Peroxide vulcanizable compositions and partially crosslinked polymer systems formed therefrom

Abstract

Embodiments of the present disclosure relate to a partially crosslinked polymer system comprising a vulcanized silane grafted thermoplastic elastomer and a carbon-carbon bond crosslinking. The vulcanized silane grafted thermoplastic elastomer includes a polymerization reaction product of a vinyl aromatic monomer unit and a conjugated diene monomer unit.

Description

[0001] Claiming priority

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application Serial No. 63 / 389,579, filed on July 15, 2022, with Attorney Docket No. 1202209, which is incorporated herein by reference in its entirety. Technical Field

[0003] Embodiments of the present disclosure are generally directed to peroxide-curable compositions and partially crosslinked polymer systems formed therefrom. Background Art

[0004] Cross-linked thermoplastic articles may have desirable properties, such as chemical and heat resistance. However, conventional processes for forming thermoplastic articles may require additional steps, time and materials to achieve the cross-link density and heat resistance required for certain applications in healthcare, automotive and electronics.

[0005] Therefore, there is a continuing need for new and more cost-effective solutions for forming thermoplastic articles having improved crosslink density and heat resistance. Summary of the invention

[0006] Embodiments of the present disclosure are directed to partially crosslinked polymer systems comprising vulcanized silane grafted thermoplastic elastomers having carbon-carbon bond crosslinks, which have advantageous crosslink density and heat resistance without requiring additional processing steps, time, and materials.

[0007] In some embodiments, the degree of hydrogenation of the thermoplastic elastomer may be greater than or equal to about 50%, greater than or equal to about 60%, greater than or equal to about 70%, greater than or equal to about 80%, greater than or equal to about 85%, greater than or equal to about 90%, or even greater than or equal to about 95%, based on the unsaturated groups of the conjugated diene monomer units in the previously partially hydrogenated thermoplastic elastomer.

[0008] According to another embodiment, a peroxide vulcanizable composition is provided. The peroxide vulcanizable composition comprises a thermoplastic elastomer and a vulcanization package. The thermoplastic elastomer comprises a vinyl aromatic monomer unit and a conjugated diene monomer unit. The vulcanization package comprises an organic peroxide and a silane.

[0009] According to another embodiment, a method for preparing a partially crosslinked polymer system is provided, wherein the partially crosslinked polymer system comprises a crosslinked reaction product of a thermoplastic elastomer and a vulcanization package, wherein the thermoplastic elastomer comprises vinyl aromatic monomer units and conjugated diene monomer units, and the vulcanization package comprises an organic peroxide and a silane. The method comprises: blending the thermoplastic elastomer, the organic peroxide and the silane so that the thermoplastic elastomer comprises carbon-carbon crosslinks and grafted silane moieties; and molding the carbon-carbon crosslinked grafted silane blend.

[0010] Other features and advantages of the embodiments described herein will be given in the detailed description below. For those skilled in the art, they can be easily understood from these descriptions, or some of the features and advantages thereof can be recognized by practicing the embodiments described herein, including the following specific embodiments and claims. DETAILED DESCRIPTION

[0011] Reference will now be made in detail to various embodiments of partially crosslinked polymer systems, particularly partially crosslinked polymer systems comprising a vulcanized silane-grafted thermoplastic elastomer having carbon-carbon bond crosslinks. The vulcanized silane-grafted thermoplastic elastomer comprises a polymerization reaction product of vinyl aromatic monomer units and conjugated diene monomer units. In some embodiments, the partially crosslinked polymer system can be a thermoplastic vulcanizate.

[0012] The present disclosure should not be understood to be limited to the embodiments described herein. Rather, these embodiments are provided to make the present disclosure thorough and complete and to fully convey the subject matter to those skilled in the art.

[0013] definition

[0014] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.The terminology used in the present disclosure is for describing particular embodiments only and is not intended to be limiting.

[0015] Herein, ranges may be expressed 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 a value is expressed as an approximation by using the preposition "about," it is understood that the particular value constitutes another embodiment. It will also be understood that the endpoints of each range are meaningful both in relation to the other endpoint and independently of the other endpoint.

[0016] Unless otherwise expressly stated, any method described herein should not be construed as requiring that its steps be performed in a particular order, nor should any device have a particular orientation. Therefore, in the absence of an actual description of the order in which its steps are to be followed in a method claim, or an actual description of the order or orientation of the components in any device claim, or an explicit description in other ways in the claims or specification that the steps should be limited to a particular order, or a description of a particular order or orientation of the device components, no order or orientation should be inferred in any respect. This applies to any possible non-explicit basis for expression, including: logical issues involving step settings, operational flows, component order or component orientation; concise meaning derived from grammatical organization or punctuation, and the number or type of embodiments described in the specification.

[0017] In this specification and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context indicates otherwise. Thus, for example, reference to "a" component includes aspects having two or more such components, unless the context indicates otherwise.

[0018] Unless otherwise indicated, the term "weight %" described herein refers to the weight fraction of a single component based on the total weight of the peroxide-curable composition.

[0019] As used herein, the term "number average molecular weight" refers to the total weight of a polymer divided by the total number of molecules as measured using gel permeation chromatography (GPC) and polystyrene standards.

[0020] As used herein, the term "melt flow rate" refers to the ability of a material melt to flow under pressure at a given temperature and a given weight as measured according to ASTM D1238.

[0021] As used herein, the term "density" refers to the mass per unit volume of a material, as measured at 23°C in accordance with ASTM D792.

[0022] As used herein, the term "specific gravity" refers to the ratio of the density of a material to the density of water, as measured at 23°C according to ASTM D792.

[0023] As used herein, the term "Mooney viscosity" refers to the viscosity reached after a spindle has been rotated for a given time interval at a specified temperature, as measured in accordance with ASTM D1646.

[0024] As used herein, the term "yield" refers to the point on a stress-strain curve that represents the limit of elastic behavior and the onset of plastic behavior.

[0025] As used herein, the term "tensile strength at yield" refers to the maximum stress that a material can withstand when stretched before starting to permanently deform, as measured in accordance with ASTM D638 at 23°C and a strain rate of 0.85 mm / s.

[0026] As used herein, the term "tensile elongation at yield" refers to the ratio between the increased length at the yield point and the initial length, which is measured at 23°C and a strain rate of 0.85 mm / s according to ASTM D638.

[0027] As used herein, the term "tensile strength at break" refers to the maximum stress a material can withstand before breaking, which is measured according to ASTM D638 at 23° C. and a strain rate of 0.85 mm / s.

[0028] As used herein, the term "tensile elongation at break" refers to the ratio of the increased length after break to the initial length, which is measured at 23°C and a strain rate of 0.85 mm / s according to ASTM D638.

[0029] As used herein, the term "Shore A Hardness" refers to the hardness of a material as measured according to ASTM D2240.

[0030] As used herein, the term "compression set" refers to the ability of a material to recover to its original thickness after being subjected to a compressive stress for a prolonged period of time, as measured at a specified temperature in accordance with ASTM D395.

[0031] As used herein, the term "polyolefin" refers to a polymer having a crystalline phase and an amorphous phase prepared from olefin monomers.

[0032] As used herein, the term "polyolefin elastomer (POE)" refers to a low crystalline (ie, less than or equal to 25% crystalline) polymer prepared from olefin monomers.

[0033] As used herein, the term "silane grafted" refers to a thermoplastic elastomer having silane side chains attached to the polymer backbone.

[0034] As used herein, the term "copolymer" refers to a polymer formed when two or more different monomers are polymerized to form a chain.

[0035] As used herein, the term "block" refers to a portion of a polymer comprising a plurality of constitutional units having at least one feature not present in an adjacent portion.

[0036] As discussed above, crosslinked thermoplastic articles may have desirable properties, such as chemical and heat resistance. However, conventional processes for forming thermoplastic articles may require additional steps, time, and materials to achieve the crosslink density and heat resistance required for certain applications in healthcare, automotive, and electronics.

[0037] Disclosed herein is a peroxide-vulcanizable composition that alleviates the above-mentioned problems. Specifically, the peroxide-vulcanizable composition disclosed herein comprises a partially crosslinked polymer system, the system comprising: a polymerization reaction product of a vinyl aromatic monomer unit and a conjugated diene monomer unit; and a curing package comprising an organic peroxide and a silane, which results in the partially crosslinked polymer system having a favorable crosslinking density (i.e., reduced tensile elongation at break) and heat resistance (i.e., reduced compression set). The curing package of the organic peroxide and the silane enables the thermoplastic elastomer to undergo carbon-carbon bond crosslinking when blending (e.g., in an extruder) without the need for additional steps or materials (e.g., a moisture curing catalyst).

[0038] Peroxide-curable compositions

[0039]

[0046] Peroxide curable compositions as disclosed herein can generally be described as a thermoplastic elastomer and a cure package.

[0040] Thermoplastic elastomer

[0041] The thermoplastic elastomer of the peroxide-curable composition comprises a vinyl aromatic monomer unit and a conjugated diene monomer unit. In some embodiments, the conjugated diene monomer unit may be selected from the group consisting of 1,3-butadiene monomer units, 2,3-dimethyl-1,3-butadiene monomer units, isoprene monomer units, and combinations thereof. In some embodiments, the vinyl aromatic monomer unit may be selected from the group consisting of styrene monomer units, α-methylstyrene monomer units, p-methylstyrene monomer units, o-methylstyrene monomer units, p-butylstyrene monomer units, p-tert-butylstyrene monomer units, and combinations thereof.

[0042] In some embodiments, the thermoplastic elastomer can be selected from the group consisting of styrene-butadiene rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene-isoprene rubber, styrene-butadiene / isoprene block polymer, styrene-butadiene-isoprene block copolymer, partially hydrogenated styrene-butadiene rubber, partially hydrogenated styrene-butadiene block copolymer, partially hydrogenated styrene-isoprene block copolymer, partially hydrogenated styrene-butadiene-isoprene rubber, partially hydrogenated styrene-butadiene / isoprene block copolymer, partially hydrogenated styrene-butadiene-isoprene block copolymer, and combinations thereof.

[0043] In some embodiments, the thermoplastic elastomer may be a block copolymer comprising a block defined by formula (I):

[0044]

[0045] wherein w, x, y and z units are randomly distributed in the block, each R1 is independently a hydrogen atom or a methyl group, and each R2 is independently a hydrogen atom or a methyl group, provided that at least one R2 in each unit is a hydrogen atom.

[0046] In an embodiment of a block copolymer comprising a block defined by formula (I), the molar percentage of the sum of the y units and z units in the block to the sum of the w, x, y units, and z units is about 30% to about 90%. In an embodiment of a block copolymer comprising a block defined by formula (I), the molar percentage of the sum of the y units and z units in the block to the sum of the w, x, y units, and z units is about 50% to about 70%. In an embodiment of a block copolymer comprising a block defined by formula (I), the molar percentage of the sum of the y units and z units in the block to the sum of the w, x, y units, and z units may be greater than or equal to about 30%, greater than or equal to about 35%, greater than or equal to about 40%, greater than or equal to about 45%, or even greater than or equal to about 50%. In embodiments comprising block copolymers containing blocks defined by formula (I), the molar percentage of the sum of y units and z units in the block to the sum of w, x, y units, and z units may be less than or equal to about 90%, less than or equal to about 85%, less than or equal to about 80%, less than or equal to about 75%, or even less than or equal to about 70%. In embodiments comprising block copolymers containing blocks defined by formula (I), the molar percentage of the sum of y units and z units in the block to the sum of w, x, y units, and z units may be from about 30% to about 90%, from about 30% to about 85%, from about 30% to about 80%, from about 30% to about 75%, from about 30% to about 70%, from about 35% to about 90%, from about 35% to about 85%, from about 35% to about 80%, from about 35% to about 75%, from about 35% to about 70%, from about 40% to about 90%. %, about 40% to about 85%, about 40% to about 80%, about 40% to about 75%, about 40% to about 70%, about 45% to about 90%, about 45% to about 85%, about 45% to about 80%, about 45% to about 75%, about 45% to about 70%, about 50% to about 90%, about 50% to about 85%, about 50% to about 80%, about 50% to about 75%, or even about 50% to about 70%, or any and all subranges formed by any of these endpoints.

[0047] In embodiments comprising block copolymers containing blocks defined by formula (I), the ratio of y units to w units may be greater than the ratio of x units to z units. In embodiments comprising block copolymers containing blocks defined by formula (I), the ratio of y units to w units may be less than the ratio of x units to z units.

[0048] In some embodiments, the thermoplastic elastomer may be a block copolymer comprising a block defined by formula (II):

[0049]

[0050] Among them, a, b, c and d units are randomly distributed in the blocks.

[0051] In embodiments comprising block copolymers containing blocks defined by formula (II), the molar percentage of the sum of c units and d units in the block to the sum of a, b, c, and d units can be from about 30% to about 90%. In embodiments comprising block copolymers containing blocks defined by formula (II), the molar percentage of the sum of c units and d units in the block to the sum of a, b, c, and d units can be from about 50% to about 70%. In embodiments comprising block copolymers containing blocks defined by formula (II), the molar percentage of the sum of c units and d units in the block to the sum of a, b, c, and d units can be greater than or equal to about 30%, greater than or equal to about 35%, greater than or equal to about 40%, greater than or equal to about 45%, or even greater than or equal to about 50%. In embodiments comprising block copolymers containing blocks defined by formula (II), the molar percentage of the sum of c units and d units in the block to the sum of a, b, c, and d units may be less than or equal to about 90%, less than or equal to about 85%, less than or equal to about 80%, less than or equal to about 75%, or even less than or equal to about 70%. In embodiments comprising block copolymers containing blocks defined by formula (II), the molar percentage of the sum of c units and d units in the block to the sum of a, b, c, and d units may be from about 30% to about 90%, from about 30% to about 85%, from about 30% to about 80%, from about 30% to about 75%, from about 30% to about 70%, from about 35% to about 90%, from about 35% to about 85%, from about 35% to about 80%, from about 35% to about 75%, from about 35% to about 70%, from about 40% to about 90%. %, about 40% to about 85%, about 40% to about 80%, about 40% to about 75%, about 40% to about 70%, about 45% to about 90%, about 45% to about 85%, about 45% to about 80%, about 45% to about 75%, about 45% to about 70%, about 50% to about 90%, about 50% to about 85%, about 50% to about 80%, about 50% to about 75%, or even about 50% to about 70%, or any and all subranges formed by any of these endpoints.

[0052] In embodiments comprising block copolymers containing blocks defined by formula (II), the ratio of c units to a units may be greater than the ratio of d units to b units. In embodiments comprising block copolymers containing blocks defined by formula (II), the ratio of c units to a units may be less than the ratio of d units to b units.

[0053] In some embodiments, the number average molecular weight of the thermoplastic elastomer may be from about 30,000 g / mol to about 400,000 g / mol. In some embodiments, the number average molecular weight of the thermoplastic elastomer may be greater than or equal to about 30,000 g / mol, greater than or equal to about 50,000 g / mol, greater than or equal to about 100,000 g / mol, or even greater than or equal to about 150,000 g / mol. In some embodiments, the number average molecular weight of the thermoplastic elastomer may be less than or equal to about 400,000 g / mol, less than or equal to about 350,000 g / mol, less than or equal to about 300,000 g / mol, or even less than or equal to about 250,000 g / mol. In some embodiments, the number average molecular weight of the thermoplastic elastomer can be about 30,000 g / mol to about 400,000 g / mol, about 30,000 g / mol to about 350,000 g / mol, about 30,000 g / mol to about 300,000 g / mol, about 30,000 g / mol to about 250,000 g / mol, about 50,000 g / mol to about 400,000 g / mol, about 50,000 g / mol to about 350,000 g / mol, about 50,000 g / mol to about 300,000 g / mol, about 50,000 g / mol to about 250,000 g / mol, about 100,000 g / mol to about 400,000 g / mol, about 50,000 g / mol to about 350,000 g / mol, about 50,000 g / mol to about 300,000 g / mol, about 50,000 g / mol to about 250,000 g / mol, about 100,000 g / mol to about g / mol to about 300,000 g / mol, about 100,000 g / mol to about 250,000 g / mol, about 150,000 g / mol to about 400,000 g / mol, about 150,000 g / mol to about 350,000 g / mol, about 150,000 g / mol to about 300,000 g / mol, about 100,000 g / mol to about 250,000 g / mol, about 150,000 g / mol to about 400,000 g / mol, about 150,000 g / mol to about 350,000 g / mol, about 150,000 g / mol to about 300,000 g / mol, or even about 150,000 g / mol to about 250,000 g / mol, or any and all subranges formed by any of these endpoints.

[0054] In some embodiments, the thermoplastic elastomer can be a triblock copolymer comprising two polystyrene end blocks. In this embodiment, the styrene content of the two polystyrene end blocks in the thermoplastic elastomer can be about 10% by weight to about 50% by weight. In some embodiments, the styrene content of the two polystyrene end blocks in the thermoplastic elastomer can be greater than or equal to about 10% by weight, greater than or equal to about 15% by weight, greater than or equal to about 20% by weight, greater than or equal to about 25% by weight, or even greater than or equal to about 27% by weight. In some embodiments, the styrene content of the two polystyrene end blocks in the thermoplastic elastomer can be less than or equal to about 50% by weight, less than or equal to about 45% by weight, less than or equal to about 40% by weight, less than or equal to about 35% by weight, or even less than or equal to about 33% by weight. In some embodiments, the styrene content of the two polystyrene end blocks in the thermoplastic elastomer can be from about 10 wt % to about 50 wt %, from about 10 wt % to about 45 wt %, from about 10 wt % to about 40 wt %, from about 10 wt % to about 35 wt %, from about 10 wt % to about 33 wt %, from about 15 wt % to about 50 wt %, from about 15 wt % to about 45 wt %, from about 15 wt % to about 40 wt %, from about 15 wt % to about 35 wt %, from about 15 wt % to about 33 wt %, from about 20 wt % to about 50 wt %, from about 20 wt % to about 45 wt %, from about 20 wt % to about 35 wt %, from about 15 wt % to about 33 wt %, % to about 40 wt %, about 20 wt % to about 35 wt %, about 20 wt % to about 33 wt %, about 25 wt % to about 50 wt %, about 25 wt % to about 45 wt %, about 25 wt % to about 40 wt %, about 25 wt % to about 35 wt %, about 25 wt % to about 33 wt %, about 27 wt % to about 50 wt %, about 27 wt % to about 45 wt %, about 27 wt % to about 40 wt %, about 27 wt % to about 35 wt %, or even about 27 wt % to about 33 wt %, or any and all subranges formed by any of these endpoints.

[0055] In some embodiments, the thermoplastic elastomer can be partially hydrogenated. Without being limited by theory, it is believed that the crosslinking of the partially hydrogenated thermoplastic elastomer occurs at the unhydrogenated site (i.e., the carbon-carbon double bond located on the conjugated diene residue), and the amount of the reactive site can be set by adjusting the hydrogenation of the thermoplastic elastomer. The amount of crosslinking can also be controlled by controlling the hydrogenation level. Reducing the degree of hydrogenation of the thermoplastic elastomer can improve the crosslinking density and heat resistance of the partially crosslinked polymer system obtained. In some embodiments, based on the unsaturated groups of the conjugated diene monomer units in the pre-partially hydrogenated thermoplastic elastomer, the degree of hydrogenation of the thermoplastic elastomer can be greater than or equal to about 50%, greater than or equal to about 60%, greater than or equal to about 70%, greater than or equal to about 80%, greater than or equal to about 85%, greater than or equal to about 90%, or even greater than or equal to about 95%. In some embodiments, the degree of hydrogenation of the thermoplastic elastomer may range from about 30% to about 99%, or from about 35% to about 95%, or from about 40% to about 90%, or from about 45% to about 85%, or from about 50% to about 80%, or from about 55% to about 75%, based on the unsaturated groups of the conjugated diene monomer units in the previously partially hydrogenated thermoplastic elastomer.

[0056] In some embodiments, the thermoplastic elastomer may be a partially hydrogenated block copolymer having a hard phase and a soft phase, generally constructed as:

[0057] A-B,

[0058] A-B-A or

[0059] A―B―A′,

[0060] Wherein, before hydrogenation, each A and A' block is a hard phase comprising vinyl aromatic monomer units, and each B block is a soft phase comprising conjugated diene monomer units. "Hard phase" refers to the portion of the block copolymer having a glass transition temperature of 90°C to 165°C. "Soft phase"

[0061] It refers to the portion of the block copolymer having a glass transition temperature of less than -20°C.

[0062] In some embodiments, the peroxide vulcanizable composition may include about 25% to about 95% by weight of a thermoplastic elastomer, or about 30% to about 90% by weight of a thermoplastic elastomer, or about 35% to about 85% by weight of a thermoplastic elastomer, or about 40% to about 80% by weight of a thermoplastic elastomer, or about 50% to about 75% by weight of a thermoplastic elastomer, or about 60% to about 70% by weight of a thermoplastic elastomer. In some embodiments, the amount of thermoplastic elastomer in the peroxide vulcanizable composition may be greater than or equal to about 25% by weight, greater than or equal to about 30% by weight, greater than or equal to about 35% by weight, greater than or equal to about 40% by weight, greater than or equal to about 50% by weight, or even greater than or equal to about 60% by weight. In some embodiments, the amount of thermoplastic elastomer in the peroxide vulcanizable composition may be less than or equal to about 80% by weight, less than or equal to about 75% by weight, less than or equal to about 70% by weight, less than or equal to about 60% by weight, or even less than or equal to about 50% by weight. In some embodiments, the amount of thermoplastic elastomer in the peroxide vulcanizable composition can be from about 25% to about 80% by weight, from about 25% to about 75% by weight, from about 25% to about 70% by weight, from about 25% to about 60% by weight, from about 25% to about 50% by weight, from about 30% to about 80% by weight, from about 30% to about 75% by weight, from about 30% to about 70% by weight, from about 30% to about 60% by weight, from about 30% to about 50% by weight, from about 35% to about 80% by weight, from about 35% to about 75% by weight, from about 30% to about 70% by weight, from about 35% to about 60% by weight, % to about 60 weight %, about 35 weight % to about 50 weight %, about 40 weight % to about 80 weight %, about 40 weight % to about 75 weight %, about 40 weight % to about 70 weight %, about 40 weight % to about 60 weight %, about 40 weight % to about 50 weight %, about 50 weight % to about 80 weight %, about 50 weight % to about 75 weight %, about 50 weight % to about 70 weight %, about 50 weight % to about 60 weight %, about 60 weight % to about 80 weight %, about 60 weight % to about 75 weight %, or even about 60 weight % to about 70 weight %, or any and all subranges formed by any of these endpoints.

[0063] Suitable commercial embodiments of thermoplastic elastomers are available from TSRC's VECTOR brand, such as styrene-butadiene-styrene (SBS) grade 2518 and styrene-isoprene-styrene (SIS) grade 4211; Kuraray's HYBRAR brand, such as styrene-isoprene-styrene (SIS) grade 5127; Kraton's KRATON brand, such as partially hydrogenated styrene-butadiene-styrene (SBS) grades G1654 and G1652; and Ashai Kasei's TUFTEC brand, such as partially hydrogenated styrene-butadiene-styrene (SBS) grade P 1083.

[0064] Vulcanization package

[0065] The cure package of the peroxide curable composition comprises an organic peroxide and a silane. As described herein, the cure package facilitates peroxide curing, resulting in crosslinking of the thermoplastic elastomer carbon-carbon bonds upon blending without the need for additional steps or materials.

[0066] During the blending of the peroxide curable composition to form a partially crosslinked polymer system, the thermoplastic elastomer can be partially grafted with the silane. The blend can be aged (e.g., heat treated or moisture cured) to allow the partially crosslinked polymer system to form silane crosslinks from the silane grafts.

[0067] A variety of silanes are believed to be suitable for use in the peroxide-curable compositions of the present invention. In some embodiments, the silane can be defined by the formula:

[0068] S i x H 4-x

[0069] Wherein, x is 1-4 and each R is individually a monovalent hydrocarbon group or a monovalent alkoxy group. In some embodiments, the monovalent hydrocarbon group may be a straight chain, a cyclic or a branched group. In some embodiments, the monovalent hydrocarbon group may include an aromatic group. In some embodiments, the monovalent hydrocarbon group may have 1-12 carbon atoms, 2-10 carbon atoms or 3-8 carbon atoms. In some embodiments, the monovalent hydrocarbon group may include a carbon-carbon double bond. In some embodiments, the monovalent alkoxy group is a monovalent hydrocarbon group attached to an oxygen atom. The monovalent hydrocarbon group of the monovalent alkoxy group may be a straight chain, a cyclic or a branched group. In some embodiments, the monovalent hydrocarbon group of the monovalent alkoxy group may include an aromatic group. In some embodiments, the monovalent hydrocarbon group of the monovalent alkoxy group may have 1-12 carbon atoms, 2-10 carbon atoms or 3-8 carbon atoms. In some embodiments, the monovalent hydrocarbon group of the monovalent alkoxy group may include a carbon-carbon double bond.

[0070] In some embodiments, the silane may include vinyl trialkoxy silane. For example, in some embodiments, the silane may include vinyl trimethoxy silane, vinyl triethoxy silane, or a combination thereof.

[0071] In some embodiments, the specific gravity of the silane may be greater than or equal to about 0.90, or even greater than or equal to about 0.95. In some embodiments, the specific gravity of the silane may be less than or equal to about 1.05, or even less than or equal to about 1. In some embodiments, the specific gravity of the silane may be from about 0.90 to about 1.05, from about 0.90 to about 1.00, from about 0.95 to about 1.05, or even from about 0.95 to about 1.00, or any and all subranges formed by any of these endpoints.

[0072] In some embodiments, the boiling point of the silane may be greater than or equal to about 75° C., or even greater than or equal to about 100° C. In some embodiments, the boiling point of the silane may be less than or equal to about 150° C., or even less than or equal to about 125° C. In some embodiments, the boiling point of the silane may be from about 75° C. to about 150° C., from about 75° C. to about 125° C., from about 100° C. to about 150° C., or even from about 100° C. to about 125° C., or any and all subranges formed by any of these endpoints.

[0073] In some embodiments, the number average molecular weight of the silane can be greater than or equal to about 50 g / mol, greater than or equal to about 100 g / mol, greater than or equal to about 150 g / mol, or even greater than or equal to about 200 g / mol. In some embodiments, the number average molecular weight of the silane can be less than or equal to about 500 g / mol, less than or equal to about 400 g / mol, or even less than or equal to about 300 g / mol. In some embodiments, the silane can have a number average molecular weight of about 50 g / mol to about 500 g / mol, about 50 g / mol to about 400 g / mol, about 50 g / mol to about 300 g / mol, about 100 g / mol to about 500 g / mol, about 100 g / mol to about 400 g / mol, about 100 g / mol to about 300 g / mol, about 150 g / mol to about 500 g / mol, about 150 g / mol to about 400 g / mol, about 150 g / mol to about 300 g / mol, about 200 g / mol to about 500 g / mol, about 200 g / mol to about 400 g / mol, or even about 200 g / mol to about 300 g / mol, or any and all subranges formed by any of these endpoints.

[0074] In some embodiments, the peroxide vulcanizable composition may include about 0.5 wt % to about 5 wt % silane. In some embodiments, the amount of silane in the peroxide vulcanizable composition may be greater than or equal to about 0.5 wt %, or even greater than or equal to about 1 wt %. In some embodiments, the amount of silane in the peroxide vulcanizable composition may be less than or equal to 5 wt %, less than or equal to 4 wt %, or even less than or equal to 3 wt %. In some embodiments, the amount of silane in the peroxide vulcanizable composition may be about 0.5 wt % to about 5 wt %, about 0.5 wt % to about 4 wt %, about 0.5 wt % to about 3 wt %, about 1 wt % to about 5 wt %, about 1 wt % to about 4 wt %, or even about 1 wt % to about 3 wt %, or any and all subranges formed by any of these endpoints.

[0075] A suitable commercial embodiment of such silanes is available from Momentive under the SILQUEST brand (eg, grade A-171).

[0076] A variety of organic peroxides are believed to be suitable for use in the peroxide-curable compositions of the present invention. In some embodiments, the organic peroxide can be defined by the formula:

[0077] ROOR

[0078] Wherein, each R is independently a monovalent hydrocarbon group. In some embodiments, the monovalent hydrocarbon group of an organic peroxide can be a straight chain, a cyclic or a branched group. In some embodiments, the monovalent hydrocarbon group of an organic peroxide can include an aromatic group. In some embodiments, the monovalent hydrocarbon group of an organic peroxide can have 1-16 carbon atoms, 3-15 carbon atoms or 5-10 carbon atoms. In some embodiments, the monovalent hydrocarbon group of an organic peroxide can include a carbon-carbon double bond. In some embodiments, an organic peroxide can include a peroxyketal peroxide, a di-tert-alkyl peroxide or a combination thereof. In some embodiments, a di-tert-alkyl peroxide can include dicumyl peroxide.

[0079] In some embodiments, the density of the organic peroxide may be greater than or equal to about 1.00 g / cm 3 , or even greater than or equal to about 1.05 g / cm 3 In some embodiments, the density of the organic peroxide may be less than or equal to about 1.20 g / cm 3 , or even less than or equal to about 1.15 g / cm 3 In some embodiments, the density of the organic peroxide may be about 1.00 g / cm 3 To about 1.20g / cm 3 , about 1.00g / cm 3To about 1.15g / cm 3 , about 1.05g / cm 3 To about 1.20g / cm 3 , or even about 1.05 g / cm 3 To about 1.15g / cm 3 , or any and all sub-ranges formed by any of these endpoints.

[0080] Without wishing to be bound by theory, it is believed that increasing the amount of organic peroxide in the peroxide vulcanizable composition can improve the crosslink density and heat resistance of the resulting partially crosslinked polymer system. In some embodiments, the peroxide vulcanizable composition can include about 0.05 wt % to about 1 wt % of the organic peroxide. In some embodiments, the amount of organic peroxide in the peroxide vulcanizable composition can be greater than or equal to about 0.05 wt %, greater than or equal to about 0.1 wt %, or even greater than or equal to about 0.2 wt %. In some embodiments, the amount of organic peroxide in the peroxide vulcanizable composition can be less than or equal to about 1 wt %, less than or equal to about 0.8 wt %, less than or equal to about 0.6 wt %, or even less than or equal to about 0.4 wt %. In some embodiments, the amount of organic peroxide in the peroxide-curable composition can be from about 0.05 wt % to about 1 wt %, from about 0.05 wt % to about 0.8 wt %, from about 0.05 wt % to about 0.6 wt %, from about 0.05 wt % to about 0.4 wt %, from about 0.1 wt % to about 1 wt %, from about 0.1 wt % to about 0.8 wt %, from about 0.1 wt % to about 0.6 wt %, from about 0.1 wt % to about 0.4 wt %, from about 0.2 wt % to about 1 wt %, from about 0.2 wt % to about 0.8 wt %, from about 0.2 wt % to about 0.6 wt %, or even from about 0.2 wt % to about 0.4 wt %, or any and all subranges formed by any of these endpoints.

[0081] Suitable commercial embodiments of organic peroxides are available from AkzoNobel under the PERKADOX brand (eg BC-FF).

[0082] Olefin polymers

[0083] In some embodiments, the peroxide curable composition may also include an olefin polymer to adjust hardness and mechanical properties, and to improve flow properties.

[0084] In some embodiments, the olefin polymer may include a polyolefin, a polyolefin elastomer, or a combination thereof.

[0085] In some embodiments, the polyolefin may include polypropylene, polyethylene, or a combination thereof.

[0086] In some embodiments, the polyolefin may include polypropylene. In some embodiments, the polyolefin may include a polypropylene homopolymer (i.e., composed of propylene monomers) or a polypropylene copolymer having greater than 50 wt. % propylene monomers and one or more additional comonomers, such as C2 and C4-C 12 α-Olefins.

[0087] In some embodiments, the polyethylene may include a polyethylene homopolymer (i.e., composed of ethylene monomers) or a polyethylene homopolymer having greater than 50% by weight of ethylene monomers and other comonomers (e.g., C3-C 12 Polyethylene copolymers of α-olefins.

[0088] In some embodiments, the polyolefin is at least one of: a high density polyethylene (e.g., greater than or equal to 0.940 g / cm 3 ) or crystalline polypropylene having a percent crystallinity of at least about 60%.

[0089] In some embodiments, the melt flow rate (230°C / 2.16kg) of the polypropylene may be greater than or equal to about 0.1 g / 10 min, greater than or equal to about 0.5 g / 10 min, greater than or equal to about 1 g / 10 min, or even greater than or equal to about 3 g / 10 min. In some embodiments, the melt flow rate (230°C / 2.16kg) of the polypropylene may be less than or equal to about 10 g / 10 min, or even less than or equal to about 5 g / 10 min. In some embodiments, the melt flow rate (230°C / 2.16 kg) of the polypropylene can be from about 0.1 g / 10 min to about 10 g / 10 min, from about 0.1 g / 10 min to about 5 g / 10 min, from about 0.5 g / 10 min to about 10 g / 10 min, from about 0.5 g / 10 min to about 5 g / 10 min, from about 1 g / 10 min to about 10 g / 10 min, from about 1 g / 10 min to about 5 g / 10 min, from about 3 g / 10 min to about 10 g / 10 min, or even from 3 g / 10 min to 5 g / 10 min, or any and all subranges formed by any of these endpoints.

[0090] In some embodiments, the density of the polyolefin may be greater than or equal to about 0.80 g / cm 3 , or even greater than or equal to about 0.85 g / cm 3 In some embodiments, the density of the polyolefin may be less than or equal to about 1.10 g / cm 3 , or even less than or equal to about 1.00 g / cm 3 In some embodiments, the density of the polyolefin may be about 0.80 g / cm 3 To about 1.10g / cm 3 , about 0.80g / cm3 To about 1.00g / cm 3 , about 0.85g / cm 3 To about 1.10g / cm 3 , or even about 0.85 g / cm 3 To about 1.15g / cm 3 , or any and all sub-ranges formed by any of these endpoints.

[0091] In some embodiments, the polyolefin may have a melting point of greater than or equal to about 100°C, greater than or equal to about 110°C, or even greater than or equal to about 120°C.

[0092] In some embodiments, the tensile strength at yield of the polyolefin may be greater than or equal to about 25 MPa, or even greater than or equal to about 30 MPa. In some embodiments, the tensile strength at yield of the polyolefin may be less than or equal to about 45 MPa, or even less than or equal to about 40 MPa. In some embodiments, the tensile strength at yield of the polyolefin may be from about 25 MPa to about 45 MPa, from about 25 MPa to about 40 MPa, from about 30 MPa to about 45 MPa, or even from about 30 MPa to about 40 MPa, or any and all subranges formed by any of these endpoints.

[0093] In some embodiments, the polyolefin may have a tensile elongation at yield of about 3% or more, or even about 5% or more. In some embodiments, the polyolefin may have a tensile elongation at yield of about 20% or less, or even about 15% or less. In some embodiments, the polyolefin may have a tensile elongation at yield of about 3% to about 20%, about 3% to about 15%, about 5% to about 20%, or even about 5% to about 15%, or any and all subranges formed by any of these endpoints.

[0094] Suitable commercial embodiments of polyolefins are available from Formosa Plastics under the FORMOLENE brand, such as polypropylene homopolymer grade 1102KR.

[0095] In some embodiments, the polyolefin elastomer may include a polypropylene elastomer.

[0096] Suitable commercial embodiments of polyolefins are available from Exxon under the VISTAMAXX brand, for example, polypropylene elastomer grades Vistamaxx 6201 and 6202.

[0097] In some embodiments, the polyolefin elastomer may include an olefin block copolymer, an ethylene alpha-olefin copolymer, or a combination thereof. In some embodiments, the polyolefin elastomer may include an olefin block copolymer. In some embodiments, the polyolefin elastomer may include an ethylene-alpha-olefin copolymer. In some embodiments, the polyolefin elastomer may include an olefin block copolymer and an ethylene-alpha-olefin copolymer.

[0098] In some embodiments, the olefin block copolymer may include ethylene-α-olefin repeating units. The ethylene-α-olefin repeating units are ethylene and C3-C 12 The polymerized reaction product of an olefin. For example, in some embodiments, the ethylene-α-olefin repeating unit may include: an ethylene-octene copolymer, an ethylene-hexene copolymer, an ethylene-butene copolymer, or a combination thereof.

[0099] In some embodiments, the melt flow rate (190°C / 2.16kg) of the olefin block copolymer may be greater than or equal to about 1 g / 10 min or even greater than or equal to about 5 g / 10 min. In some embodiments, the melt flow rate (190°C / 2.16kg) of the olefin block copolymer may be less than or equal to about 25 g / 10 min, or even less than or equal to about 20 g / 10 min. In some embodiments, the melt flow rate (190°C / 2.16kg) of the olefin block copolymer may be from about 1 g / 10 min to about 25 g / 10 min, from about 1 g / 10 min to about 20 g / 10 min, from about 5 g / 10 min to about 25 g / 10 min, or even from about 5 g / 10 min to about 20 g / 10 min, or any and all subranges formed by any of these endpoints.

[0100] In some embodiments, the density of the olefin block copolymer may be greater than or equal to about 0.80 g / cm 3 , or even greater than or equal to about 0.85 g / cm 3 In some embodiments, the density of the olefin block copolymer may be less than or equal to about 0.95 g / cm 3 , or even less than or equal to about 0.90 g / cm 3 In some embodiments, the density of the olefin block copolymer may be about 0.80 g / cm 3 To about 0.95g / cm 3 , about 0.80g / cm 3 To about 0.90g / cm 3 , about 0.85g / cm 3 To about 0.95g / cm 3 , or even about 0.85 g / cm 3 To about 0.90g / cm 3, or any and all sub-ranges formed by any of these endpoints.

[0101] In some embodiments, the olefin block copolymer may have a Shore A hardness of greater than or equal to about 50, or even greater than or equal to about 60. In some embodiments, the olefin block copolymer may have a Shore A hardness of less than or equal to about 85, or even less than or equal to about 75. In some embodiments, the olefin block copolymer may have a Shore A hardness of about 50 to about 85, about 50 to about 75, about 60 to about 85, or even about 60 to about 75, or any and all subranges formed by any of these endpoints.

[0102] Suitable commercial embodiments of olefin block copolymers are available from The Dow Chemical Company under the Infuse brand (eg, 9500 and 9817).

[0103] Ethylene-α-olefin copolymers are ethylene and C3-C 12 The polymerized reaction product of an olefin. For example, in some embodiments, the ethylene-α-olefin copolymer may include an ethylene-octene copolymer, an ethylene-hexene copolymer, an ethylene-butene copolymer, or a combination thereof.

[0104] In some embodiments, the melt flow rate (190°C / 2.16kg) of the ethylene-alpha olefin copolymer may be greater than, or equal to, 0.1 g / 10 min, or even greater than, or equal to, 0.25 g / 10 min. In some embodiments, the melt flow rate (190°C / 2.16kg) of the ethylene-alpha olefin copolymer may be less than, or equal to, 3 g / 10 min, or even less than, or equal to, 1 g / 10 min. In some embodiments, the melt flow rate (190°C / 2.16kg) of the ethylene-alpha olefin copolymer may be 0.1 g / 10 min to 3 g / 10 min, 0.1 g / 10 min to 1 g / 10 min, 0.25 g / 10 min to 3 g / 10 min, or even 0.25 g / 10 min to 1 g / 10 min, or any and all subranges formed by any of these endpoints.

[0105] In some embodiments, the density of the ethylene-α-olefin copolymer may be greater than or equal to 0.80 g / cm 3 , or even greater than or equal to 0.85 g / cm 3 In some embodiments, the density of the ethylene-α-olefin copolymer may be less than or equal to 0.95 g / cm 3 , or even less than or equal to 0.90 g / cm 3 In some embodiments, the density of the ethylene-α-olefin copolymer may be 0.80 g / cm 3 Up to 0.95g / cm3 、0.80g / cm 3 Up to 0.90g / cm 3 , 0.85g / cm 3 Up to 0.95g / cm 3 , or even 0.85g / cm 3 Up to 0.90g / cm 3 , or any and all sub-ranges formed by any of these endpoints.

[0106] In some embodiments, the Mooney viscosity (ML 1+4, 121° C.) of the ethylene-α-olefin copolymer may be greater than, or equal to, 20, greater than, or equal to, 30, or even greater than, or equal to, 40. In some embodiments, the Mooney viscosity (ML 1+4, 121° C.) of the ethylene-α-olefin copolymer may be less than, or equal to, 70, less than, or equal to, 60, or even less than, or equal to, 50. In some embodiments, the Mooney viscosity (ML 1+4, 121° C.) of the ethylene-α-olefin copolymer may be from 20 to 70, from 20 to 60, from 20 to 50, from 30 to 70, from 30 to 60, from 30 to 50, from 40 to 70, from 40 to 60, or even from 40 to 50, or any and all subranges formed by any of these endpoints.

[0107] In some embodiments, the ethylene-α-olefin copolymer may have a Shore A hardness of greater than, or equal to, 40, or even greater than, or equal to, 45. In some embodiments, the ethylene-α-olefin copolymer may have a Shore A hardness of less than, or equal to, 60, or even less than, or equal to, 65. In some embodiments, the ethylene-α-olefin copolymer may have a Shore A hardness of 40 to 60, 40 to 55, 45 to 60, or even 45 to 55, or any and all subranges formed by any of these endpoints.

[0108] Suitable commercial embodiments of ethylene-alpha-olefin copolymers are available from The Dow Chemical Company under the Engage brand, for example XLT 8677.

[0109] In some embodiments, the peroxide vulcanizable composition may include an olefin polymer of about 2 wt % to about 50 wt %, or an olefin polymer of about 4 wt % to about 40 wt % or an olefin polymer of about 6 wt % to about 30 wt %. In some embodiments, the amount of the olefin polymer in the peroxide vulcanizable composition may be greater than or equal to about 2 wt %, greater than or equal to about 4 wt %, or even greater than or equal to about 6 wt %. In some embodiments, the amount of the olefin polymer in the peroxide vulcanizable composition may be less than or equal to about 50 wt %, less than or equal to about 40 wt %, less than or equal to about 30 wt %, less than or equal to about 20 wt %, less than or equal to about 17 wt %, less than or equal to about 15 wt %, less than or equal to about 13 wt %, or even less than or equal to about 10 wt %. In some embodiments, the amount of olefin polymer in the peroxide-curable composition can be from 2 wt % to about 50 wt %, from about 2 wt % to about 40 wt %, from about 2 wt % to about 30 wt %, from about 2 wt % to about 20 wt %, from about 2 wt % to about 17 wt %, from about 2 wt % to about 15 wt %, from about 2 wt % to about 13 wt %, from about 2 wt % to about 10 wt %, from about 4 wt % to about 50 wt %, from about 4 wt % to about 40 wt %, from about 4 wt % to about 30 wt %, from about 4 wt % to about 20 wt %. %, about 4 wt % to about 17 wt %, about 4 wt % to about 15 wt %, about 4 wt % to about 13 wt %, about 4 wt % to about 10 wt %, about 6 wt % to about 50 wt %, about 6 wt % to about 40 wt %, about 6 wt % to about 30 wt %, about 6 wt % to about 20 wt %, about 6 wt % to about 17 wt %, about 6 wt % to about 15 wt %, about 6 wt % to about 13 wt %, or even about 6 wt % to about 10 wt %, or any and all subranges formed by any of these endpoints.

[0110] Plasticizers

[0111] In some embodiments, the peroxide curable composition may further include a plasticizer. A plasticizer may help improve flow in the peroxide curable composition.

[0112] In some embodiments, the plasticizer may include a non-polar plasticizer (eg, mineral oil).

[0113] In some embodiments, the peroxide vulcanizable composition may include about 10% to about 60% by weight of a plasticizer, or about 15% to about 55% by weight of a plasticizer, or about 20% to about 50% by weight of a plasticizer. In some embodiments, the amount of plasticizer in the peroxide vulcanizable composition may be greater than or equal to about 10% by weight, greater than or equal to about 15% by weight, greater than or equal to about 20% by weight, greater than or equal to about 25% by weight, greater than or equal to about 30% by weight, or even greater than or equal to about 35% by weight. In some embodiments, the amount of plasticizer in the peroxide vulcanizable composition may be less than or equal to about 60% by weight, less than or equal to about 55% by weight, less than or equal to about 50% by weight, less than or equal to about 45% by weight, less than or equal to about 40% by weight, less than or equal to about 35% by weight, or even less than or equal to about 30% by weight. In some embodiments, the amount of plasticizer in the peroxide vulcanizable composition may be about 10% to about 60% by weight.

[0114] A suitable commercial embodiment of a plasticizer is available from Petro-Canada under the PURETOL brand (eg, grade PSO 380).

[0115] Tackifier

[0116] In some embodiments, the peroxide-curable composition may also include a tackifier for adhesive applications (eg, hot melt adhesives).

[0117] In some embodiments, the tackifier may include a hydrocarbon resin. Exemplary hydrocarbon resins may include aliphatic resins (e.g., C5 resins), aromatic resins (e.g., C9 resins), dicyclopentadiene resins, and resins comprising a combination of two or more of aliphatic monomers, aromatic monomers, and dicyclopentadiene. In some embodiments, the hydrocarbon resin may be hydrogenated. In some embodiments, the number average molecular weight of the hydrocarbon resin may be less than or equal to about 2,000 g / mol, less than or equal to about 1,500 g / mol, less than or equal to about 1,200 g / mol, less than or equal to about 1,100 g / mol, less than or equal to about 1,000 g / mol, or less than or equal to about 900 g / mol.

[0118] In some embodiments, the peroxide vulcanizable composition may include about 15 wt % to about 50 wt % tackifier, or about 17 wt % to about 40 wt % tackifier, or about 20 wt % to about 30 wt % tackifier. In some embodiments, the amount of tackifier in the peroxide vulcanizable composition may be greater than or equal to about 15 wt %, greater than or equal to about 17 wt %, or even greater than or equal to about 20 wt %. In some embodiments, the amount of tackifier in the peroxide vulcanizable composition may be less than or equal to about 50 wt %, less than or equal to about 40 wt %, less than or equal to about 30 wt %, less than or equal to about 27 wt %, or even less than or equal to about 25 wt %. In some embodiments, the amount of tackifier in the peroxide-curable composition can be from about 15 wt % to about 50 wt %, from about 15 wt % to about 40 wt %, from about 15 wt % to about 30 wt %, from about 15 wt % to about 27 wt %, from about 15 wt % to about 25 wt %, from about 17 wt % to about 50 wt %, from about 17 wt % to about 40 wt %, from about 17 wt % to about 30 wt %, from about 17 wt % to about 27 wt %, from about 17 wt % to about 25 wt %, from about 20 wt % to about 50 wt %, from about 20 wt % to about 40 wt %, from about 20 wt % to about 30 wt %, from about 20 wt % to about 27 wt %, or even from about 20 wt % to about 25 wt %, or any and all subranges formed by any of these endpoints.

[0119] A suitable commercial embodiment of a tackifier is available from Eastman Chemicals under the PLASTOLYN brand (eg, grade R1140).

[0120] Co-vulcanizable polymers

[0121] In some embodiments, the peroxide curable composition may further include a co-curable polymer that can be cured by the peroxide and crosslinked with the thermoplastic elastomer.

[0122] In some embodiments, the co-vulcanizable polymer may include ethylene vinyl acetate. In some embodiments, the vinyl acetate content of the ethylene vinyl acetate may be greater than or equal to about 10 wt%, greater than or equal to about 25 wt%, greater than or equal to about 40 wt%, or even greater than or equal to about 55 wt%, based on the total weight of the ethylene vinyl acetate. In some embodiments, the vinyl acetate content of the ethylene vinyl acetate may be less than or equal to about 80 wt%, less than or equal to about 70 wt%, or even less than or equal to about 60 wt%. In some embodiments, the ethylene vinyl acetate can have a vinyl acetate content of about 10 wt % to about 80 wt %, about 10 wt % to about 70 wt %, about 10 wt % to about 60 wt %, about 25 wt % to about 80 wt %, about 25 wt % to about 70 wt %, about 25 wt % to about 60 wt %, about 40 wt % to about 80 wt %, about 40 wt % to about 70 wt %, about 40 wt % to about 60 wt %, about 55 wt % to about 80 wt %, about 55 wt % to about 70 wt %, or even 55 wt % to about 60 wt %, or any and all subranges formed by any of these endpoints.

[0123] In some embodiments, the peroxide vulcanizable composition may include about 25 wt % to about 45 wt % of the copolymer, or about 27 wt % to about 43 wt % of the copolymer, or about 30 wt % to about 40 wt % of the copolymer. In some embodiments, the amount of the copolymer in the peroxide vulcanizable composition may be greater than or equal to about 25 wt %, greater than or equal to about 27 wt %, or even greater than or equal to about 30 wt %. In some embodiments, the amount of the copolymer in the peroxide vulcanizable composition may be less than or equal to 45 wt %, less than or equal to 43 wt %, or even less than or equal to 40 wt %. In some embodiments, the amount of the copolymer in the peroxide-curable composition can be from about 25 wt % to about 45 wt %, from about 25 wt % to about 43 wt %, from about 25 wt % to about 40 wt %, from about 27 wt % to about 45 wt %, from about 27 wt % to about 43 wt %, from about 27 wt % to about 40 wt %, from about 30 wt % to about 45 wt %, from about 30 wt % to about 43 wt %, or even from about 30 wt % to about 40 wt %, or any and all subranges formed by any of these endpoints.

[0124] Suitable commercial embodiments of co-curable polymers are available from The Dow Chemical Company under the ELVAX brand, for example, grade 265.

[0125] additive

[0126] In some embodiments, the peroxide curable composition may further include additives. In some embodiments, the additives may include adhesion promoters; biocides; antifogging agents; antistatic agents; foaming and blowing agents; binders and binding polymers; dispersants; flame retardants and smoke suppressants; mineral fillers; initiators; lubricants; mica; pigments, colorants and dyes; processing aids; mold release agents; silanes, titanates and zirconates; slip agents and antiblock agents; stearates; ultraviolet absorbers; viscosity modifiers; waxes; or combinations thereof.

[0127] Partially cross-linked polymer systems

[0128] The peroxide-curable compositions described herein can be used to form partially crosslinked polymer systems without the need for additional steps or materials, the systems having favorable crosslink density (i.e., reduced tensile elongation at break) and heat resistance (i.e., reduced compression set) after blending. In some embodiments, the partially crosslinked polymer system can be a thermoplastic vulcanizate.

[0129] The partially cross-linked polymer system disclosed herein can generally be described as a vulcanized silane-grafted thermoplastic elastomer with carbon-carbon crosslinks. In some embodiments, the partially cross-linked polymer system can include carbon-carbon crosslinks and grafted silane moieties. In some embodiments, the partially cross-linked polymer system includes carbon-carbon crosslinks and silane crosslinks. In some embodiments, the partially cross-linked polymer system extruded can have a certain amount of silane crosslinks. Moisture may be required to achieve additional silane crosslinks.

[0130] In some embodiments, the partially cross-linked polymer system may include a tensile elongation at break of about 30% to about 725%. In some embodiments, the tensile elongation at break of the partially cross-linked polymer system may be greater than or equal to about 30%, greater than or equal to about 50%, greater than or equal to about 100%, greater than or equal to about 150%, or even greater than or equal to about 200%. In some embodiments, the tensile elongation at break of the partially cross-linked polymer system may be less than or equal to about 725%, less than or equal to about 700%, less than or equal to about 650%, less than or equal to about 600%, less than or equal to about 550%, less than or equal to about 500%, or even less than or equal to about 450%. In some embodiments, the tensile elongation at break of the partially cross-linked polymer system may include from about 30% to about 725%, from about 30% to about 700%, from about 30% to about 650%, from about 30% to about 600%, from about 30% to about 550%, from about 30% to about 500%, from about 30% to about 450%, from about 50% to about 725%, from about 50% to about 700%, from about 50% to about 650%, from about 50% to about 600%, from about 50% to about 550%, from about 50% to about 500%, from about 50% to about 450%, from about 100% to about 725%, from about 100% to about 700%, from about 100% to about 650%, from about 100% to about 600% %, about 100% to about 550%, about 100% to about 500%, about 100% to about 450%, about 150% to about 725%, about 150% to about 700%, about 150% to about 650%, about 150% to about 600%, about 150% to about 550%, about 150% to about 500%, about 150% to about 450%, about 200% to about 725%, about 200% to about 700%, about 200% to about 650%, about 150% to about 600%, about 150% to about 550%, about 150% to about 500%, about 150% to about 450%, or any and all subranges formed by any of these endpoints.

[0131] In some embodiments, the partially crosslinked polymer system may have a compression set of about 20% to about 90% measured at 100° C. In some embodiments, the partially crosslinked polymer system may have a compression set of greater than or equal to about 20%, greater than or equal to about 30%, greater than or equal to about 40%, or even greater than or equal to about 50% measured at 100° C. In some embodiments, the partially crosslinked polymer system may have a compression set of less than or equal to about 90%, less than or equal to about 80%, or even less than or equal to about 70% measured at 100° C. In some embodiments, the compression set of the partially cross-linked polymer system can include about 20% to about 90%, about 20% to about 80%, about 20% to about 70%, about 30% to about 90%, about 30% to about 80%, about 30% to about 70%, about 40% to about 90%, about 40% to about 80%, about 40% to about 70%, about 50% to about 90%, about 50% to about 80%, or even about 50% to about 70%, or any and all subranges formed by any of these endpoints.

[0132] In some embodiments, the partially crosslinked polymer system may have a Shore A hardness of greater than or equal to about 25, greater than or equal to about 30, greater than or equal to about 35, greater than or equal to about 40, or even greater than or equal to about 45. In some embodiments, the partially crosslinked polymer system may have a Shore A hardness of less than or equal to about 90, less than or equal to about 85, less than or equal to about 80, less than or equal to about 75, or even less than or equal to about 70. In some embodiments, the Shore A hardness of the partially crosslinked polymer system can include about 25 to about 90, about 25 to about 85, about 25 to about 80, about 25 to about 75, about 25 to about 70, about 30 to about 90, about 30 to about 85, about 30 to about 80, about 30 to about 75, about 30 to about 70, about 35 to about 90, about 35 to about 85, about 35 to about 80, about 35 to about 75, about 35 to about 70, about 40 to about 90, about 40 to about 85, about 40 to about 80, about 40 to about 75, about 40 to about 70, about 45 to about 90, about 45 to about 85, about 45 to about 80, about 45 to about 75, or even about 45 to about 70, or any and all subranges formed by any of these endpoints.

[0133] In some embodiments, the tensile strength at break of the partially crosslinked polymer system may be greater than or equal to about 1.5 MPa, greater than or equal to about 2.0 MPa, greater than or equal to about 2.5 MPa, or even greater than or equal to about 3.0 MPa. In some embodiments, the tensile strength at break of the partially crosslinked polymer system may be less than or equal to about 8.0 MPa, less than or equal to about 7.5 MPa, less than or equal to about 7.0 MPa, less than or equal to about 6.5 MPa, or even less than or equal to about 6.0 MPa. In some embodiments, the tensile strength at break of the partially cross-linked polymer system may include about 1.5 MPa to about 8.0 MPa, about 1.5 MPa to about 7.5 MPa, about 1.5 MPa to about 7.0 MPa, about 1.5 MPa to about 6.5 MPa, about 1.5 MPa to about 6.0 MPa, about 2.0 MPa to about 8.0 MPa, about 2.0 MPa to about 7.5 MPa, about 2.0 MPa to about 7.0 MPa, about 2.0 MPa to about 6.5 MPa, about 2.0 MPa to about 6.0 MPa. , about 2.5 MPa to about 8.0 MPa, about 2.5 MPa to about 7.5 MPa, about 2.5 MPa to about 7.0 MPa, about 2.5 MPa to about 6.5 MPa, about 2.5 MPa to about 6.0 MPa, about 3.0 MPa to about 8.0 MPa, about 3.0 MPa to about 7.5 MPa, about 3.0 MPa to about 7.0 MPa, about 3.0 MPa to about 6.5 MPa, or even about 3.0 MPa to about 6.0 MPa, or any and all sub-ranges formed by any of these endpoints.

[0134] Processing

[0135]

[00136] In some embodiments, the thermoplastic elastomeric articles described herein may be manufactured in a batch process or a continuous process.

[0136] In some embodiments, the components of the peroxide-curable composition, including thermoplastic elastomer, organic peroxide, and silane, may be added to an extruder (27MM Leistriz twin screw extruder (L / D 52)) and blended. In some embodiments, blending (e.g., in the barrel of the extruder) may be performed at a temperature of 150° C. to 220° C. In some embodiments, blending results in crosslinking of carbon-carbon bonds on the thermoplastic elastomer and grafting of silane moieties.

[0137] As described herein, the vulcanization package of both organic peroxide and silane enables the thermoplastic elastomer to be cross-linked by carbon-carbon bonds when blended (e.g., in an extruder) without the need for additional steps or materials (e.g., moisture-curing catalysts). Therefore, in some embodiments, the step of blending thermoplastic elastomer, organic peroxide, and silane is carried out in the absence of a catalyst. In addition, the step of blending thermoplastic elastomer, organic peroxide, and silane can be carried out in the absence of moisture (e.g., water). Therefore, silane can also be grafted to thermoplastic elastomer in an extruder. However, due to the absence of moisture, silane cross-linking or not occurring in an extruder, or only occurring in an extruder to a very small extent in the case of any cross-linking occurring by chance. Therefore, when leaving the extruder, the thermoplastic elastomer does not contain silane grafting and silane grafting cross-linking, or substantially does not contain silane grafting and silane grafting cross-linking.

[0138] In some embodiments, when extruded, the partially crosslinked polymer system has an extrusion tensile elongation at break of greater than or equal to about 30%, and the tensile elongation of the partially crosslinked polymer system at room temperature for 24 hours remains within 5% of the extrusion tensile elongation at break. In some embodiments, when extruded, the partially crosslinked polymer system has an extrusion compression set of greater than or equal to about 20%, and the compression set of the partially crosslinked polymer system at room temperature for 24 hours remains within 5% of the extrusion compression set at break.

[0139] Blending (also called admixing) devices are well known to those skilled in the art and generally include feeding means, in particular at least one hopper for powdered materials and / or at least one injection pump for liquid materials; high shear mixing means, such as a co-rotating or counter-rotating twin-screw extruder, usually comprising a feed screw placed in a heating barrel (or tube); a delivery head, which gives the extrudate its shape; and means for cooling the extrudate by air cooling or by water circulation. The extrudate is generally in the form of a rod that continuously leaves the device and which can be cut or formed into pellets. However, other forms can be obtained by assembling a die of the desired shape on the delivery die.

[0140] In some embodiments, the carbon-carbon cross-linked silane grafted blend is formed.

[0141] In some embodiments, the formed carbon-carbon cross-linked silane grafted blend can be aged (eg, heat treated or cured) such that a partially cross-linked polymer system includes silane cross-links.

[0142] Example

[0143] Table 1 below shows the sources of ingredients used to form Comparative Examples C1-C10 and Examples E1-E22.

[0144] Table 1

[0145]

[0146] Tables 2 to 8 below show the formulations and certain properties used to form Comparative Examples C1 to C10 and Examples E1 to E22.

[0147] To prepare the plaques of Examples E1 to E22 and Comparative Examples C1 to C10, the formulation compositions listed in Tables 2 to 8 were added to a 27MM Leistriz twin screw extruder (L / D / 52) and blended at a barrel temperature of 193° C. and a rate of 5 rpm. The mixed formulations were extruded at a rate of 5 g / sec.

[0148] The plaques of Examples E6 and E8 were aged after extrusion at the temperature and relative humidity (RH) listed in the table for the time periods prior to measuring the listed properties.

[0149] Comparative Examples C8 and C9 were blended with 1.5% tin catalyst masterbatch (MB) after extrusion. MB has a polyether carrier (MARK 1038, Galata Chemicals) containing 1.5% dibutyltin dilaurate. The blended formulations were injection molded (i.e., formed) to form panels. The panels were conditioned at the temperature and relative humidity (RH) listed in the table for a period of time before measuring the listed properties.

[0150] Table 2

[0151]

[0152] Table 2 (continued)

[0153]

[0154]

[0155] Table 3

[0156]

[0157] Table 3 (continued)

[0158]

[0159]

[0160] Table 4

[0161]

[0162] Table 4 (continued)

[0163]

[0164]

[0165] Table 5

[0166]

[0167] Table 6

[0168]

[0169] Table 7

[0170]

[0171] Table 8

[0172]

[0173] As shown in Tables 2-8, Examples E1 to E22 are partially crosslinked polymer systems formed from peroxide-vulcanizable compositions including thermoplastic elastomers, silanes (SILQUEST A-171) and organic peroxides (PERKADOX BC-FF), and Comparative Examples C1 to C10 are non-crosslinked thermoplastic articles formed from compositions containing thermoplastic rubbers (without silanes and organic peroxides). Compared to Comparative Examples C1 to C10, Examples E1 to E22 show reduced tensile elongation at break and reduced compression set. As shown in Examples E1 to E22 and Comparative Examples C1 to C10, peroxide-vulcanizable compositions containing thermoplastic elastomers, silanes and organic peroxides produce partially crosslinked polymer systems having improved crosslink density and heat resistance compared to articles formed without compositions containing silanes and organic peroxides.

[0174] As shown in Table 3, Example E7 is a partially crosslinked polymer system formed from a peroxide-curable composition including a thermoplastic elastomer having 64% hydrogenation (KRATON G1654 (64% hydrogenation)), and Example E5 is a partially crosslinked polymer system formed from a peroxide-curable composition including a thermoplastic elastomer having 85% hydrogenation (KRATON G1654 (85% hydrogenation)), and Example E7 shows a reduced tensile elongation at break and a reduced compression set compared to Example E5. As shown in Examples E5 and E7, a reduced degree of hydrogenation of the thermoplastic elastomer in the peroxide-curable composition can improve the crosslink density and heat resistance of the partially crosslinked polymer system obtained.

[0175] As shown in Table 3, Example E6 is a partially crosslinked polymer system formed from a peroxide-curable composition containing a silane and aged, and Example E5 is a partially crosslinked polymer system formed from a peroxide-curable composition containing a silane but not aged, and Example E6 shows reduced tensile elongation at break and reduced compression set compared to Example E5. As shown in Examples E5 and E6, aging the partially crosslinked polymer system in the presence of moisture results in silane crosslinking, further increasing the crosslink density and heat resistance.

[0176] As shown in Table 4, Examples E11 and E12 are partially crosslinked polymer systems formed from a peroxide-curable composition including a thermoplastic elastomer having 64% hydrogenation (KRATON G1654 (64% hydrogenation)), and Examples E9 and E10 are partially crosslinked polymer systems formed from a peroxide-curable composition including a thermoplastic elastomer having 85% hydrogenation (KRATON G1654 (85% hydrogenation)), and Examples E11 and E12 show reduced tensile elongation at break and reduced compression set compared to Examples E9 and E10. As shown in Examples E9 to E12, the reduced degree of hydrogenation of the thermoplastic elastomer in the peroxide-curable composition improves the crosslink density and heat resistance of the partially crosslinked polymer system obtained.

[0177] As shown in Table 4, Examples E10 and E12 are partially crosslinked polymer systems formed from peroxide-vulcanizable compositions containing 0.4 wt% of an organic peroxide (PERKADOX BC-FF), and Examples E9 and E11 are partially crosslinked polymer systems formed from peroxide-vulcanizable compositions containing 0.2 wt% of an organic peroxide, respectively, and Examples E10 and E12 show reduced tensile elongation at break and reduced compression set compared to Examples E9 and E11. As shown in Examples E9 to E12, increasing the amount of organic peroxide in the peroxide-vulcanizable composition improves the crosslink density and heat resistance of the partially crosslinked polymer system obtained.

[0178] As shown in Table 5, Example E15 is a partially crosslinked polymer system formed from a peroxide-vulcanizable composition including a thermoplastic elastomer having 64% hydrogenation (KRATON G1652 (64% hydrogenation)), and Example E14 is a partially crosslinked polymer system formed from a peroxide-vulcanizable composition including a thermoplastic elastomer having 85% hydrogenation (KRATON G1652 (85% hydrogenation)). Compared with Example E14, Example E14 shows a reduced tensile elongation at break and a reduced compression set. Compared with Example E13, Example E13 is a partially crosslinked polymer system formed from a peroxide-vulcanizable composition including a thermoplastic elastomer having 90% hydrogenation (KRATON G1652 (90% hydrogenation)). As shown in Examples E13 to E15, reducing the degree of hydrogenation of the thermoplastic elastomer in the peroxide-curable composition improves the crosslink density and heat resistance of the resulting partially crosslinked polymer system.

[0179] As shown in Table 7, Examples E18 and E19 are partially crosslinked polymer systems formed from a peroxide-curable composition without a catalyst, and Comparative Examples C8 and C9 are partially crosslinked polymer systems formed from a peroxide-curable composition with a catalyst and aged, and Examples E18 and E19 achieve desirable tensile elongation at break (e.g., greater than or equal to 30%) and compression set (e.g., greater than or equal to 20%) compared to Comparative Examples C8 and C9. As shown in Examples E18 and E19 and Comparative Examples C8 and C9, improved crosslink density and heat resistance can be achieved after blending without the need for additional steps or materials.

[0180] As shown in Table 8, Example E22 is a partially crosslinked polymer system formed from a peroxide-vulcanizable composition comprising 0.18 wt % organic peroxide (PERKADOX BC-FF), and Example E21 is a partially crosslinked polymer system formed from a peroxide-vulcanizable composition comprising 0.16 wt % organic peroxide, and Example E22 exhibits reduced tensile elongation at break and reduced compression set compared to Example E21. Example E21 exhibits reduced tensile elongation at break and reduced compression set compared to Example E20, which is a partially crosslinked polymer system formed from a peroxide-vulcanizable composition comprising 0.13 wt % organic peroxide. As shown in Examples E20 to E22, an increase in the amount of organic peroxide in the peroxide-vulcanizable composition improves the crosslink density and heat resistance of the partially crosslinked polymer system obtained.

[0181] Obviously, modifications and variations are possible without departing from the scope of the disclosure as defined in the appended claims.More specifically, although some aspects of the present disclosure are identified herein as preferred or particularly advantageous, it is contemplated that the present disclosure is not necessarily limited to these aspects.

Claims

1. A partially cross-linked polymer system comprising: A vulcanized silane-grafted thermoplastic elastomer comprising carbon-carbon crosslinks, The silane-grafted thermoplastic elastomer comprises the polymerization reaction product of a vinyl aromatic monomer and a conjugated diene monomer.

2. The partially cross-linked polymer system according to claim 1, wherein The partially cross-linked polymer system has a tensile elongation at break of about 30% to about 725%; and The compression set measured at 100°C is from about 20% to about 90%.

3. The partially cross-linked polymer system according to claim 1 or claim 2, wherein: The conjugated diene monomer is selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, isoprene, and combinations thereof.

4. A partially crosslinked polymer system as claimed in any one of the preceding claims, wherein The vinyl aromatic monomer is selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene, p-tert-butylstyrene, and combinations thereof.

5. A partially crosslinked polymer system as claimed in any one of the preceding claims, wherein The thermoplastic elastomer is selected from the group consisting of styrene-butadiene rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene-isoprene rubber, styrene-butadiene / isoprene block polymer, styrene-butadiene-isoprene block copolymer, partially hydrogenated styrene-butadiene rubber, partially hydrogenated styrene-butadiene block copolymer, partially hydrogenated styrene-isoprene block copolymer, partially hydrogenated styrene-butadiene-isoprene rubber, partially hydrogenated styrene-butadiene / isoprene block copolymer, partially hydrogenated styrene-butadiene-isoprene block copolymer, and combinations thereof.

6. A partially crosslinked polymer system as claimed in any one of the preceding claims, wherein Thermoplastic elastomers are block copolymers comprising blocks defined by formula (I): wherein w, x, y and z units are randomly distributed in the block, each R1 is independently a hydrogen atom or a methyl group, and each R2 is independently a hydrogen atom or a methyl group, provided that at least one R2 in each unit is a hydrogen atom; and the molar percentage of the sum of the y units and the z units in the block to the sum of the w, x, y units and the z units is about 30% to about 90%.

7. The partially cross-linked polymer system according to claim 6, wherein The mole percentage of the sum of the y units and the z units in the block is about 50% to about 70% of the sum of the w, x, y units and z units.

8. The partially cross-linked polymer system according to claim 6, wherein The ratio of y units to w units is greater than the ratio of x units to z units.

9. The partially cross-linked polymer system according to claim 6, wherein The ratio of y units to w units is less than the ratio of x units to z units.

10. The partially crosslinked polymer system according to any one of claims 1 to 5, wherein The thermoplastic elastomer is a block copolymer comprising a block defined by formula (II): The a, b, c and d units are randomly distributed in the block, and the molar percentage of the sum of the c units and the d units in the block is about 30% to about 90% of the sum of the a, b, c and d units.

11. The partially crosslinked polymer system according to claim 10, wherein The sum of c units and d units accounts for about 50 to about 70 mole percent of the sum of a, b, c, and d units in the block.

12. The partially cross-linked polymer system according to claim 10, wherein The ratio of c units to a units is greater than the ratio of d units to b units.

13. The partially cross-linked polymer system according to claim 10, wherein The ratio of c units to a units is smaller than the ratio of d units to b units.

14. A partially crosslinked polymer system as claimed in any one of the preceding claims, wherein The number average molecular weight of the thermoplastic elastomer is from about 30,000 g / mol to about 400,000 g / mol.

15. A partially crosslinked polymer system as claimed in any one of the preceding claims, wherein The thermoplastic elastomer is a triblock copolymer including two polystyrene end blocks, and the styrene content of the two polystyrene end blocks in the thermoplastic elastomer is from about 10 wt % to about 50 wt %.

16. The partially crosslinked polymer system according to any one of claims 1 to 5, wherein Partially crosslinked polymer systems are block copolymers with a hard phase and a soft phase, generally constructed as follows: A-B, A-B-A or A-B-A′, where, Each A and A' block is a hard phase comprising vinyl aromatic monomer units, and each B block is a soft phase comprising conjugated diene monomer units.

17. A partially crosslinked polymer system as claimed in any one of the preceding claims, wherein Partially crosslinked polymer systems are silane crosslinked.

18. A partially crosslinked polymer system as claimed in any one of the preceding claims, wherein Partially crosslinked polymer systems are thermoplastic vulcanizates.

19. A partially crosslinked polymer system as claimed in any one of the preceding claims, wherein Partially crosslinked polymer systems also include olefin polymers.

20. A peroxide-curable composition comprising: A thermoplastic elastomer comprising vinyl aromatic monomer units and conjugated diene monomer units; and Curing package containing organic peroxides and silanes.

21. The peroxide-curable composition of claim 20, wherein: The peroxide curable composition comprises from about 25 wt % to about 95 wt % of the thermoplastic elastomer, or from about 30 wt % to about 85 wt % or from about 35 wt % to about 75 wt % of the thermoplastic elastomer.

22. A peroxide-curable composition according to claim 20 or claim 21, wherein The conjugated diene monomer unit is selected from the group consisting of 1,3-butadiene monomer unit, 2,3-dimethyl-1,3-butadiene monomer unit, piperylene monomer unit, isoprene monomer unit and combinations thereof.

23. The peroxide-curable composition of any one of claims 20 to 22, wherein The vinyl aromatic monomer units are selected from the group consisting of styrene monomer units, α-methylstyrene monomer units, p-methylstyrene monomer units, o-methylstyrene monomer units, p-butylstyrene monomer units, p-tert-butylstyrene monomer units, and combinations thereof.

24. The peroxide-curable composition of any one of claims 20 to 23, wherein The thermoplastic elastomer is partially hydrogenated.

25. The peroxide-curable composition of claim 24, wherein: The thermoplastic elastomer has a degree of hydrogenation of greater than or equal to about 50%, or greater than or equal to about 60%, or greater than or equal to about 70%.

26. The peroxide-curable composition of any one of claims 20 to 25, wherein The thermoplastic elastomer is selected from the group consisting of styrene-butadiene rubber, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene-isoprene rubber, styrene-butadiene / isoprene block polymer, styrene-butadiene-isoprene block copolymer, partially hydrogenated styrene-butadiene rubber, partially hydrogenated styrene-butadiene block copolymer, partially hydrogenated styrene-isoprene block copolymer, partially hydrogenated styrene-butadiene-isoprene rubber, partially hydrogenated styrene-butadiene / isoprene block copolymer, partially hydrogenated styrene-butadiene-isoprene block copolymer, and combinations thereof.

27. The peroxide-curable composition of any one of claims 20 to 26, wherein Thermoplastic elastomers are block copolymers comprising blocks defined by formula (I): wherein w, x, y and z units are randomly distributed in the block, each R1 is independently a hydrogen atom or a methyl group, and each R2 is independently a hydrogen atom or a methyl group, provided that at least one R2 in each unit is a hydrogen atom; and the molar percentage of the sum of the y units and the z units in the block to the sum of the w, x, y units and the z units is about 30% to about 90%.

28. The peroxide-curable composition of claim 27, wherein: The mole percentage of the sum of the y units and the z units in the block is about 50% to about 70% of the sum of the w, x, y units and z units.

29. The peroxide-curable composition of claim 27, wherein: The ratio of y units to w units is greater than the ratio of x units to z units.

30. The peroxide-curable composition of claim 27, wherein: The ratio of y units to w units is less than the ratio of x units to z units.

31. The peroxide-curable composition of any one of claims 20 to 26, wherein The thermoplastic elastomer is a block copolymer comprising a block defined by formula (II): The a, b, c and d units are randomly distributed in the block, and the molar percentage of the sum of the c units and the d units in the block is about 30% to about 90% of the sum of the a, b, c and d units.

32. The peroxide-curable composition of claim 31, wherein: The mole percentage of the sum of the c units and the d units in the block is about 50% to about 70% of the sum of the a, b, c and d units.

33. The peroxide-curable composition of claim 31, wherein: The ratio of c units to a units is greater than the ratio of d units to b units.

34. The peroxide-curable composition of claim 31, wherein: The ratio of c units to a units is smaller than the ratio of d units to b units.

35. The peroxide-curable composition of any one of claims 20 to 34, wherein The number average molecular weight of the thermoplastic elastomer is from about 30,000 g / mol to about 400,000 g / mol.

36. The peroxide-curable composition of any one of claims 20 to 35, wherein The thermoplastic elastomer is a triblock copolymer including two polystyrene end blocks, and the styrene content of the two polystyrene end blocks in the thermoplastic elastomer is from about 10 wt % to about 50 wt %.

37. The peroxide-curable composition of any one of claims 20 to 26, wherein Thermoplastic elastomers are hydrogenated block copolymers with a hard phase and a soft phase, generally constructed as follows: A-B, A-B-A or A-B-A′, where, Prior to hydrogenation, each A and A' block is a hard phase comprising vinyl aromatic monomer units, and each B block is a soft phase comprising conjugated diene monomer units.

38. The peroxide-curable composition of any one of claims 20 to 37, wherein The peroxide-curable composition comprises from about 0.5 wt % to about 5 wt % of the silane.

39. The peroxide-curable composition of any one of claims 20 to 38, wherein The silane includes vinyltrimethoxysilane, vinyltriethoxysilane, or a combination thereof.

40. The peroxide-curable composition of any one of claims 20 to 39, wherein The peroxide-curable composition comprises from about 0.05 wt. % to about 1 wt. % of an organic peroxide.

41. The peroxide-curable composition of any one of claims 20 to 40, wherein The organic peroxide includes peroxyketal peroxide, di-tert-alkyl peroxide or a combination thereof.

42. The peroxide-curable composition of claim 41, wherein: The di-tert-alkyl peroxides include dicumyl peroxide.

43. The peroxide-curable composition of any one of claims 20 to 42, wherein The peroxide curable composition also comprises an olefin polymer.

44. The peroxide-curable composition of claim 43, wherein: The peroxide curable composition comprises from about 2 wt % to about 50 wt % olefin polymer, or from about 4 wt % to about 40 wt % olefin polymer, or from about 6 wt % to about 30 wt % olefin polymer.

45. A peroxide-curable composition according to claim 43 or claim 44, wherein The olefin polymer includes polyolefins, polyolefin elastomers, or combinations thereof.

46. ​​The peroxide-curable composition of any one of claims 20 to 45, wherein The peroxide-curable composition also comprises a plasticizer.

47. The peroxide-curable composition of claim 46, wherein: The peroxide curable composition comprises from about 10 wt % to about 60 wt % plasticizer, or from about 15 wt % to about 55 wt % plasticizer, or from about 20 wt % to about 50 wt % plasticizer.

48. A peroxide-curable composition according to claim 46 or claim 47, wherein Plasticizers include mineral oil.

49. The peroxide-curable composition of any one of claims 20 to 48, wherein The peroxide curable composition also comprises a tackifier.

50. The peroxide-curable composition of claim 49, wherein: The peroxide curable composition comprises from about 15 wt % to about 50 wt % tackifier, or from about 17 wt % to about 40 wt % tackifier, or from about 20 wt % to about 30 wt % tackifier.

51. A peroxide-curable composition according to claim 49 or claim 50, wherein: Tackifiers include hydrocarbon resins.

52. The peroxide-curable composition of any one of claims 20 to 51, wherein The peroxide curable composition also comprises a copolymer.

53. The peroxide-curable composition of claim 52, wherein: The peroxide-curable composition comprises from about 25 wt % to about 45 wt % of the copolymer, or from about 27 wt % to about 43 wt % of the copolymer, or from about 30 wt % to about 40 wt % of the copolymer.

54. A peroxide-curable composition according to claim 52 or claim 53, wherein: Copolymers include ethylene vinyl acetate.

55. A partially crosslinked polymer system prepared from the peroxide-curable composition of any one of claims 20 to 54.

56. The partially crosslinked polymer system of claim 55, wherein The partially crosslinked polymer system contains carbon-carbon crosslinks and grafted silane moieties.

57. The partially crosslinked polymer system of claim 55, wherein Partially crosslinked polymer systems include carbon-carbon crosslinks and silane crosslinks.

58. The partially crosslinked polymer system of any one of claims 55 to 57, wherein Partially crosslinked polymer systems are thermoplastic vulcanizates.

59. A method for preparing a partially crosslinked polymer system, the partially crosslinked polymer system comprising the crosslinked reaction product of a thermoplastic elastomer and a cure package, the thermoplastic elastomer comprising vinyl aromatic monomer units and conjugated diene monomer units, the cure package comprising an organic peroxide and a silane, the method comprising the steps of: blending a thermoplastic elastomer, an organic peroxide, and a silane so that the thermoplastic elastomer contains carbon-carbon bond crosslinks and grafted silane moieties; as well as Extrusion of carbon-carbon crosslinked silane grafted blends.

60. The method of claim 59, wherein: The step of blending the thermoplastic elastomer, the organic peroxide and the silane is carried out in the absence of a catalyst.

61. The method of claim 59, wherein: The step of blending the thermoplastic elastomer, the organic peroxide and the silane is carried out in the absence of moisture.

62. The method of any one of claims 59 to 60, wherein: When extruded, the partially crosslinked polymer system has an extrusion tensile elongation at break of greater than or equal to about 30%, and the partially crosslinked polymer system maintains a tensile elongation at break within 5% of the extrusion tensile elongation at break for 24 hours at room temperature.

63. The method of any one of claims 59 to 62, wherein: When extruded, the partially crosslinked polymer system has an extrusion compression set greater than or equal to about 20%, and the partially crosslinked polymer system retains a compression set at break within 5% of the extrusion compression set at room temperature for 24 hours.

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