Graftable polymer compositions with propylene-based polymer, maleic anhydride, and BIS(4-phenacryloyloxyphenyl) disulfide or BIS(4-methacryloyloxyphenyl) disulfide

Abstract

Embodiments are directed to a graftable polymer composition. In embodiments, the graftable polymer composition includes a propylene-based polymer, maleic anhydride, a free radical initiator, and bis(4-phenacryloyloxyphenyl) disulfide (BPST). In other embodiments, the graftable polymer composition includes a propylene-based polymer, maleic anhydride, a free radical initiator, a coagent, and bis(4-methacryloyloxyphenyl) disulfide (BPMA). Further embodiments are directed to grafted compositions formed from the graftable polymer compositions.

Description

[0001] 86830-WO-PCT / DOW 86830 WO GRAFTABLE POLYMER COMPOSITIONS WITH PROPYLENE- BASED POLYMER, MALEIC ANHYDRIDE, AND BIS(4- PHENACRYLOYLOXYPHENYL) DISULFIDE OR BIS(4- METHACRYLOYLOXYPHENYL) DISULFIDE CROSS-REFERENCE TO RELATED APPLICATIONS [1] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 669,770 filed July 11, 2024, the contents of which are incorporated in their entirety herein. TECHNICAL FIELD [2] Embodiments of the present disclosure generally relate to graftable polymer compositions and specifically relate to graftable polymer compositions with propylene-based polymer, maleic anhydride, and bis(4-phenacryloyloxyphenyl) disulfide or bis(4- methacryloyloxyphenyl) disulfide. BACKGROUND [3] Grafted olefin-based polymers, and grafted propylene-based polymers in particular are widely used as compatibilizer and tie resin in various applications, including film and packaging, automotive, and infrastructure. Unfortunately, using conventional processes to graft propylene-based polymers may lead to difficulties, such as chain scission that occurs during melt grafting. Thus, grafting tends to react on shorter oligomers rather than on polymer backbone. As a result, the grafted product may be less effective in some applications due to, for example, inefficient bonding to a barrier layer, lower adhesion, delamination, and loss of packaging integration during storage or heat process. [4] Accordingly, there is a need for improved grafted propylene-based polymers with reduced chain scission. SUMMARY [5] The embodiments of the present disclosure meet this need by utilizing bis(4- phenacryloyloxyphenyl) disulfide (BPST) or bis(4-methacryloyloxyphenyl) disulfide (BPMA) in combination with a coagent. This resulted in graftable polymer compositions that may be grafted to produce a grafted composition with reduced chain scission (e.g., greater 86830-WO-PCT / DOW 86830 WO weight average molecular weight Mw as compared to a grafted composition lacking BPST or BPMA). [6] In some embodiments, a graftable polymer composition comprises: a propylene- based polymer; maleic anhydride; a free radical initiator; and bis(4-phenacryloyloxyphenyl) disulfide (BPST). [7] In other embodiments, a grafted composition comprises: a maleic anhydride-grafted propylene-based polymer; and bis(4-phenacryloyloxyphenyl) disulfide (BPST). [8] In some embodiments, a graftable polymer composition comprise: a propylene-based polymer; maleic anhydride; a free radical initiator; a coagent; and bis(4- methacryloyloxyphenyl) disulfide (BPMA). [9] In other embodiments, a grafted composition comprises: a maleic anhydride-grafted propylene-based polymer; a coagent; and bis(4-methacryloyloxyphenyl) disulfide (BPMA).

[0010] Additional features and advantages will be set forth in the detailed description, which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows and the claims.

[0011] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. DETAILED DESCRIPTION

[0012] Specific embodiments of the present application will now be described. The disclosure may be embodied in different forms and should not be construed as limited to the embodiments set forth in this disclosure. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0013] DEFINITIONS

[0014] Unless stated to the contrary, implicit from the context, or customary in the art, all test methods are current as of the filing date of this disclosure. 86830-WO-PCT / DOW 86830 WO

[0015] The amount of a component (e.g., propylene-based polymer, maleic anhydride, free- radical initiator, BPST, BPMA, and coagent) in a graftable polymer composition or a grafted composition is provided herein in weight percent (wt%), based on a total weight of the graftable polymer composition or the grafted composition, unless otherwise noted.

[0016] Ranges may be expressed herein as from “about” one particular value, and / or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0017] The terms "comprising", "including", "having”, and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether 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.

[0018] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight.

[0019] The term “composition,” as used herein, 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.

[0020] The term "propylene-based polymer," as used herein, refers to a polymer that contains more than 50 mole percent polymerized propylene monomer (based on the total amount of polymerizable monomers) and, optionally, may contain at least one comonomer. Propylene-based polymer includes propylene homopolymer, and propylene copolymer (meaning units derived from propylene and one or more comonomers). The terms "propylene-based polymer" and "polypropylene" may be used interchangeably. 86830-WO-PCT / DOW 86830 WO

[0021] The term “polymer,” as used herein, refers to a compound prepared by polymerizing monomers, whether of the same or a different type, that in polymerized form provide the multiple and / or repeating “units” or “mer units” that make up a polymer. The generic term polymer thus embraces the term homopolymer, usually employed to refer to polymers prepared from only one type of monomer, and the term copolymer, usually employed to refer to polymers prepared from at least two types of monomers. It also embraces all forms of copolymer, e.g., random, block, etc. The term “propylene / α-olefin polymer” is indicative of copolymer as described above prepared from polymerizing propylene respectively and one or more additional, polymerizable α-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.

[0022] “Impact modified propylene-based copolymer” and the like terms mean a propylene-based polymer composition that has been impact-modified such that the composition's impact strength at room temperature or below is maintained or increased as compared to said given composition's impact strength at the same temperature without the added impact modifier.

[0023] "Block copolymer" or “segmented copolymer” refers to a polymer comprising two or more chemically distinct regions or segments (referred to as "blocks") joined in a linear manner, that is, a polymer comprising chemically differentiated units that are joined (covalently bonded) end-to-end with respect to polymerized functionality (e.g., polymerized propylenic functionality), rather than in pendent or grafted fashion. Block copolymers comprise sequences ("blocks") of the same monomer unit, covalently bound to sequences of unlike type. The blocks can be connected in a variety of ways, such as A—B in diblock and A—B—A triblock structures, where A represents one block and B represents a different block. In a multi-block copolymer, A and B can be connected in a number of different ways and be repeated multiply. It may further comprise additional blocks of different type. Multi- block copolymers may be linear multi-block, multi block star polymers (in which all blocks bond to the same atom or chemical moiety) or comb-like polymers where the B blocks are 86830-WO-PCT / DOW 86830 WO attached at one end to an A backbone. The block copolymers can be linear or branched. With respect to the block copolymers, the blocks may differ in the amount of comonomer incorporated therein. The blocks may also differ in the type of comonomer, density, the amount of crystallinity, the crystallite size attributable to a polymer of such composition, the type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching, including long chain branching or hyper-branching, the homogeneity, or any other chemical or physical property. The block copolymers are characterized by unique distributions of polymer polydispersity (PDI or Mw / Mn), block length distribution, and / or block number distribution, e.g., due to the effect of the shuttling agent(s) in combination with the catalyst(s).

[0024] EMBODIMENTS

[0025] Embodiments of the present disclosure are directed to graftable polymer compositions comprising a propylene-based polymer, maleic anhydride, and either BPST or BPMA with a coagent. The grafted compositions may be formed from a graftable polymer composition comprising the propylene-based polymer, maleic anhydride, either BPST or BPMA with a coagent, and a radical initiator. That is, the grafted composition may be the reaction product of grafting the graftable polymer composition.

[0026] Propylene-based Polymer

[0027] Propylene-based polymer imparts desirable mechanical properties, heat stability, and chemical resistance to the graftable polymer compositions described herein.

[0028] Nonlimiting examples of suitable propylene-based polymer may include polypropylene homopolymer, polypropylene-based elastomer, polypropylene-based block copolymer, propylene-based impact copolymer, and combinations thereof.

[0029] In embodiments, the propylene-based polymer comprises polypropylene homopolymer.

[0030] In embodiments, the propylene-based polymer comprises polypropylene-based elastomer. “Propylene-based elastomer” comprises at least one copolymer with at least about 50 weight percent of units derived from propylene and at least about 4 weight percent of units derived from a comonomer other than propylene. Suitable propylene-based elastomers are taught in US Patent Nos. 6,906,160; 6,919,407; 6,927,256; 6,960,535; 7,250,470; 7,250,471; 86830-WO-PCT / DOW 86830 WO and 7,344,775, each of which are incorporated by reference in their entireties. In embodiments, the propylene-based elastomer may comprise propylene-ethylene elastomer.

[0031] In embodiments, the propylene-based polymer may comprise a melt flow rate (MFR) from 0.1 g / 10 min to 50 g / 10 min, from 0.1 g / 10 min to 25 g / 10 min, from 0.1 g / 10 min to 10 g / 10 min, from 0.1 g / 10 min to 5 g / 10 min, from 1 g / 10 min to 50 g / 10 min, from 1 g / 10 min to 25 g / 10 min, from 1 g / 10 min to 10 g / 10 min, from 1 g / 10 min to 5 g / 10 min, from 10 g / 10 min to 50 g / 10 min, from 10 g / 10 min to 25 g / 10 min, or even from 25 g / 10 min to 50 g / 10 min, , or any and all sub-ranges formed from any of these endpoints.

[0032] In embodiments, the propylene-based polymer comprises impact modified propylene-based copolymer.

[0033] In embodiments, the propylene-based polymer may comprise post consumer recycle polypropylene.

[0034] The graftable polymer composition may comprises a minimum about of propylene- based polymer (e.g., greater than or equal to 70 wt%) to ensure the grafted composition has desirable mechanical properties, heat stability, and chemical resistance. The amount of propylene-based polymer may be limited (e.g., less than or equal to 99 wt% or 97.5 wt%) to ensure that enough BPST or BPMA and coagent are present to achieve grafting with reduced chain scission. Accordingly, in embodiments including BPST, the graftable composition may comprise from 70 wt% to 99 wt% of the propylene-based polymer. In embodiments including BPMA, the graftable composition may comprise from 70 wt% to 97.5 wt% of the propylene- based polymer. In embodiments, the amount of the BPST or BPMA in the graftable polymer composition may be greater than or equal to 70 wt%, greater than or equal to 75 wt%, greater than or equal to 80 wt%, greater than or equal to 85 wt%, greater than or equal to 90 wt%, or even greater than or equal 95 wt%. In embodiments, the amount of the BPST or BPMA in the graftable polymer composition may be less than or equal to 99 wt%, less than or equal to 97.5 wt%, less than or equal to 96 wt%, or even less than or equal to 94 wt%. In embodiments, the amount of the BPST or BPMA in the graftable polymer composition may be from 70 wt% to 99 wt%, from 70 wt% to 97.5 wt%, from 70 wt% to 96 wt%, from 70 wt% to 94 wt%, from 75 wt% to 99 wt%, from 75 wt% to 97.5 wt%, from 75 wt% to 96 wt%, from 75 wt% to 94 wt%, from 80 wt% to 99 wt%, from 80 wt% to 97.5 wt%, from 80 wt% to 96 wt%, from 80 wt% to 94 wt%, from 85 wt% to 99 wt%, from 85 wt% to 97.5 wt%, from 85 wt% to 96 wt%, 86830-WO-PCT / DOW 86830 WO from 85 wt% to 94 wt%, from 90 wt% to 99 wt%, from 90 wt% to 97.5 wt%, from 90 wt% to 96 wt%, from 90 wt% to 94 wt%, from 95 wt% to 99 wt%, from 95 wt% to 97.5 wt%, or even from 95 wt% to 96 wt%, or any and all sub-ranges formed from any of these endpoints.

[0035] Maleic Anhydride

[0036] Maleic anhydride imparts desirable properties to the resulting grafted composition such that the grafted composition may be used as a compatibilizer or a tie resin, for example.

[0037] In embodiments, the maleic anhyrdride may comprise a melting point from 40 °C to 70 °C, from 40 °C to 65 °C, from 40 °C to 60 °C, from 45 °C to 70 °C, from 45 °C to 65 °C, from 45 °C to 60 °C, from 50 °C to 70 °C, from 50 °C to 65 °C, or even from 50 °C to 60 °C, or any and all sub-ranges formed from any of these endpoints.

[0038] In embodiments, the maleic anhydride may comprise a density from 1.40 g / cm3to 1.60 g / cm3, from 1.40 g / cm3to 1.55 g / cm3, from 1.40 g / cm3to 1.50 g / cm3, from 1.45 g / cm3to 1.60 g / cm3, from 1.45 g / cm3to 1.55 g / cm3, or even from 1.45 g / cm3to 1.50 g / cm3, or any and all sub-ranges formed from any of these endpoints.

[0039] The graftable composition may comprise a minimum amount of maleic anhydride (e.g., greater than or equal to 0.5 wt%) to ensure grafting of the maleic anhydride to the propylene-based polymer. The amount of maleic anhydride may be limited (e.g., less than or equal to 10 wt%) to prevent maleic anhydride side reactions and undesirable gelling and coloration. Accordingly, in embodiments, the graftable polymer composition may comprise from 0.5 wt% to 10 wt% of the maleic anhydride. In embodiments, the amount of maleic anhydride in the graftable polymer composition may be greater than or equal to 0.5 wt%, greater than or equal to 1 wt%, or even greater than or equal to 1.5 wt%. In embodiments, the amount of maleic anhydride in the graftable polymer composition may be less than or equal to 10 wt%, less than or equal to 8 wt%, less than or equal to 6 wt%, less than or equal to 4 wt%, or even less than or equal to 2 wt%. In embodiments, the amount of maleic anhydride in the graftable polymer composition may be from 0.5 wt% to 10 wt%, from 0.5 wt% to 8 wt%, from 0.5 wt% to 6 wt%, from 0.5 wt% to 4 wt%, from 0.5 wt% to 2 wt%, from 1 wt% to 10 wt%, from 1 wt% to 8 wt%, from 1 wt% to 6 wt%, from 1 wt% to 4 wt%, from 1 wt% to 2 wt%, from 1.5 wt% to 10 wt%, from 1.5 wt% to 8 wt%, from 1.5 wt% to 6 wt%, from 1.5 wt% to 4 wt%, or even from 1.5 wt% to 2 wt%, or any and all sub-ranges formed from any of these endpoints. 86830-WO-PCT / DOW 86830 WO

[0040] BPST and BPMA

[0041] As described in further detail below, BPST or BPMA with a coagent ensures grafting with reduced chain scission.

[0042] In embodiments, the graftable polymer composition and the resulting grafted composition may comprise BPST. BPST has Structure 1 shown below:

[0043] As mentioned hereinabove, conventional processes, such as radical processes, to graft propylene-based polymers made lead to difficulties, such as chain scission that occurs in the presence of radicals. Grafting may occur while reducing chain scission if tertiary radicals propagate to and are stabilized by a vinyl compound prior to chain scission. As shown in Structure 1, BPST includes a phenyl ring adjacent to the vinyl group, which may increase reactivity toward a tertiary carbon radical by stronger stabilization energy via resonance, thereby preventing chain scission.

[0044] In other embodiments, the graftable polymer composition and the resulting grafted composition may comprise BPMA. BPMA has Structure 2 shown below: STRUCTURE 2

[0045] Compared to BPST, which bears a styrene-like substructure for resonance stabilization, as described herein, BPMA has less resonance stabilization and, therefore, has 86830-WO-PCT / DOW 86830 WO lower reactivity toward a tertiary radical. As such, a coagent may be added to help improve reactive toward a tertiary radical, thereby preventing chain scission.

[0046] The graftable composition may comprise a minimum amount of BPST or BPMA (e.g., greater than or equal to 0.5 wt%) to ensure grafting with reduced chain scission. The amount of BPST or BPMA may be limited (e.g., less than or equal to 10 wt%) to prevent undesirable crosslinking. Accordingly, in embodiments, the graftable polymer composition may comprise from 0.5 wt% to 10 wt% of the BPST or the BPMA. In embodiments, the amount of the BPST or BPMA in the graftable composition may be greater than or equal to 0.5 wt%, greater than or equal to 0.75 wt%, greater than or equal to 1 wt%, greater than or equal to 2 wt%, or even greater than or equal to 3 wt%. In embodiments, the amount of the BPST or BPMA in the graftable composition may be less than or equal to 10 wt%, less than or equal to 8 wt%, less than or equal to 6 wt%, or even less than or equal to 4 wt%. In embodiments, the amount of the BPST or BPMA in the graftable composition may be from 0.5 wt% to 10 wt%, from 0.5 wt% to 8 wt%, from 0.5 wt% to 6 wt%, from 0.5 wt% to 4 wt%, from 0.75 wt% to 10 wt%, from 0.75 wt% to 8 wt%, from 0.75 wt% to 6 wt%, from 0.75 wt% to 4 wt%, from 1 wt% to 10 wt%, from 1 wt% to 8 wt%, from 1 wt% to 6 wt%, from 1 wt% to 4 wt%, from 2 wt% to 10 wt%, from 2 wt% to 8 wt%, from 2 wt% to 6 wt%, from 2 wt% to 4 wt%, from 3 wt% to 10 wt%, from 3 wt% to 8 wt%, from 3 wt% to 6 wt%, or even from 3 wt% to 4 wt%, or any and all sub-ranges formed from any of these endpoints.

[0047] Coagent

[0048] As described herein, BPMA has relatively low resonance stabilization and a relatively low reactivity toward a tertiary radical. As such, a coagent may be added to help improve reactive toward a tertiary radical, thereby preventing chain scission.

[0049] In embodiments, the coagent may comprise styrene; divinyl benzene; 1,1,1- trimethylolpropane trimethacrylate; pentaerythrityl tetramethacrylate (PETM); trimethylolpropanetiacrylate (TMPTA); pentaerythritol tetraacrylate (PETA); pentaerythritol tetrallyl ether; diallyl maleate; triallyl cyanurate; diallyl itaconate; triallylisocyanurate (TAIC); 4-vinylnapthalene, or a combination thereof. In embodiments, the coagent may comprise styrene, pentaerythritol tetraacrylate (PETA), or a combination thereof.

[0050] The graftable polymer composition may comprise a minimum amount of coagent (e.g., greater than or equal to 0.5 wt%) to prevent chain scission. The amount of the coagent 86830-WO-PCT / DOW 86830 WO may be limited (e.g., less than or equal to 15 wt%) to ensure a sufficient amount of propylene- based polymer is present to achieve desired results. Accordingly, in embodiments, the graftable polymer composition may comprise from 0.5 wt% to 15 wt% of the coagent. In embodiments, the amount of the coagent in the graftable polymer composition may be greater than or equal to 0.5 wt%, greater than or equal to 1 wt%, greater than or equal to 2 wt%, greater than or equal to 3 wt%, greater than or equal to 4 wt%, or even greater than or equal to 5 wt%. In embodiments, the amount of the coagent in the graftable polymer composition may be less than or equal to 15 wt%, less than or equal to 10 wt%, less than or equal to 9 wt%, less than or equal to 8 wt%, less than or equal to 7 wt%, or even less than or equal to 6 wt%. In embodiments, the amount of the coagent in the graftable polymer composition may be from 0.5 wt% to 15 wt%, from 0.5 wt% to 10 wt%, from 0.5 wt% to 9 wt%, from 0.5 wt% to 8 wt%, from 0.5 wt% to 7 wt%, from 0.5 wt% to 6 wt%, from 1 wt% to 15 wt%, from 1 wt% to 10 wt%, from 1 wt% to 9 wt%, from 1 wt% to 8 wt%, from 1 wt% to 7 wt%, from 1 wt% to 6 wt%, from 2 wt% to 15 wt%, from 2 wt% to 10 wt%, from 2 wt% to 9 wt%, from 2 wt% to 8 wt%, from 2 wt% to 7 wt%, from 2 wt% to 6 wt%, from 3 wt% to 15 wt%, from 3 wt% to 10 wt%, from 3 wt% to 9 wt%, from 3 wt% to 8 wt%, from 3 wt% to 7 wt%, from 3 wt% to 6 wt%, from 4 wt% to 15 wt%, from 4 wt% to 10 wt%, from 4 wt% to 9 wt%, from 4 wt% to 8 wt%, from 4 wt% to 7 wt%, from 4 wt% to 6 wt%, from 5 wt% to 15 wt%, from 5 wt% to 10 wt%, from 5 wt% to 9 wt%, from 5 wt% to 8 wt%, from 5 wt% to 7 wt%, or even from 5 wt% to 6 wt%, or any and all sub-ranges formed from any of these endpoints.

[0051] Free Radical Initiator

[0052] Free radical initiator enables grafting of the graftable polymer composition, thereby forming the grafted composition. The free radical initiator decomposes whereby forming free radicals and the reaction of primary radicals with polymer composition.

[0053] In embodiments, the free radical initiator may comprise an organic peroxide. Nonlimiting examples of suitable organic peroxide include bis(1,1-dimethylethyl) peroxide; bis(1,1-dimethylpropyl) peroxide; 2,5-dimethyl-2,5-bis(1,1-dimethylethylperoxy) hexane; 2,5-dimethyl-2,5-bis(1,1-dimethylethylperoxy) hexyne; 4,4-bis(1,1-dimethylethylperoxy) valeric acid; butyl ester; 1,1-bis(1,1-dimethylethylperoxy)-3,3,5-trimethylcyclohexane; benzoyl peroxide; tert-butyl peroxybenzoate; di-tert-amyl peroxide (“DTAP”), bis(α-t-butyl- peroxyisopropyl) benzene (“BIBP”); isopropylcymyl t-butyl peroxide; t- butylcumylperoxide; di-t-butyl peroxide; 2,5-bis(t-butylperoxy)-2,5-dimethylhexane; 2,5- 86830-WO-PCT / DOW 86830 WO bis(tbutylperoxy)-2,5-dimethylhexyne-3,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane; isopropylcumyl cumylperoxide; butyl 4,4-di(tert-butylperoxy) valerate; di(isopropylcumyl) peroxide; dicumyl peroxide, and combinations thereof. In embodiments, the free radical initiator may comprise dicumyl peroxide.

[0054] The graftable polymer composition may comprise a minimum amount of free radical initiator (e.g., greater than or equal to 0.1 wt%) to initiate grafting of the graftable polymer composition. The amount of the free radical initiator may be limited (e.g., less than or equal to 5 wt%) to prevent chain scission. Accordingly, in embodiments, the graftable polymer composition may comprise from 0.1 wt% to 10 wt% free radical initiator. In embodiments, the amount of the free radical initiator in the graftable polymer composition may be greater than or equal to 0.1 wt%, greater than or equal to 0.25, greater than or equal to 0.5 wt%, or even greater than or equal to 0.75 wt%. In embodiments, the amount of the free radical initiator in the graftable polymer composition may be less than or equal to 5 wt%, less than or equal to 3 wt%, or even less than or equal to 1 wt%. In embodiments, the amount of free radical initiator in the graftable polymer composition may be from 0.1 wt% to 5 wt%, from 0.1 wt% to 3 wt%, from 0.1 wt% to 1 wt%, from 0.25 wt% to 5 wt%, from 0.25 wt% to 3 wt%, from 0.25 wt% to 1 wt%, from 0.5 wt% to 5 wt%, from 0.5 wt% to 3 wt%, from 0.5 wt% to 1 wt%, from 0.75 wt% to 5 wt%, from 0.75 wt% to 3 wt%, or even from 0.75 wt% to 1 wt%, or any and all sub-ranges formed from any of these endpoints.

[0055] In embodiments, a weight ratio of free radical initiator to BPST or BPMA may be from 1:6 to 1:2 to ensure reduced chain scission and prevent undesirable crosslinking. In embodiments, a weight ratio of free radical initiator to BPST or BPMA may be from 1:6 to 1:2; from 1:6 to 1:3; from 1:6 to 1:4; from 1:5 to 1:2; from 1:5 to 1:3; or even from 1:5 to 1:4; or any and all sub-ranges formed from any of these endpoints.

[0056] Blend Component

[0057] In embodiments, the graftable polymer composition and / or the grafted composition includes a blend component. Nonlimiting examples of suitable blend component include ethylene vinyl acetate (EVA), polyolefins (e.g., polypropylene other than the propylene- based polymer grafted with maleic anhydride), polymers (e.g., polystyrene, ABS, SBS and the like) and combinations thereof. Non-limiting examples of suitable polyolefins include polyethylene; polypropylene; polybutylene (e.g., polybutene-1); polypentene-1; polyhexene- 86830-WO-PCT / DOW 86830 WO 1; polyoctene-1; polydecene-1; poly-3-methylbutene-1; poly-4-methylpentene-l; polyisoprene; polybutadiene; poly-1,5-hexadiene; interpolymers derived from olefins; interpolymers derived from olefins and other polymers such as polyvinyl chloride, polystyrene, and polyurethane; and combinations thereof.

[0058] In an embodiment, the polyolefin is a homopolymer such as polyethylene, polypropylene, polybutylene, polypentene-1, poly-3-methylbutene-1, poly-4-methylpentene- 1, polyisoprene, polybutadiene, poly-1,5-hexadiene, polyhexene-1, polyoctene-1 and polydecene-1.

[0059] Nonlimiting example of suitable polypropylene as a blend component (other than the propylene-based polymer that is grafted with maleic anhydride) include low density polypropylene (LDPP), high density polypropylene (HDPP), high-melt strength polypropylene (HMS-PP) and combination thereof. Nonlimiting examples of polyethylene include ultra low density polyethylene (ULDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), high molecular weight high density polyethylene (HMW-HDPE), ultra high molecular weight polyethylene (UHMW-PE) and combinations thereof. In an embodiment, the blend component is a high-melt strength polypropylene (HMS-PP), a low density polyethylene (LDPE) or a combination thereof.

[0060] Additives

[0061] The graftable composition and / or the grafted composition may contain one or more optional additives. Nonlimiting examples of suitable additives include grafting initiators, blowing agent, blowing agent activators (e.g., zinc oxide, zinc stearate and the like), coagents (e.g., triallyl cyanurate), plasticizers, processing oils, processing aids, carbon black, colorants or pigments, stability control agents, nucleating agents, fillers, antioxidants, acid scavengers, ultraviolet (UV) stabilizers, flame retardants, lubricants, processing aids, extrusion aids, and combinations thereof. When present, the total amount of additive can be from greater than 0% to 80%, or from 0.001% to 70%, or from 0.01% to 60 %, or from 0.1 % to 50 %, or from 0.1 % to 40%, or from 0.1% to 20%, or from 0.1 % to 10 %, or from 0.1% to 5% of the total weight of the composition.

[0062] In embodiments, the graftable composition and / or the grafted composition includes an antioxidant. Non-limiting examples of suitable antioxidants include aromatic or hindered 86830-WO-PCT / DOW 86830 WO amines such as alkyl diphenylamines, phenyl-a-naphthylamine, alkyl or aralkyl substituted phenyl-a-naphthylamine, alkylated p-phenylene diamines, tetramethyl- diaminodiphenylamine and the like; phenols such as 2,6-di-t-butyl-4-methylphenol; 1,3,5- trimethyl-2,4,6-tris(3',5,-di-t-butyl-4,-hydroxybenzyl)benzene; tetrakis[(methylene(3,5 -di-t- buty1-4-hydroxyhydrocinnamate)]methane (e.g., IRGANOX™ 1010, from Ciba Geigy, NewYork); acryloyl modified phenols; octadecyl-3,5- di-t-butyl-4-hydroxycinnamate (e.g., IRGANOX 1076, commercially available from Ciba Geigy); phosphites and phosphonites; hydroxylamines; benzofuranone derivatives; and combinations thereof. When used, the amount of the antioxidant in the composition can be from greater than 0 to 5%, or from 0.0001 to 2.5%, or from 0.001 to 1%, or from 0.001 to 0.5% of the total weight of the composition.

[0063] In embodiments, the graftable composition and / or the grafted composition includes a UV stabilizer. Non-limiting examples of suitable UV stabilizers include benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidines, carbon black, hindered amines, nickel quenchers, hindered amines, phenolic antioxidants, metallic salts, zinc compounds and combinations thereof. When used, the amount of the UV stabilizer can be from greater than 0 to 5%, or from 0.01 % to 3 %, or from 0.1 % to 2 %, or from 0.1% to 1% of the total weight of the composition.

[0064] In embodiments, the graftable composition and / or the grafted composition includes a colorant or a pigment. Non-limiting examples of suitable colorants or pigments include inorganic pigments such as metal oxides such as iron oxide, zinc oxide, and titanium dioxide, mixed metal oxides, carbon black, organic pigments such as anthraquinones, anthanthrones, azo and monoazo compounds, arylamides, benzimidazolones, BONA lakes, diketopyrrolo- pyrroles, dioxazines, disazo compounds, diarylide compounds, flavanthrones, indanthrones, isoindolinones, isoindolines, metal complexes, monoazo salts, naphthols, b-naphthols, naphthol AS, naphthol lakes, perylenes, perinones, phthalocyanines, pyranthrones, quinacridones, and quinophthalones, and combinations thereof. When used, the amount of the colorant or pigment in the composition can be from greater than 0 to 10%, or from 0.1% to 5 %, or from 0.25% to 2% of the total weight of the composition.

[0065] In embodiments, the graftable composition and / or the grafted composition includes a filler. Nonlimiting examples of suitable fillers include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina such as alumina 86830-WO-PCT / DOW 86830 WO trihydrate, glass microsphere, ceramic microsphere, thermoplastic microsphere, barite, wood flour, glass fibers, carbon fibers, marble dust, cement dust, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanates and combinations thereof.

[0066] In embodiments, the filler is barium sulfate, talc, calcium carbonate, silica, glass, glass fiber, alumina, titanium dioxide, or a mixture thereof. In a further embodiment, the filler is talc, calcium carbonate, barium sulfate, glass fiber or a mixture thereof. When used, the amount of the filler in the composition can be from greater than 0 to 80%, or from 0.1 to 60%, or from 0.5 to 40%, or from 1 to 30%, or from 10 to 40% of the total weight of the composition.

[0067] In embodiments, the graftable composition and / or the grafted composition includes a lubricant. Nonlimiting examples of suitable lubricants include fatty alcohols and their dicarboxylic acid esters, fatty acid esters of short chain alcohols, fatty acids, fatty acid amides, metal soaps, oligomeric fatty acid esters, fatty acid esters of long-chain alcohols, montan waxes, polyethylene waxes, polypropylene waxes, natural and synthetic paraffin waxes, fluoropolymers and combinations thereof. When used, the amount of the lubricant in the composition can be from greater than 0% to 5%, or from 0.1 to 4%, or from 0.1% to 3% of the total weight of the composition.

[0068] In embodiments, the graftable composition and / or the grafted composition includes an antistatic agent. Non-limiting examples of suitable antistatic agents include conductive fillers (e.g., carbon black, metal particles and other conductive particles), fatty acid esters (e.g., glycerol monostearate), ethoxylated alkylamines, diethanolamides, ethoxylated alcohols, alkylsulfonates, alkylphosphates, quaternary ammonium salts, alkylbetaines and combinations thereof. Where used, the amount of the antistatic agent in the composition can be from greater than 0 % to 5 %, or from 0.01 to 3 %, or from 0.1 to 2 % of the total weight of the composition.

[0069] In embodiments, the graftable composition and / or the grafted composition includes a blowing agent. A "blowing agent" is a substance that is capable of producing a cellular structure in the composition via a foaming process. The blowing agent is used for foaming the grafted composition. Nonlimiting examples of suitable blowing agent include an inorganic physical blowing agent, such as air, argon, nitrogen, carbon dioxide, argon, helium, 86830-WO-PCT / DOW 86830 WO oxygen, and neon, and an organic physical blowing agent, such as an aliphatic hydrocarbon, e.g., propane, n- butane, isobutane, n-pentane, isopentane, and n-hexane, an alicyclic hydrocarbon, e.g., cyclohexane and cyclopentane, a halogenated hydrocarbon, e.g., chlorofluoromethane, trifluoromethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, methyl chloride, ethyl chloride, and methylene chloride, and a dialkyl ether, e.g., dimethyl ether, diethyl ether, and methyl ethyl ether.

[0070] Non-limiting examples of suitable organic blowing agents include aliphatic hydrocarbons having 1-6 carbon atoms, aliphatic alcohols having 1-3 carbon atoms, and fully and partially halogenated aliphatic hydrocarbons having 1-4 carbon atoms. Non-limiting examples of suitable aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n- pentane, isopentane, neopentane, and the like. Non-limiting examples of suitable aliphatic alcohols include methanol, ethanol, n-propanol, and isopropanol. Non- limiting examples of suitable fully and partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons, and chlorofluorocarbons. Non-limiting examples of suitable fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC152a), 1,1,1- trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1- trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane. Non-limiting examples of suitable partially halogenated chlorocarbons and chlorofluorocarbons include methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro- 1-fluoroethane (HCFC-141b), l-chloro- l,ldifluoroethane (HCFC-142b), l,l-dichloro-2,2,2- trifluoroethane (HCFC-123) and l-chloro- l,2,2,2-tetrafluoroethane(HCFC-124). Non-limiting examples of suitable fully halogenated chlorofluorocarbons include trichloromonofluoromethane (OPOI 1}, dichlorodifluoromethane (CFO-12}, trichlorotrifluoroethane (CFO-113), 1,1,1- trifluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFO-114), chloroheptafluoropropane, and dichlorohexafluoropropane. Non-limiting examples of suitable chemical blowing agents include azodicarbonamide, azodiisobutyro- nitrile, benezenesulfonhydrazide, 4,4-oxybenzene sulfonyl-semicarbazide, p-toluene sulfonyl semi-carbazide, barium azodicarboxylate, N,N'- dimethyl-N,N'- dinitrosoterephthalamide, and trihydrazino triazine.

[0071] Grafted Composition 86830-WO-PCT / DOW 86830 WO

[0072] The graftable polymer compositions as described herein, including an propylene- based polymer, maleic anhydride, and either BPST or BPMA with a coagent, may be melt blended at a temperature from 100 °C to 250 °C, from 100 °C to 200 °C, from 100 °C to 180 °C, from 120 °C to 250 °C, from 120 °C to 200 °C, from 120 °C to 180 °C, from 140 °C to 250 °C, from 140 °C to 200 °C, from 140 °C to 180 °C, from 160 °C to 250 °C, from 160 °C to 200 °C, or even from 160 °C to 180 °C to trigger a grafting reaction and form the grafted composition.

[0073] The grafted compositions may comprise a maleic anhydride-grafted propylene-based polymer and BPST or BPMA with a coagent.

[0074] In embodiments, the grafted compositions may comprise from 85 wt% to 99 wt% of the maleic anhydride-grafted propylene-based polymer. In embodiments, the grafted compositions may comprise from 70 wt% to 98 wt% of the maleic anhydride-grafted propylene-based polymer. In embodiments, the amount of the maleic anhydride-grafted propylene-based polymer in the grafted composition may be greater than or equal to 70 wt%, greater than or equal to 80 wt%, greater than or equal to 85 wt%, greater than or equal to 90 wt%, or even greater than or equal to 95 wt%. In embodiments, the amount of the maleic anhydride-grafted propylene-based polymer in the grafted composition may be less than or equal to 99 wt%, less than or equal to 98 wt%, less than or equal to 96 wt%, or even less than or equal to 94 wt%. In embodiments, the amount of the maleic anhydride-grafted propylene- based polymer in the grafted composition may be from 70 wt% to 99 wt%, from 70 wt% to 98 wt%, from 70 wt% to 96 wt%, from 70 wt% to 94 wt%, from 75 wt% to 99 wt%, from 75 wt% to 98 wt%, from 75 wt% to 96 wt%, from 75 wt% to 94 wt%, from 80 wt% to 99 wt%, from 80 wt% to 98 wt%, from 80 wt% to 96 wt%, from 80 wt% to 94 wt%, from 85 wt% to 99 wt%, from 85 wt% to 98 wt%, from 85 wt% to 96 wt%, from 85 wt% to 94 wt%, from 90 wt% to 99 wt%, from 90 wt% to 98 wt%, from 90 wt% to 96 wt%, from 90 wt% to 94 wt%, from 95 wt% to 99 wt%, from 95 wt% to 98 wt%, or even from 95 wt% to 96 wt%, or any and all sub-ranges formed from any of these endpoints.

[0075] In embodiments, the grafted compositions may comprise from 1 wt% to 15 wt% of the BPST. In embodiments, the amount of the BPST in the grafted composition may be greater than or equal to 1 wt%, greater than or equal to 3 wt%, or even greater than or equal to 5 wt%. In embodiments, the amount of the BPST in the grafted composition may be less than or equal to 15 wt%, less than or equal to 13 wt%, less than or equal to 10 wt%, less than 86830-WO-PCT / DOW 86830 WO or equal to 7 wt%, less than or equal to 5 wt%, or even less than or equal to 3 wt%. In embodiments, the amount of the BPST in the grafted composition may be from 1 wt% to 15 wt%, from 1 wt% to 13 wt%, from 1 wt% to 10 wt%, from 1 wt% to 7 wt%, from 1 wt% to 5 wt%, from 1 wt% to 3 wt%, from 3 wt% to 15 wt%, from 3 wt% to 13 wt%, from 3 wt% to 10 wt%, from 3 wt% to 7 wt%, from 3 wt% to 5 wt%, from 5 wt% to 15 wt%, from 5 wt% to 13 wt%, from 5 wt% to 10 wt%, or from 5 wt% to 7 wt%, or any and all sub-ranges formed from any of these endpoints.

[0076] In embodiments, the grafted compositions may comprise from 1 wt% to 13 wt% of the BPMA. In embodiments, the amount of the BPMA in the grafted composition may be greater than or equal to 1 wt%, greater than or equal to 3 wt%, or even greater than or equal to 5 wt%. In embodiments, the amount of the BPMA in the grafted composition may be less than or equal to 13 wt%, less than or equal to 10 wt%, less than or equal to 7 wt%, less than or equal to 5 wt%, or even less than or equal to 3 wt%. In embodiments, the amount of the BPMA in the grafted composition may be from 1 wt% to 13 wt%, from 1 wt% to 10 wt%, from 1 wt% to 7 wt%, from 1 wt% to 5 wt%, from 1 wt% to 3 wt%, from 3 wt% to 13 wt%, from 3 wt% to 10 wt%, from 3 wt% to 7 wt%, from 3 wt% to 5 wt%, from 5 wt% to 13 wt%, from 5 wt% to 10 wt%, or from 5 wt% to 7 wt%, or any and all sub-ranges formed from any of these endpoints.

[0077] In embodiments, the grafted compositions may comprise from 1 wt% to 17 wt% of the coagent. In embodiments, the amount of the coagent in the grafted composition may be greater than or equal to 1 wt%, greater than or equal to 3 wt%, or even greater than or equal to 5 wt%. In embodiments, the amount of the coagnet in the grafted composition may be less than or equal to 17 wt%, less than or equal to 15 wt%, less than or equal to 13 wt%, less than or equal to 10 wt%, less than or equal to 7 wt%, less than or equal to 5 wt%, or even less than or equal to 3 wt%. In embodiments, the amount of the coagent in the grafted composition may be from 1 wt% to 17 wt%, from 1 wt% to 15 wt%, from 1 wt% to 13 wt%, from 1 wt% to 10 wt%, from 1 wt% to 7 wt%, from 1 wt% to 5 wt%, from 1 wt% to 3 wt%, from 3 wt% to 17 wt%, from 3 wt% to 15 wt%, from 3 wt% to 13 wt%, from 3 wt% to 10 wt%, from 3 wt% to 7 wt%, from 3 wt% to 5 wt%, from 5 wt% to 17 wt%, from 5 wt% to 15 wt%, from 5 wt% to 13 wt%, from 5 wt% to 10 wt%, or from 5 wt% to 7 wt%, or any and all sub-ranges formed from any of these endpoints. 86830-WO-PCT / DOW 86830 WO

[0078] In embodiments, the grafted compositions may comprise a maleic anhydride grafting level from 0.1 wt% to 3 wt%. In embodiments, the maleic anhydride grafting level may be greater than or equal to 0.1 wt% or even greater than or equal to 0.2 wt%. In embodiments, the maleic anhydride grafting level may be less than or equal to 3 wt%, less than or equal to 2 wt%, less than or equal to 1 wt%, or even less than or equal to 0.5 wt%. In embodiments, the maleic anhydride grafting level may be from 0.1 wt% to 3 wt%, from 0.1 wt% to 2 wt%, from 0.1 wt% to 1 wt%, from 0.1 wt% to 0.5 wt%, from 0.2 wt% to 3 wt%, from 0.2 wt% to 2 wt%, from 0.2 wt% to 1 wt%, or from 0.2 wt% to 0.5 wt%, or any and all sub-ranges formed from any of these endpoints.

[0079] As described herein, the grafted compositions have reduced chain scission (e.g., greater Mw as compared to a grafted composition lacking BPST or BPMA). In embodiments, the grafted composition may comprise a Mwgreater than or equal to 125,000 g / mol; greater than or equal to 150,000 g / mol; or even greater than or equal to 175,000 g / mol. In embodiments, the grafted composition may comprise a Mw less than or equal to 500,000 g / mol; less than or equal to 400,000 g / mol; less than or equal to 300,000 g / mol; or even less than or equal to 200,000 g / mol. In embodiments, the grafted composition may comprise a Mw from 125,000 g / mol to 500,000 g / mol; from 125,000 g / mol to 400,000 g / mol; from 125,000 g / mol to 300,000 g / mol; from 125,000 g / mol to 200,000 g / mol; from 150,000 g / mol to 500,000 g / mol; from 150,000 g / mol to 400,000 g / mol; from 150,000 g / mol to 300,000 g / mol; from 150,000 g / mol to 200,000 g / mol; from 175,000 g / mol to 500,000 g / mol; from 175,000 g / mol to 400,000 g / mol; from 175,000 g / mol to 300,000 g / mol; or even from 175,000 g / mol to 200,000 g / mol; or any and all sub-ranges formed from any of these endpoints.

[0080] In embodiments, the grafted composition may comprise a Mn from 15,000 g / mol to 70,000 g / mol; from 15,000 g / mol to 50,000 g / mol; from 15,000 g / mol to 30,000 g / mol; from 20,000 g / mol to 70,000 g / mol; from 20,000 g / mol to 50,000 g / mol; or even from 20,000 g / mol to 30,000 g / mol; or any and all sub-ranges formed from any of these endpoints.

[0081] In embodiments, the grafted composition may comprise a polydispersity index Mw / Mnfrom 4.0 to 12.0, from 4.0 to 10.0, from 4.0 to 8.0, from 6.0 to 12.0, from 6.0 to 10.0, or even from 6.0 to 8.0, or any and all sub-ranges formed from any of these endpoints.

[0082] In embodiments, the grafted composition may comprise a Mz from 100,000 g / mol to 1,000,000 g / mol; from 100,000 g / mol to 800,000 g / mol; from 100,000 g / mol to 600,000 86830-WO-PCT / DOW 86830 WO g / mol; from 300,000 g / mol to 1,000,000 g / mol; from 300,000 g / mol to 800,000 g / mol; from 300,000 g / mol to 600,000 g / mol; from 500,000 g / mol to 1,000,000 g / mol; from 500,000 g / mol to 800,000 g / mol; or even from 500,000 g / mol to 600,000 g / mol; or any and all sub- ranges formed from any of these endpoints.

[0083] In embodiments, the grafted composition may not be crosslinked, which may be desirable in certain applications, as indicated by a mass recovery greater than or equal to 90%.

[0084] In embodiments, the grafted composition may comprise a melt flow rate MFR less than or equal to 100 g / 10 min such that the grafted composition has a desired viscosity for use in certain applications. In embodiments, the grafted composition may comprise a melt flow rate MFR less than or equal to 100 g / 10 min, less than or equal to 75 g / 10 min, less than or equal to 50 g / 10 min, or even less than or equal to 25 g / 10 min.

[0085] TEST METHODS

[0086] Density

[0087] Density was measured in accordance with ASTM D792, with results reported in g / cm3at 25 °C.

[0088] Melt Flow Rate (MFR)

[0089] MFR (for propylene-based polymers) was measured in accordance with ASTM D 1238, Condition 230 °C / 2.16 kg with results reported in grams per 10 minutes (g / 10 min).

[0090] Differential Scanning Calorimetry (DSC)

[0091] DSC was conducted using a Mettler Toledo DSC822e differential scanning calorimeter to measure melting point.

[0092] Maleic Anhydride Grating Level – Fourier Transform Infrared Spectroscopy (FTIR) Analysis

[0093] The level of functionalization (wt%) for maleic anhydride (MAH) is determined by the ratio of the peak height of the MAH (FTIRMAH) to the peak height of the polymer reference (FTIRref). The peak height of MAH is at wave number 1790 cm-1and the height of the inflection point, which can be used as the polymer reference, is at 2751 cm-1. The ratio of peak heights is multiplied by the appropriate calibration constants (A and B) and the products of the ratios and calibration constants are added together with a y-intercept (C) to equal the 86830-WO-PCT / DOW 86830 WO MAH wt%. When polyethylene / polypropylene is the reference polymer, the MAH wt% is calculated according to the following MAH wt% formula:

[0094] The calibration constants can be determined using acid-base titration standards, which are known in the field. Acid-base titration was used to determine the concentration of maleic anhydride in samples used as calibration standards. These standards were then used to generate the FTIR calibration model. The actual calibration constant may differ slightly depending on the instrument and the polymers. The MAH wt% formula takes different sample thicknesses into account to normalize the data.

[0095] A sample of the maleic anhydride grafted polyolefin can be prepared for FTIR analyst in a heating press. The sample of the adhesive layer is about 0.05 mm to about 0.15 mm in thickness and is placed between suitable protective films, such as MYLAR™ or TEFLON™, to protect it from the platens of the heating press. Aluminum foil should not be used as a protective film because maleic anhydride reacts with aluminum. The sample is then placed in the heating press at about 150-180 °C and the platens should be under about 10 tons of pressure for about five minutes. The sample remains in the heating press for about one hour and then is allowed to cool to room temperature before being scanned in the FTIR.

[0096] Gel Permeation Chromatography (GPC)

[0097] The chromatographic system consisted of a Polymer Char GPC-IR (Valencia, Spain) high temperature GPC chromatograph, equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set at 160 °C, and the column compartment was set at 150° Celsius. The columns were one Agilent PLgel MIXED 7.5 x 50 mm, 20 µm linear mixed-bed guard column and four Agilent PLgel MIXED-A 7.5 x 300 mm, 20 µm linear mixed-bed columns. The chromatographic solvent was 1,2,4-trichlorobenzene, which contained 300 ppm of butylated hydroxytoluene (BHT) and was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0098] Calibration of the GPC column set was performed using Agilent EasiCal Polystyrene standards (EasiCal PS-1 and EasiCal PS-2). Each EasiCal system consisted of two different spatulas supporting a mixture of 5 polymer standards (approximately 5 mg) to obtain 20 molecular weights points ranging from approximately 580 to 6,570,000 g / mole. Individual 86830-WO-PCT / DOW 86830 WO spatulas were added to septa-capped vials, sealed, and loaded into the Polymer Char autosampler. Polymer Char Instrument Control Software was utilized to add 8 mL of solvent to each vial and the standards were dissolved for 15 minutes at 160 °C under high-speed shaking prior to injection to the chromatography system. A third order polynomial was used to fit the nominal polystyrene standard peak molecular weights to obtain molecular weight equivalent calibration points at each chromatographic slice. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).: where M is the molecular weight, A has a value of 0.41 and B is equal to 1.0.

[0099] The total plate count of the GPC column set was performed with decane (3% v / v in 1,2,4-trichlorobenzene (TCB) introduced via micropump). The plate count for the chromatographic system should be greater than 18,000 for the 4 Agilent “Mixed A” 30 cm 20-micron linear mixed-bed columns.

[0100] Samples were prepared in a semi-automatic manner with the Polymer Char Instrument Control Software, wherein the samples were weight-targeted at 2 mg / ml, and the solvent was added to a septa-capped sealed vial via the Polymer Char high temperature autosampler. The samples were dissolved for two hours at 160° Celsius under high-speed shaking.

[0101] The calculations of Mn(GPC), Mw(GPC),and Mz(GPC)were based on GPC results using the internal IR5 detector (measurement channel) of the Polymer Char GPC-IR chromatograph according to Equations 2-4. Using Polymer Char GPCOne™ software, the baseline- subtracted IR chromatogram at each equally-spaced data collection point (i) was converted to the polyethylene equivalent molecular weight, obtained from the narrow standard calibration curve, for the equivalent chromatographic data point (i). Equations 2-4 are as follows: 86830-WO-PCT / DOW 86830 WO

[0102] In order to monitor the deviations over time, a flowrate marker (3% v / v decane in solvent) was introduced into each sample via a micropump controlled with the Polymer Char GPC-IR system. This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate(nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak were then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run. After calibrating the system based on a flow marker peak, the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation 5. Processing of the flow marker peak was done via the Polymer Char GPCOne™ Software. Acceptable flowrate correction is such that the effective flowrate should be within + / -0.7% of the nominal flowrate. Flowrate(effective)= Flowrate(nominal)* (RV(FM Calibrated) / RV(FM Sample)) (EQ 5)

[0103] Mass recovery was determined in a way consistent with that used within PolymerChar GPCOne Software using the total signal areas of a sample eluted by the GPC method via IR5 broad filter detector measurement channel and adjusted using a mass constant as determined with a vendor recommended polyethylene homopolymer standard. Mass recovery is calculated as Equation 6: Mass recovery = 100 x [(initial analyte - filtered analyte) / initial analyte] (EQ 6) using the analyte mass values obtained in the PolymerChar SoGPC test. It is understood that polymers with internal crosslinking form insoluble gels that are quantifiably detectable by low mass recovery analysis.

[0104] EXAMPLES

[0105] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail by the following examples.

[0106] Materials

[0107] Materials used in Comparative Compositions C1-C3 and Example Compositions E1 and E2 are provided in Table 1 below. 86830-WO-PCT / DOW 86830 WO

[0108] Table 1

[0109] Synthesis of BPST

[0110] To synthesize BPST, 2-phenylacryloyl chloride (5.00 g, 30.0 mmol) was dissolved in 150 mL dichloromethane (DCM) and was stirred at 0 ℃ in an ice bath. bis(4- hydroxyphenyl) disulfide (2.5 g, 10 mmol, supplied by Ambeed, Inc.) and 4- dimethylaminopyridine (DMAP) (20 mg, 0.08 mmol, supplied by Sigma-Aldrich) were added to the mixture, resulting in a milky yellowish solution. Triethylamine (supplied by Sigma- Aldrich) was added dropwise. The solution developed purple hue upon addition and gradually turned back to be milky yellowish. Triethylamine was continually added until the solution was no longer purple. 10% more triethylamine was added dropwise to ensure completion. In total, about 5 mL (36 mmol) triethylamine was added. The mixture returned to room temperature and stirred overnight for 18 hours. 500 mL of 0.1 M K2CO3solution (supplied by Sigma-Aldrich) was poured into the mixture and stirred for 1 hour. 500 mL DCM was then added, and the aqueous phase was removed by a separation funnel. The organic phase was further extracted with DI water twice and dried over magnesium sulfate. Then DCM was then removed by a rotary evaporator. The crude product was purified twice by first dissolving in 15 mL DCM at 40 ℃ and then recrystallized at room temperature for 5 hours and dried in a vacuum oven at 80 °C for 24 hours to yield BiPheS phenylacrylate

[0111] Preparation of Grafted Compositions

[0112] Maleic anhydride melt grafting reaction occurred in a Haake Mixer with nitrogen purge and in a ventilated enclosure. Propylene-based polymer was added to the mixer and 86830-WO-PCT / DOW 86830 WO melt mixed at 10 rpm. BPST was then added, followed by maleic anhydride and BPST. The blend was mixed at 180 °C and 50 rpm for 10 minutes prior to collecting the sample.

[0113] Properties

[0114] The compositions and properties of Comparative Compositions C1-C3 and Example Compositions E1 and E2 are provided in Table 2 below.

[0115] Table 2

[0116] As shown, Comparative Compositions C2 and C3 and Example Compositions E1 and E2 were grafted, as indicated by a grafting level greater than 0 wt%. However, Example Compositions E1 and E2, grafted compositions including BPST, had a greater Mw as compared to Comparative Compositions C2 and C3, grafted compositions lacking BPST. A exemplified by Table 2, graftable polymer compositions including BPST as described herein may be used to form grafted compositions with reduced chain scission.

[0117] While particular embodiments of the present disclosure have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the disclosure. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this disclosure.

Claims

86830-WO-PCT / DOW 86830 WO CLAIMS 1. A graftable polymer composition comprising: a propylene-based polymer; maleic anhydride; a free radical initiator; and bis(4-phenacryloyloxyphenyl) disulfide (BPST).

2. The graftable polymer composition of claim 1, wherein the propylene-based polymer is selected from the group consisting of polypropylene homopolymer, polypropylene-based elastomer, polypropylene-based block copolymer, propylene-based impact copolymer, and combinations thereof.

3. The graftable polymer composition of any one of the preceding claims, wherein the free radical initiator comprises an organic peroxide.

4. The graftable polymer composition of any one of the preceding claims, wherein the graftable polymer composition comprises: from 70 wt% to 99 wt% of the propylene-based polymer; from 0.5 wt% to 10 wt% of the maleic anhydride; from 0.1 wt% to 5 wt% of the free radical initiator; and from 0.5 wt% to 10 wt% of the BPST.

5. The graftable polymer composition of any one of the preceding claims, wherein the graftable polymer composition comprises a weight ratio of free radical initiator to BPST from 1:6 to 1:

2.

6. A grafted composition comprising: a maleic anhydride-grafted propylene-based polymer; and bis(4-phenacryloyloxyphenyl) disulfide (BPST).

7. The grafted composition of claim 6, wherein the maleic anhydride-grafted propylene- based polymer comprises a maleic anhydride grafting level from 0.1 wt% to 3 wt%.86830-WO-PCT / DOW 86830 WO 8. A graftable polymer composition comprising: a propylene-based polymer; maleic anhydride; a free radical initiator; a coagent; and bis(4-methacryloyloxyphenyl) disulfide (BPMA).

9. The graftable polymer composition of claim 8, wherein the coagent comprises styrene; divinyl benzene; 1,1,1-trimethylolpropane trimethacrylate; pentaerythrityl tetramethacrylate (PETM); trimethylolpropanetiacrylate (TMPTA); pentaerythritol tetraacrylate (PETA); pentaerythritol tetrallyl ether; diallyl maleate; triallyl cyanurate; diallyl itaconate; triallylisocyanurate (TAIC); 4-vinylnapthalene; or a combination thereof.

10. The graftable polymer composition of claim 8 or claim 9, wherein the propylene-based polymer is selected from the group consisting of polypropylene homopolymer, polypropylene- based elastomer, polypropylene-based block copolymer, propylene-based impact copolymer, and combinations thereof.

11. The graftable polymer composition of any one of claims 8-10, wherein the free radical initiator comprises an organic peroxide.

12. The graftable polymer composition of any one of claims 8-11, wherein the graftable polymer composition comprises: from 70 wt% to 97.5 wt% of the propylene-based polymer; from 0.5 wt% to 10 wt% of the maleic anhydride; from 0.1 wt% to 5 wt% of the free radical initiator; from 0.5 wt% to 15 wt% of the coagent; and from 0.5 wt% to 10 wt% of the BPMA.

13. The graftable polymer composition of any one of claims 8-12, wherein the graftable polymer composition comprises a weight ratio of free radical initiator to BPMA from 1:6 to 1:2.86830-WO-PCT / DOW 86830 WO 14. A grafted composition comprising: a maleic anhydride-grafted propylene-based polymer; a coagent; and bis(4-methacryloyloxyphenyl) disulfide (BPMA).

15. The grafted composition of claim 14, wherein the maleic anhydride-grafted propylene- based polymer comprises a maleic anhydride grafting level from 0.1 wt% to 3 wt%.

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