder having a <NUM> diameter screw. The barrel temperature of the injection molder was approximately <NUM>-<NUM>, and the mold temperature was approximately <NUM>. The resulting bars measured approximately <NUM> long, approximately <NUM> wide, and approximately <NUM> thick.

The melt flow rate (MFR) was determined on the pelletized compositions according to (ASTM D1238) at <NUM> with a load of <NUM> for polypropylene.

The notched Izod impact strength for the bars was measured according to ISO method <NUM>/A. The notched Izod impact strength was measured at +<NUM> on bars that had been conditioned at either +<NUM> or -<NUM>. The flexural modulus, reported as chord modulus, for the bars was measured according to ISO method <NUM>.

Xylene solubles were determined by a modified version of ASTM D5492 - <NUM> and are a measure of the amount of rubber present in the heterophasic polypropylene copolymers. Approximately <NUM> of polymer was weighed out and placed into a round-bottom flask along with a stir bar. <NUM> of xylene was added to the polymer in the flask. The polymer xylene mixture was heated to reflux temperature while vigorously stirring. Once the reflux temperature was reached, the solution was stirred for an additional <NUM> then cooled to room temperature. The resulting polymer/xylene mixture was gently stirred to break up any precipitated polymer gel then poured through a No. <NUM> filter paper, both the filtrate containing the soluble fraction and the insoluble fraction were collected. A <NUM> aliquot of the filtrate was taken with a Class A pipet and transferred into a weighed pan. The pan containing the filtrate was then placed on a temperature-controlled hot plate maintaining a temperature of <NUM> to evaporate the xylene. Once most of the xylene was evaporated, the pan was transferred to a vacuum oven set at a temperature of <NUM> ± <NUM>. The pressure was reduced to less than <NUM> kPa and the sample was dried for approximately <NUM> hours or until a constant weight was achieved. The pan mass was then subtracted giving the mass of the residual soluble polymer. The percentage of soluble polymer in the original sample was calculated using the following equation: <MAT> In the equation, Ss is the soluble fraction of sample expressed as a percentage; Vbo is the original volume of solvent in milliliters; Vb1 is the volume of the aliquot used for soluble determination in millilieters; W<NUM> is the mass of pan and soluble in grams; W<NUM> is the mass of pan in grams; and Wo is the mass of the original sample in grams.

This example demonstrates the production of several polymer compositions according to the invention and the enhanced physical properties exhibited by these polymer compositions.

A total of eight polymer compositions (Samples 1A-1C and Comparative Samples 1A-1E (C. 1A-1E)) were produced using a heterophasic polymer composition, a second polymer composition containing post-consumer recycled polymer, a peroxide, and a compatibilizing agent. In particular, the heterophasic polymer composition was a polypropylene impact copolymer, namely Pro-Fax SG702 from LyondellBasell, which contained approximately <NUM>% xylene solubles. The second polymer composition was a post-consumer recycled polypropylene available from Entropex LLC of Sarnia, Ontario, Canada. The peroxide was Varox DBPH available from Vanderbilt Chemicals, LLC. The compatibilizing agent was diphenylfulvene. The loading of the second polymer composition, peroxide, and compatibilizing agent in each polymer composition is set forth in Table <NUM> below. For each polymer composition, the polypropylene impact copolymer provided the balance of the polymer composition.

The components for each polymer composition were mixed and extruded into pellets as described above, and a portion of the pellets for each composition were injection molded into bars according to the general procedure described above. The extruded pellets were used to determine the melt flow rate (MFR) exhibited by the polymer composition, and the injection molded bars were tested to determine flexural modulus and Izod impact strength as described above. The results of this testing are set forth in Table <NUM> below.

As can be seen from the data in Tables <NUM> and <NUM>, the polymer compositions containing PCR resin (i.e., the second polymer composition) and no compatibilizing agent generally exhibit diminished flexural properties (lower chord modulus) and impact resistance (lower Izod impact) relative to the virgin polypropylene impact copolymer (C. By way of contrast, those polymer compositions containing a compatibilizing agent (i.e., Samples 1A, 1B, 1C, 1D, and 1E) all exhibited an increase in Izod impact strength relative to the virgin polypropylene impact copolymer (C. Indeed, the Izod impact strength of Samples 1A, 1B, and 1C was nearly three times that of the virgin polypropylene impact copolymer. Further, these improvements in Izod impact strength were accomplished while also dramatically increasing the melt flow rate of the polymer composition, which should translate into processing benefits during manufacture.

A total of four polymer compositions (Sample 2A and Comparative Samples 2A-2C) were produced using various combinations of a heterophasic polymer composition, a second polymer composition containing post-consumer recycled polymer, a peroxide, and a compatibilizing agent. In particular, the heterophasic polymer composition was a polypropylene impact copolymer, namely Pro-Fax SG702 from LyondellBasell, which contained approximately <NUM>% xylene solubles. The second polymer composition was a post-consumer recycled polypropylene available from Entropex LLC of Sarnia, Ontario, Canada. The peroxide was Varox DBPH available from Vanderbilt Chemicals, LLC. The compatibilizing agent used in Sample 2A is diphenylfulvene, and in Comparative Samples 2A-2C no compatibilizing agent was used. The loading of the second polymer composition, peroxide, and compatibilizing agent in each polymer composition is set forth in Table <NUM> below. For each polymer composition, the polypropylene impact copolymer provided the balance of the polymer composition.

The data in Tables <NUM> and <NUM> show that polymer compositions produced according to the method of the invention (Sample 2A) exhibited increased Izod impact relative to a similar polymer composition produced without a compatibilizing agent (C. Indeed, Sample 2A exhibited Izod impact strength that was essentially the same as the virgin polypropylene impact copolymer (C. 2A), which is surprising given that the polymer compositions all contain <NUM> wt. % of a polymer composition containing PCR polymer. Further, Sample 2A exhibited an increase in the chord modulus relative to the virgin polypropylene impact copolymer. Again, these improvements in flexural properties and impact resistance were achieved while increasing the melt flow rate of the polymer composition relative to the virgin polypropylene impact copolymer. Lastly, the data in the tables show that these improvements can be obtained using a variety of different compatibilizing agents.

A total of seven polymer compositions (Samples 3A-3C and Comparative Samples 3A-3D) were produced using various combinations of a heterophasic polymer composition, a second polymer composition containing post-consumer recycled polymer, a peroxide, and a compatibilizing agent. In particular, the heterophasic polymer composition was a polypropylene impact copolymer, namely PP7414 from ExxonMobil, which contained approximately <NUM>% xylene solubles. The second polymer composition was a post-consumer recycled polypropylene available from Entropex LLC of Sarnia, Ontario, Canada. The peroxide was Varox DBPH available from Vanderbilt Chemicals, LLC. The compatibilizing agent was diphenylfulvene. The loading of the second polymer composition, peroxide, and compatibilizing agent in each polymer composition is set forth in Table <NUM> below. For each polymer composition, the polypropylene impact copolymer provided the balance of the polymer composition.

The data in Tables <NUM> and <NUM> show that polymer compositions produced according to the method of the invention (Samples 3A, 3B, and 3C) exhibited increases in Izod impact strength relative to the virgin polypropylene impact copolymer (C. Further, these increases in Izod impact strength were accomplished while also appreciably increasing the melt flow rate of the polymer composition relative to the virgin polypropylene impact copolymer and the mixture of the polypropylene impact copolymer and second polymer composition (C.

A total of nine polymer compositions (Samples 4A-4C and Comparative Samples 4A-4F) were produced using various combinations of a heterophasic polymer composition, a second polymer composition containing post-consumer recycled polymer, a peroxide, and a compatibilizing agent. In particular, the heterophasic polymer composition was a polypropylene impact copolymer, namely Pro-Fax SG702 from LyondellBasell, which contained approximately <NUM>% xylene solubles. The second polymer composition was a post-consumer recycled polypropylene available, namely KW <NUM> from KW Plastics of Troy, Alabama. The peroxide was Varox DBPH available from Vanderbilt Chemicals, LLC. The compatibilizing agent was diphenylfulvene. The loading of the second polymer composition, peroxide, and compatibilizing agent in each polymer composition is set forth in Table <NUM> below. For each polymer composition, the polypropylene impact copolymer provided the balance of the polymer composition.

Claim 1:
A method for producing a polymer composition, comprising the steps of:
(a) providing a compatibilizing agent which (i) comprises two or more functional groups capable of reacting with a free radical in a radical addition reaction, and (ii) is a compound of the formula (EX)
<CHM>
wherein R<NUM>-R<NUM> each independently are H, halogen, or alkyl, aryl or heteroaryl, each optionally substituted, and R<NUM> and R<NUM> each independently are H, or alkyl, alkenyl, amino, aryl or heteroaryl, each optionally substituted, or R<NUM> and R<NUM> together form a single substituent selected from aryl and heteroaryl, each optionally substituted;
(b) providing a heterophasic polymer composition comprising a propylene polymer phase and an ethylene polymer phase;
(c) providing a second polymer composition comprising recycled polyolefin polymer;
(d) mixing the compatibilizing agent, the heterophasic polymer composition, and the second polymer composition; and
(e) generating free radicals in the propylene polymer phase and the ethylene polymer phase of the heterophasic polymer composition and in the polymer of the second polymer composition, whereby at least a portion of the compatibilizing agent reacts with the free radicals.