Crosslinked compositions from olefin / silane interpolymers

Abstract

A method of forming a crosslinked composition is disclosed, the method comprising heat treating a composition comprising: a) an olefin / silane interpolymer, b) a curing catalyst, and c) a polyvinyl compound. A composition is disclosed, the composition comprising: a) an olefin / silane interpolymer, b) a curing catalyst, and c) a polyvinyl compound.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 043,193, filed on June 24, 2020, which is incorporated herein by reference in its entirety. Background Art

[0003] Hydrosilylation crosslinking agents and crosslinking catalysts such as Pt catalysts have been used to crosslink olefin-based polymers and polymer blends (see US 5672660, US 6476132, US 8865800, US 2017 / 0145131, and JP9137002A). 3 ) 2 H) Olefin-based polymers can be prepared by copolymerizing ethylene and / or other α-olefins with monomers such as octenylsilane, hexenylsilane and allylsilane (see US 6624254 and US 6258902). Such interpolymers can be further functionalized and / or crosslinked.

[0004] It has been found that containing, for example, -Si(CH 3 ) 2 H-functional olefin-based interpolymers can be crosslinked using polyvinyl compounds by hydrosilylation reaction with a catalyst such as a "Pt-containing" catalyst. These crosslinked formulations can be prepared by co-dissolving the polymer and components in a common solvent followed by removal of the solvent; or by melt blending the components by adding thermal energy and then mixing to homogenize and evenly disperse the curing components. It has been found that when the formulated polymer is heated above its melting point, polyvinyl compounds react with silane groups (e.g., -Si(CH 3 ) 2 H) reaction in the presence of a catalyst results in the formation of covalently bonded crosslinks, for example, between adjacent interpolymer chains. See, for example Figure 1 . Summary of the invention

[0005] A method of forming a crosslinked composition, the method comprising heat treating a composition comprising:

[0006] a) olefin / silane interpolymer,

[0007] b) a curing catalyst, and

[0008] c) Polyvinyl compounds.

[0009] A composition comprising the following components:

[0010] a) olefin / silane interpolymer,

[0011] b) a curing catalyst, and

[0012] c) Polyvinyl compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 Schematic diagram of the hydrosilylation of an olefin / silane interpolymer in the presence of a curing catalyst.

[0014] Figure 2 Depicted are two sequential DSC scans of an olefin / silane interpolymer (80 wt% interpolymer / 20 wt% PBd) with 20 ppm Pt catalyst.

[0015] Figure 3 Depicted is a graph of the magnitude of "Complex Viscosity vs. Temperature" for an olefin / silane interpolymer containing 3.0 wt% ODMS and formulated with 2 wt% very low molecular weight polybutadiene resin having 90 mole % 1,2 vinyl content, 10 ppm Pt catalyst, and 100 ppm bis(2-ethylhexyl) maleate.

[0016] Figure 4 Depicted is a graph of the magnitude of Complex Viscosity vs. Temperature for a neat ethylene / octene / silane interpolymer containing 1.3 wt% ODMS and 41.9 wt% octene.

[0017] Figure 5 Depicted is a graph of the magnitude of Complex Viscosity vs. Temperature for an olefin / silane interpolymer containing 1.3 wt% ODMS and formulated with 1 wt% very low molecular weight polybutadiene resin containing 90 mole % 1,2 vinyl content and 10 ppm Pt catalyst.

[0018] Figure 6 An isotherm of a melt blended olefin / silane interpolymer (98 wt%), polybutadiene polyvinyl crosslinker (2 wt%), and 100 ppm Pt catalyst is depicted showing shear storage modulus growth over time. Shear storage modulus growth can be directly related to crosslink density.

[0019] Figure 7 Isotherms are depicted for melt blended olefin / silane interpolymer (98 wt%), polybutadiene polyvinyl crosslinker (2 wt%), and 10 ppm or 100 ppm Pt catalyst showing the shear storage modulus growth over time.

[0020] Figure 8Three dynamic mechanical analysis (DMA) curves for a temperature ramp from 25°C to 200°C at 2°C / min are depicted for olefin / silane interpolymer samples containing no Pt, 10 ppm Pt without inhibitor, and 10 ppm and 1000 ppm ETCH inhibitor.

[0021] Fig. 9 Isotherms of melt blended olefin / silane interpolymer (98 wt%), polybutadiene polyvinyl crosslinker (2 wt%), 1000 ppm of various inhibitors, and 100 ppm of Pt catalyst are depicted showing the shear storage modulus growth over time.

[0022] Fig.10 Isotherms at 120°C and 180°C are depicted for a sample containing 98 wt% olefin / silane interpolymer, 2 wt% polybutadiene, 1000 ppm inhibitor (ETCHA or Surfynol-61), and 100 ppm Pt catalyst.

[0023] Fig.11 Seven dynamic mechanical analysis (DMA) curves for a temperature ramp from 25°C to 200°C at 2°C / min for samples having 98 wt% olefin / silane interpolymer, 2 wt% polybutadiene, 100 ppm Pt and 200 ppm, 750 ppm or 1500 ppm of IRGANOX 1010, IRGOFOS 1680 or IRGANOX 1076 are depicted. DETAILED DESCRIPTION

[0024] As discussed above, in a first aspect of the present invention, there is provided a method of forming a cross-linked composition, the method comprising heat treating a composition comprising:

[0025] a) olefin / silane interpolymer,

[0026] b) a curing catalyst, and

[0027] c) Polyvinyl compounds.

[0028] The above method may comprise a combination of two or more embodiments as described herein.Each component a, b and c may comprise a combination of two or more embodiments as described herein.

[0029] In a second aspect of the present invention, there is also provided a composition comprising the following components:

[0030] a) olefin / silane interpolymer,

[0031] b) a curing catalyst, and

[0032] c) Polyvinyl compounds.

[0033] The above composition may comprise a combination of two or more embodiments as described herein.Each component a, b and c may comprise a combination of two or more embodiments as described herein.

[0034] Unless otherwise stated, the following embodiments apply to both the first and second aspects of the present invention.

[0035] In one embodiment or a combination of two or more embodiments each described herein, the olefin / silane interpolymer of component a is an ethylene / α-olefin / silane interpolymer, and further an ethylene / α-olefin / silane terpolymer.

[0036] In one embodiment or a combination of two or more embodiments described herein, the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of: 2 C=CH-R 1 -Si(R)(R')-H, wherein R1 is an alkylene group, and R and R' are each independently an alkyl group, and R and R' may be the same or different.

[0037] In one embodiment or combination of two or more embodiments individually described herein, the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of: Where R 2 It is an alkylene group.

[0038] In one embodiment or combination of two or more embodiments individually described herein, the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of:

[0039]

[0040] In one embodiment or a combination of two or more embodiments individually described herein, the curing catalyst of component b comprises platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

[0041] In one embodiment or a combination of two or more embodiments individually described herein, the polyvinyl compound of component c is selected from the following i) to iv):

[0042] i) Wherein R3 is selected from alkylene or arylene;

[0043] ii) a polydiene comprising at least one of the following structures: (CR1R2-CR3=CR4-CR5R6) n -(CR7R8-CR9(CR10=CR11R12)) m-, wherein each of R1 to R12 is independently hydrogen (H) or alkyl, and n≥1 and m≥1, and further each of R1 to R12 is hydrogen, and further n is 1 to 50, or 1 to 40, or 1 to 30, or 1 to 20, and m is 1 to 50, or 1 to 40, or 1 to 30, or 1 to 20;

[0044] iii) H 3 C-CH 2 -C[R4-OC(O)-CH=CH 2 ] 3 , wherein R4 is an alkylene group or an arylene group; or

[0045] iv) has the following structure – [Si(CH=CH 2 )(R5)-O] n - a cyclic siloxane wherein R5 is an alkyl group and n is 3 to 6.

[0046] In one embodiment or a combination of two or more embodiments described herein, the polyvinyl compound of component c is selected from the following: dodecadiene, divinylbenzene, tetravinyltetramethylcyclotetrasiloxane (ViD4), trimethylolpropane triacrylate (TMPTA), or polybutadiene, wherein the polybutadiene contains ≥80 mol%, ≥85 mol%, or ≥90 mol% of 1,2 vinyl groups based on the total vinyl content and has a melt viscosity of 30 cP to 500 cP, or 30 cP to 400 cP, or 30 cP to 300 cP, or 30 cP to 200 cP, or 30 cP to 150 cP, or 30 cP to 100 cP at 45°C.

[0047] In one embodiment or a combination of two or more embodiments each described herein, the composition further comprises component d: a curing inhibitor. In one embodiment or a combination of two or more embodiments each described herein, the curing inhibitor is selected from the following:

[0048]

[0049] If ViD4 is not used as component c.

[0050] Note that when ViD4 is used as a curing inhibitor (component d), it is generally present in an amount of 0.01 to 0.10 wt % based on the weight of the composition. When ViD4 is used as a polyvinyl compound (component c), it is generally present in an amount of 1.0 to 5.0 wt % based on the weight of the composition.

[0051] In one embodiment or a combination of two or more embodiments individually described herein, the composition further comprises a component e selected from IRGANOX 1010, IRGANOX 1076, or a combination thereof.

[0052] In one embodiment or a combination of two or more embodiments each described herein, the composition is heat treated at a temperature of ≥40°C, or ≥45°C, or ≥50°C, or ≥55°C, or ≥60°C, or ≥65°C, or ≥70°C. In one embodiment or a combination of two or more embodiments each described herein, the composition is heat treated at a temperature of ≤200°C, or ≤180°C, or ≤160°C, or ≤140°C, or ≤120°C, or ≤100°C.

[0053] In one embodiment or a combination of two or more embodiments individually described herein, the method further comprises adding component c to component a before or simultaneously with adding component b to component a prior to heat treating the composition comprising components ac.

[0054] In one embodiment or a combination of two or more embodiments individually described herein, the composition further comprises a filler, and the further filler is present in an amount from 1.0 wt%, or 2.0 wt%, or 5.0 wt% to 10 wt%, or 15 wt%, or 20 wt%, wherein each weight percentage is based on the weight of the composition.

[0055] Also provided are cross-linked compositions formed by the inventive methods described herein or from the inventive compositions described herein.

[0056] Also provided is an article comprising at least one component formed from a composition of any one embodiment or a combination of two or more embodiments described herein. In one embodiment or a combination of two or more embodiments (each of which is described herein), the article is a film. In one embodiment or a combination of two or more embodiments described herein, the article is an automotive part and a building material or a computer part.

[0057] Silane monomer

[0058] As used herein, a silane monomer comprises at least one (type) of Si-H group. In one embodiment, the silane monomer is selected from Formula 1:

[0059] A-(SiBC-O) x -Si-EFH (Formula 1),

[0060] wherein A is an alkenyl group;

[0061] B is a hydrocarbyl group or hydrogen, C is a hydrocarbyl group or hydrogen, and wherein B and C can be the same or different;

[0062] H is hydrogen, and x ≥ 0;

[0063] E is a hydrocarbyl group or hydrogen, and F is a hydrocarbyl group or hydrogen, and wherein E and F can be the same or different.

[0064] Some examples of silane monomers include hexenylsilane, allylsilane, vinylsilane, octenylsilane, hexenyldimethylsilane, octenyldimethylsilane, vinyldimethylsilane, vinyldiethylsilane, vinyldi(n-butyl)silane, vinylmethyloctadecylsilane, vinyldiphenylsilane, vinyldibenzylsilane, allyldimethylsilane, allyldiethylsilane, allyldi(n-butyl)silane, allylmethyloctadecylsilane, allyldiphenylsilane, bis-hexenylsilane, and allyldibenzylsilane. Mixtures of the above alkenylsilanes may also be used.

[0065] More specific examples of the silane monomer include the following: (5-hexenyl-dimethylsilane (HDMS), 7-octenyldimethylsilane (ODMS), allyldimethylsilane (ADMS), 3-butenyldimethylsilane, 1-(but-3-en-1-yl)-1,1,3,3-tetramethyldisiloxane (BuMMH), 1-(hex-5-en-1-yl)-1,1,3,3-tetramethyldisiloxane (HexMMH), (2-bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-dimethylsilane (NorDMS) and 1-(2-bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyl-disiloxane (NorMMH).

[0066] Curing catalyst

[0067] As used herein, a curing catalyst is a catalyst that accelerates the curing of pendant silane moieties (e.g., —Si(CH 3 ) 2H) and the compound of the reaction between the vinyl group of the polyvinyl compound. Suitable catalysts include catalysts based on platinum or other metals (such as tin or nickel, Ir or Rh). In one embodiment described herein or a combination of two or more embodiments, the catalyst comprises Pt, Sn, Ni, Ir or Rh, further comprises Pt, Sn or Ni, further comprises Pt or Sn, further comprises Pt. The most well-known of these catalysts is Karstedt catalyst (i.e., platinum (0) -1,3-divinyl -1,1,3,3-tetramethyldisiloxane complex solution), as shown in the following structure. Karstedt catalyst is commercially available as a xylene solution containing 2 wt % Pt (Sigma Aldrich).

[0068]

[0069] Polyvinyl compounds

[0070] Polyvinyl compounds contain two or more vinyl groups (-CH=CH 2 ) groups. Preferred polyvinyl agents tend to be lower molecular weight compounds that exhibit sufficient solubility or thermodynamic miscibility with the olefin / silane interpolymer to allow for uniform distribution of the component in the formulation to achieve the desired level of crosslinking necessary. Suitable compounds include tetravinyltetramethylcyclotetra-siloxane (ViD4), low molecular weight polybutadiene with a predominantly 1,2-addition (about 90 mole % 1,2-vinyl), dodecadiene, divinylbenzene, trimethylolpropane triacrylate (TMPTA), and the like.

[0071] Less preferred agents that may still provide some crosslinking activity tend to be higher molecular weight compounds that contain a low density of vinyl groups or have significant polarity or exhibit limited solubility in formulated olefin / silane interpolymers. Some examples of these less suitable agents include ethylene-co-propylene-co-ethylidene norbornene (EPDM) copolymers and polybutadiene with a high percentage of 1,4 addition (containing 50 mole % or more of internal cis or trans vinylidene groups).

[0072] Curing inhibitor

[0073] As used herein, curing inhibitors delay the hydrosilylation reaction with polyvinyl compounds. Inhibitors can also be added to the formulation to delay the onset of crosslinking by hydrosilylation. These inhibitors can be temporarily complexed with vinyl groups, such as in Pt catalyst complexes, to prevent catalyst activity. It was found that different types of inhibitors and inhibitor loadings resulted in different crosslinking rates that varied with temperature. This discovery allows for a high degree of tunability in designing the polymer processability window when considering premature crosslinking of melt-blended catalyst-containing formulations.

[0074] Melt-processible, cross-linkable formulations can be prepared by incorporating hydrosilylation inhibitors into a mixture containing, for example, -Si(CH 3 ) 2 The invention relates to a hydrosilylation agent for hydrosilylation of a polyvinyl compound. The hydrosilylation agent is preferably a polyvinyl compound, such as a polyvinyl compound, a polyvinyl compound, and a polyvinyl compound. The polyvinyl compound may be prepared by combining a H-functionalized olefin / silane interpolymer, a polyvinyl compound, and a Pt catalyst. These inhibitory compounds competitively bind to the Pt catalyst, thereby delaying the hydrosilylation reaction with the polyvinyl compound. As the temperature rises, the inhibitor disengages from the catalyst, enabling a crosslinking reaction based on hydrosilylation to be performed. Suitable hydrosilylation inhibitors include dioctyl maleate, surfynol-61, ETCH, ETCHA, phosphite-based antioxidants such as IRGAFOS 168 (or IRGAFOS 1680), and tetravinyltetramethyl-cyclotetrasiloxane (ViD4).

[0075] additive

[0076] The composition of the present invention may include one or more additives. The additives include, but are not limited to, UV stabilizers, antioxidants, fillers, scorch retardants and flame retardants, tackifiers, waxes, compatibilizers, adhesion promoters, processing aids, end-capping agents, anti-blocking agents, antistatic agents, mold release agents, anti-sticking additives, colorants, dyes, pigments, and combinations thereof.

[0077] In one embodiment or a combination of two or more embodiments (each of which is described herein), the inventive composition further comprises a thermoplastic polymer that differs from the olefin / silane interpolymer (component a) in one or more characteristics such as monomer type and / or amount, Mn, Mw, Mz, MWD, V0.1, V100, RR (V0.1 / V100), or any combination thereof; and additional monomer type and / or amount, Mn, Mw, MWD, or any combination thereof. Polymers include, but are not limited to, ethylene-based polymers, propylene-based polymers, and olefin multi-block interpolymers. Suitable ethylene-based polymers include, but are not limited to, linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), homogeneously branched linear ethylene-based polymers, and homogeneously branched substantially linear ethylene-based polymers (i.e., homogeneously branched long chain branched ethylene polymers). Examples of propylene-based polymers include polypropylene homopolymers and propylene / ethylene copolymers.

[0078] definition

[0079] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure.

[0080] As used herein, the term "composition" includes mixtures of materials including the composition as well as reaction products and decomposition products formed from the composition materials. Any reaction products or decomposition products are typically present in trace or residual amounts.

[0081] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer encompasses the term homopolymer (used to refer to polymers prepared from only one type of monomer, it being understood that trace amounts of impurities may be incorporated into the polymer structure) and the term interpolymer as defined below. Trace amounts of impurities (such as catalyst residues) may be incorporated into and / or within the polymer. Typically, the polymer is stabilized with very low amounts ("ppm" amounts) of one or more stabilizers.

[0082] As used herein, the term "interpolymer" refers to polymers prepared by the polymerization of at least two different types of monomers. The term interpolymer thus includes the term copolymer (used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0083] As used herein, the term "olefin-based polymer" refers to polymers that contain, in polymerized form, 50 weight percent or majority weight percent olefins, such as ethylene or propylene (based on the weight of the polymer), and optionally may contain one or more comonomers.

[0084] As used herein, the term "propylene-based polymer" refers to a polymer that contains, in polymerized form, a majority weight percent propylene (based on the weight of the polymer) and optionally may contain one or more comonomers.

[0085] As used herein, the term "ethylene-based polymer" refers to a polymer that, in polymerized form, comprises 50 weight percent or majority weight percent ethylene (based on the weight of the polymer), and optionally may include one or more comonomers.

[0086] As used herein, the term "ethylene / α-olefin interpolymer" refers to a random interpolymer comprising, in polymerized form, 50 weight percent or majority weight percent ethylene (based on the weight of the interpolymer) and an α-olefin.

[0087] As used herein, the term "ethylene / α-olefin copolymer" refers to a random copolymer comprising, in polymerized form, 50 weight percent or majority amount of ethylene monomer (based on the weight of the copolymer) and α-olefin as the only two monomer types.

[0088] As used herein, the term "olefin / silane interpolymer" refers to a random interpolymer containing 50 weight percent or a majority weight percent of olefin (based on the weight of the interpolymer) and silane monomers in polymerized form. As used herein, the interpolymer contains at least one Si-H group, and the phrase "at least one Si-H group" refers to the type of "Si-H" group. It is understood in the art that the interpolymer will contain a plurality of such Si-H types. Olefin / silane interpolymers are formed by copolymerization of at least olefin and silane monomers. Examples of silane monomers are shown in Formula 1 described herein.

[0089] As used herein, the term "ethylene / silane interpolymer" refers to a random interpolymer that contains 50 weight percent or majority weight percent ethylene (based on the weight of the interpolymer) and silane monomers in polymerized form. As used herein, the interpolymer contains at least one Si-H group, as discussed above. Ethylene / silane interpolymers are formed by copolymerization of at least ethylene and silane monomers.

[0090] As used herein, the term "ethylene / α-olefin / silane interpolymer" refers to a random interpolymer that contains, in polymerized form, 50 weight percent or majority weight percent ethylene (based on the weight of the interpolymer), α-olefin, and silane monomers. As used herein, the interpolymer contains at least one Si-H group, as discussed above. Ethylene / silane interpolymers are formed by copolymerization of at least ethylene, α-olefin, and silane monomers.

[0091] As used herein, the term "ethylene / α-olefin / silane terpolymer" refers to a random terpolymer containing, in polymerized form, 50 weight percent or majority weight percent ethylene (based on the weight of the terpolymer), α-olefin, and silane monomers as the only three monomer types. As used herein, the terpolymer contains at least one Si-H group, as discussed above. Ethylene / silane terpolymers are formed by copolymerization of ethylene, α-olefin, and silane monomers.

[0092] As used herein, the terms "hydrocarbon group," "hydrocarbyl group," and similar terms refer to a chemical group that contains only carbon and hydrogen atoms.

[0093] As used herein, the term "crosslinked composition" refers to a composition having a network structure due to the formation of chemical bonds between polymer chains. The formation of this network structure can be indicated by an increase in complex viscosity or shear storage modulus as discussed herein.

[0094] As used herein, the term "crosslinked olefin / silane interpolymer" refers to an olefin / silane interpolymer having a network structure due to chemical bonds formed between polymer chains. The formation of this network structure can be indicated by an increase in complex viscosity or shear storage modulus as discussed herein.

[0095] As used herein, the term "heat treatment" and similar terms with respect to compositions containing olefin / silane interpolymers refers to applying heat to the composition. Heat can be applied by conduction (e.g., heating coils), by convection (e.g., heat transfer through a fluid such as water or air), and / or by radiation (e.g., heat transfer using electromagnetic waves). Preferably, heat is applied by conduction or convection. Note that the temperature at which the heat treatment is performed refers to the temperature of the composition (e.g., the melting temperature of the composition).

[0096] As used herein, the term "alkenyl group" refers to an organic chemical group containing at least one carbon-carbon double bond (C=C). In a preferred embodiment, the alkenyl group is a hydrocarbon group containing at least one carbon-carbon double bond and also only one carbon-carbon double bond.

[0097] As used herein, R1=R 1 , R2=R 2 , R3=R 3, and so on. As described herein, in each of the linkers (L1-L5), the wavy line represents the attachment (bond) between the corresponding linking group and the rest of the olefin / silane interpolymer.

[0098] The terms "comprising," "including," "having," and derivatives thereof are not intended to exclude the presence of any additional components, steps, or procedures, whether or not the components, steps, or procedures are specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of excludes from the scope of any subsequently recited component, step, or procedure, except those that are not essential to operability. The term "consisting of excludes any component, step, or procedure not specifically recited or listed.

[0099] As used herein, with respect to a polymer (or interpolymer or terpolymer or copolymer), the phrase "major weight percent" refers to the amount of monomer present in the largest amount in the polymer.

[0100] List of some method and composition features

[0101] A] A method of forming a crosslinked composition, the method comprising heat treating a composition comprising:

[0102] a) olefin / silane interpolymer,

[0103] b) a curing catalyst, and

[0104] c) Polyvinyl compounds.

[0105] B] The process according to A] above, wherein the olefin / silane interpolymer of (component a) is an ethylene / α-olefin / silane interpolymer, and further an ethylene / α-olefin / silane terpolymer.

[0106] C] A process according to B] above, wherein the α-olefin of the ethylene / α-olefin / silane interpolymer is a C3-C20 α-olefin, and additionally a C3-C10 α-olefin, and additionally propylene, 1-butene, 1-hexene, 1-octene and 1-decene, and additionally propylene, 1-butene, 1-hexene or 1-octene, and additionally propylene, 1-butene or 1-octene, and additionally 1-butene or 1-octene, and additionally 1-octene.

[0107] D] A method according to any one of A]-C] (A] to C] above, wherein the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of: H 2 C=CH-R 1 -Si(R)(R')-H, where R 1 is an alkylene group, and R and R' are each independently an alkyl group, and R and R' may be the same or different.

[0108] E] A process according to any one of A] to D] above, wherein the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of: Where R 2 It is an alkylene group.

[0109] F] A process according to any one of A] to E] above, wherein the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of:

[0110]

[0111] G] The method according to any one of A] to F] above, wherein the curing catalyst (component b) comprises platinum (Pt) and further comprises platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

[0112] H] A method according to any one of A] to G] above, wherein the polyvinyl compound of component c is selected from the following i) to iv):

[0113] i) Wherein R3 is selected from alkylene or arylene;

[0114] ii) a polydiene comprising at least one of the following structures: (CR1R2-CR3=CR4-CR5R6) n -(CR7R8-CR9(CR10=CR11R12)) m -, wherein each of R1 to R12 is independently hydrogen (H) or alkyl, and n≥1 and m≥1, and further each of R1 to R12 is hydrogen, and further n is 1 to 50, or 1 to 40, or 1 to 30, or 1 to 20, and m is 1 to 50, or 1 to 40, or 1 to 30, or 1 to 20;

[0115] iii) H 3 C-CH 2 -C[R4-OC(O)-CH=CH 2 ] 3 , wherein R4 is an alkylene group or an arylene group; or

[0116] iv) has the following structure – [Si(CH=CH2 )(R5)-O] n - a cyclic siloxane wherein R5 is an alkyl group and n is 3 to 6.

[0117] I] The method according to any one of A] to H] above, wherein the vinyl compound of component c is selected from the following: dodecadiene, divinylbenzene, tetravinyltetramethylcyclo-tetrasiloxane (ViD4), trimethylolpropane triacrylate (TMPTA), or polybutadiene, wherein the polybutadiene contains ≥80 mol%, ≥85 mol% or ≥90 mol% of 1,2 vinyl groups based on the total vinyl content and has a melt viscosity of 30 cP to 500 cP, or 30 cP to 400 cP, or 30 cP to 300 cP, or 30 cP to 200 cP, or 30 cP to 150 cP, or 30 cP to 100 cP at 45°C.

[0118] J] The method according to any one of A] to I] above, wherein the composition further comprises component d: a curing inhibitor.

[0119] K] The method according to J] above, wherein the curing inhibitor of component d is selected from the following:

[0120] If ViD4 is not used as component c.

[0121] L] The method according to J] or K] above, wherein the curing inhibitor of component d is

[0122]

[0123] M] The method according to any one of J] to L] above, wherein the curing inhibitor of component d is added in an amount required to increase the temperature at which the onset of crosslinking occurs (as measured by DMA (see Experimental Section below)) by ≥20°C, or ≥30°C, or ≥40°C, or ≥50°C, compared to the same composition without component d. Note that, as used herein, the temperature at the onset of crosslinking is the temperature (T) at which the complex viscosity value or the shear storage modulus value increases by >10% relative to the corresponding value at "T-10°C".

[0124] N] The method according to any one of A] to M] above, wherein the composition further comprises a component e selected from the following:

[0125] or a combination thereof.

[0126] O] A method according to N] above, wherein component e is added in an amount required to reduce the temperature at which the onset of crosslinking occurs (as measured by DMA (see below)) by ≤10°C, or ≤15°C, or ≤20°C compared to the same composition without component e.

[0127] P] According to any one of A]-O] above, the composition further comprises a filler, and the further filler is present in an amount of 1.0 wt%, or 2.0 wt%, or 5.0 wt% to 10 wt%, or 15 wt%, or 20 wt%, wherein each weight percentage is based on the weight of the composition.

[0128] Q] A method according to any one of A] to P] above, wherein the composition is heat treated at a temperature of ≥40°C, or ≥45°C, or ≥50°C, or ≥55°C, or ≥60°C, or ≥65°C, or ≥70°C.

[0129] R] A method according to any one of A] to Q] above, wherein the composition is heat treated at a temperature of ≤ 200°C, or ≤ 180°C, or ≤ 160°C, or ≤ 140°C, or ≤ 120°C, or ≤ 100°C.

[0130] S] The method according to any one of A] to R] above, further comprising, before heat treating the composition comprising components ac, adding component c to component a before or simultaneously with adding component b to component a.

[0131] T] The method according to S] above, further comprising adding component c to component a before adding component b to component a.

[0132] U] The method according to S] above, further comprising adding component c to component a before or simultaneously with adding component b to component a.

[0133] V] The method according to any one of A] to U] above, wherein component b is present in an amount of 5 ppm to 200 ppm, or 10 ppm to 100 ppm, based on the weight of the composition.

[0134] W] The method according to any one of A] to V] above, wherein the weight ratio of the curing catalyst (component b) to the polyvinyl compound (component c) is ≥ 0.0005, or ≥ 0.0050 or ≥ 0.0100.

[0135] X] The method according to any one of A] to W] above, wherein the weight ratio of the curing catalyst (component b) to the polyvinyl compound (component c) is ≤10, or ≤8.0 or ≤6.0.

[0136] Y] The method according to any one of A] to X] above, wherein the composition comprises ≥50.0 wt.%, or ≥55.0 wt.%, or ≥60.0 wt.%, or ≥65.0 wt.%, or ≥70.0 wt.%, or ≥75.0 wt.%, or ≥80.0 wt.%, or ≥85.0 wt.%, or ≥90.0 wt.% of component a, based on the weight of the composition.

[0137] Z] The method according to any one of A] to Y] above, wherein the composition comprises ≤99.9 wt%, or ≤99.5 wt%, or ≤99.0 wt%, or ≤98.5 wt% or ≤98.0 wt% of component a, based on the weight of the composition.

[0138] A2] A method according to A]-Z] above, wherein the composition has a weight ratio of component a to component c of ≥2.00, or ≥2.50, or ≥3.00, or ≥3.50, or ≥4.00.

[0139] B2] A method according to any one of A] to A2] above, wherein the composition has a weight ratio of component a to component c of ≤100, or ≤95, or ≤90, or ≤85, or ≤80.

[0140] C2] The method according to any one of A] to B2] above, wherein the composition comprises ≥0.20 wt%, or ≥0.30 wt%, or ≥0.40 wt%, or ≥0.50 wt%, or ≥0.60 wt%, or ≥0.70 wt%, or ≥0.80 wt%, or ≥0.90 wt%, or ≥1.00 wt% of component c, based on the weight of the composition.

[0141] D2] The method according to any one of A] to C2] above, wherein the composition comprises ≤50.0 wt%, or ≤40.0 wt%, or ≤30.0 wt%, or ≤20.0 wt%, or ≤10.0 wt%, or ≤5.0 wt% of component c, based on the weight of the composition.

[0142] E2] The method according to any one of A] to D2] above, wherein the composition comprises ≥0 wt%, or ≥0.005 wt%, or ≥0.01 wt%, or ≥0.02 wt%, or ≥0.04 wt%, or ≥0.06 wt%, or ≥0.08 wt% of component d, based on the weight of the composition.

[0143] F2] The method according to any one of A] to E2] above, wherein the composition comprises ≤20.0 wt%, or ≤15.0 wt%, or ≤10.0 wt%, or ≤5.0 wt%, or ≤2.0 wt%, or ≤1.0 wt%, or ≤0.80 wt%, or ≤0.60 wt%, or ≤0.40 wt%, or ≤0.20 wt% or ≤0.10 wt% of component d, based on the weight of the composition.

[0144] G2] A method according to any one of A] to F2] above, wherein the composition further comprises a solvent (a substance that dissolves at least components a to c (usually a liquid under ambient conditions)).

[0145] H2] The method according to any one of A] to G2] above, wherein the composition comprises ≤1.0 wt%, or ≤0.5 wt%, or ≤0.05 wt%, or ≤0.01 wt% of solvent based on the weight of the composition.

[0146] I2] The method according to any one of A] to F2] above, wherein the composition does not contain a solvent.

[0147] J2] The method according to any one of A] to I2] above, wherein the copolymer of component a comprises ≥ 0.20 wt%, or ≥ 0.40 wt%, or ≥ 0.60 wt%, or ≥ 0.80 wt%, or ≥ 1.00 wt%, or ≥ 1.20 wt% of silane (monomer) in polymerized form, based on the weight of the copolymer.

[0148] K2] The method according to any one of A] to J2] above, wherein the copolymer of component a comprises, in polymerized form, ≤10 wt%, or ≤5.0 wt%, or ≤4.0 wt%, or ≤3.8 wt%, or ≤3.6 wt%, or ≤3.4 wt%, or ≤3.2 wt%, or ≤3.0 wt% of silane (monomer), based on the weight of the copolymer.

[0149] L2] A method according to any one of A] to K2] above, wherein the copolymer of component a comprises ≥20 wt%, or ≥22 wt%, or ≥24 wt%, or ≥26 wt%, or ≥28 wt%, or ≥30 wt% of α-olefin in polymerized form, based on the weight of the copolymer.

[0150] M2] A method according to any one of A] to L2] above, wherein the copolymer of component a comprises, in polymerized form, ≤60 wt%, or ≤58 wt%, or ≤56 wt%, or ≤54 wt%, or ≤52 wt%, or ≤50 wt% of α-olefin, based on the weight of the copolymer.

[0151] N2] A process according to any one of A] to M2] above, wherein the interpolymer of component a has a molecular weight distribution (MWD = Mw / Mn) of ≥ 1.6, or ≥ 1.8, or ≥ 1.9, or ≥ 2.0.

[0152] O2] A process according to any one of A] to N2] above, wherein the interpolymer of component a has a molecular weight distribution MWD of ≤3.0, or ≤2.9, or ≤2.8, or ≤2.7, or ≤2.6.

[0153] P2] The method according to any one of A] to O2] above, wherein the copolymer of component a has a number average molecular weight (Mn) of ≥10,000 g / mol, or ≥12,000 g / mol, or ≥14,000 g / mol, or ≥16,000 g / mol.

[0154] Q2] The method according to any one of A] to P2] above, wherein the copolymer of component a has a number average molecular weight (Mn) of ≤100,000 g / mol, or ≤95,000 g / mol, or ≤90,000 g / mol, or ≤85,000 g / mol, or ≤80,000 g / mol, or ≤75,000 g / mol, or ≤70,000 g / mol.

[0155] R2] The method according to any one of A] to Q2] above, wherein the copolymer of component a has a weight average molecular weight (Mw) of ≥30,000 g / mol, or ≥35,000 g / mol, or ≥40,000 g / mol, or ≥45,000 g / mol, or ≥50,000 g / mol, or ≥55,000 g / mol, or ≥60,000 g / mol.

[0156] S2] According to the method described in any one of A] to R2] above, the copolymer of component a has a weight average molecular weight (Mw) of ≤200,000 g / mol, or ≤190,000 g / mol, or ≤180,000 g / mol, or ≤170,000 g / mol, or ≤160,000 g / mol, or ≤155,000 g / mol.

[0157] T2] The method according to any one of A] to S2] above, wherein the melting temperature Tm of the copolymer of component a is ≥40°C, or ≥45°C, or ≥50°C, or ≥55°C, or ≥60°C.

[0158] U2] The method according to any one of A] to T2] above, wherein the melting temperature Tm of the interpolymer of component a is ≤ 120°C, or ≤ 115°C, or ≤ 110°C, or ≤ 105°C, or ≤ 100°C.

[0159] V2] A process according to any one of A] to U2] above, wherein the interpolymer of component a has a % crystallinity of ≥1.8%, or ≥2.0%, or ≥2.1%, or ≥2.2%, or ≥2.3%, or ≥2.4%.

[0160] W2] A process according to any one of A] to V2] above, wherein the interpolymer of component a has a % crystallinity of ≤22%, ≤20%, or ≤18%, ≤16%, or ≤14%, or ≤13%, or ≤12%.

[0161] X2] A cross-linked composition formed by the method described in any one of A] to W2] above.

[0162] Y2] A crosslinked composition according to X2] above, wherein the crosslinked composition comprises a crosslinked olefin / silane interpolymer, the crosslinked olefin / silane interpolymer comprising a linking group selected from the following L1 to L5 as a crosslink between interpolymer molecules:

[0163] L1), wherein each R1 is an alkylene group, R3 is an alkylene group or an arylene group, and R and R' are each independently an alkyl group, and R and R' may be the same or different;

[0164] L2), where

[0165] Each R1 is an alkylene group, R and R' are each independently an alkyl group, and R and R' may be the same or different, and n is 0 to 20;

[0166]

[0167] L3), wherein each R1 is an alkylene group, R4 is an alkylene group or an arylene group, and R and R' are each independently an alkyl group, and R and R' may be the same or different;

[0168] L4), wherein each R1 is an alkylene group, R4 is an alkylene group or an arylene group, and R and R' are each independently an alkyl group, and R and R' may be the same or different;

[0169] L5), wherein each R1 is an alkylene group, R and R' are each independently an alkyl group, and R and R' may be the same or different.

[0170] Z2] A crosslinked composition according to Y2] above, wherein the crosslinked olefin / silane interpolymer comprises a linking group selected from L1 as the crosslink between interpolymer molecules.

[0171] A3] The cross-linked composition according to Z2] above, wherein "-CH 2-CH 2 -R3-CH 2 -CH 2 The "-" portion is derived from dodecadiene or divinylbenzene.

[0172] B3] A crosslinked composition according to Y2] above, wherein the crosslinked olefin / silane interpolymer comprises a linking group selected from L2 as the crosslink between interpolymer molecules.

[0173] C3] The cross-linked composition according to B3] above, wherein "-CH 2 -CH 2 -CH(CH 3 )-[CH 2 CH(CH=CH 2 )] n -CH 2 -CH 2 The "-" portion is derived from a polybutadiene comprising ≥80 mol%, ≥85 mol%, or ≥90 mol% of 1,2 vinyl groups based on the total vinyl content and having a melt viscosity at 45°C of 30 cP to 500 cP, or 30 cP to 400 cP, or 30 cP to 300 cP, or 30 cP to 200 cP, or 30 cP to 150 cP, or 30 cP to 100 cP.

[0174] D3] A crosslinked composition according to Y2] above, wherein the crosslinked olefin / silane interpolymer comprises a linking group selected from L3 or L4 as the crosslink between interpolymer molecules.

[0175] E3] The cross-linking composition according to D3] above, wherein for the linking group L3, "-CH 2 -CH 2 -C(O)-OR 4 -C(CH 2 -CH 3 )[R 4 -OC(O)-CH=CH 2 ]-R 4 -OC(O)-CH 2 -CH 2 The "-" portion is derived from trimethylolpropane triacrylate (TMPTA).

[0176] F3] The cross-linking composition according to D3] above, wherein for the linking group L4, the trivalent "containing -R4-C(CH 2 -CH 3 The )(R4-)(R4-)" portion is derived from trimethylolpropane triacrylate (TMPTA).

[0177] G3] A crosslinked composition according to Y2] above, wherein the crosslinked olefin / silane interpolymer comprises a linking group selected from L5 as the crosslink between interpolymer molecules.

[0178] H3] A composition comprising the following components:

[0179] a) olefin / silane interpolymer,

[0180] b) a curing catalyst, and

[0181] c) Polyvinyl compounds.

[0182] I3] A composition according to H3] above, wherein the olefin / silane interpolymer of component a is an ethylene / α-olefin / silane interpolymer, and further is an ethylene / α-olefin / silane terpolymer.

[0183] J3] A composition according to I3] above, wherein the α-olefin of the ethylene / α-olefin / silane interpolymer is a C3-C20 α-olefin, and is additionally a C3-C10 α-olefin, and is additionally propylene, 1-butene, 1-hexene, 1-octene and 1-decene, and is additionally propylene, 1-butene, 1-hexene or 1-octene, and is additionally propylene, 1-butene or 1-octene, and is additionally 1-butene or 1-octene, and is additionally 1-octene.

[0184] K3] A composition according to any one of H3] to J3] above, wherein the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of: 2 C=CH-R 1 -Si(R)(R')-H, wherein R1 is an alkylene group, and R and R' are each independently an alkyl group, and R and R' may be the same or different.

[0185] L3] A composition according to any one of H3] to K3] above, wherein the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of: Where R 2 It is an alkylene group.

[0186] M3] A composition according to any one of H3] to L3] above, wherein the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of:

[0187]

[0188] N3] A composition according to any one of H3] to M3] above, wherein the curing catalyst (component b) comprises platinum (Pt) and further comprises platinum (0)-1,3-divinyl-1,1,3,3-tetramethyl-disiloxane.

[0189] O3] A composition according to any one of the above H3]-N3], wherein the polyvinyl compound of component c is selected from the following i)-iv):

[0190] i) Wherein R3 is selected from alkylene or arylene;

[0191] ii) a polydiene comprising at least one of the following structures: (CR1R2-CR3=CR4-

[0192] CR5R6)n-(CR7R8-CR9(CR10=CR11R12))m-, wherein each of R1 to R12 is independently hydrogen (H) or alkyl, and n≥1 and m≥1, and further each of R1 to R12 is hydrogen, and further n is 1 to 50, or 1 to 40, or 1 to 30, or 1 to 20, and m is 1 to 50, or 1 to 40, or 1 to 30, or 1 to 20;

[0193] iii) H3C-CH2-C[R4-OC(O)-CH=CH3]3, wherein R4 is an alkylene group or an arylene group; or

[0194] iv) has the following structure – [Si(CH=CH 2 )(R5)-O] n - a cyclic siloxane wherein R5 is an alkyl group and n is 3 to 6.

[0195] P3] A composition according to any one of H3] to O3] above, wherein the polyvinyl compound of component c is selected from the following: dodecadiene, divinylbenzene, tetravinyltetra-methylcyclotetrasiloxane (ViD4), trimethylolpropane triacrylate (TMPTA), or polybutadiene, wherein the polybutadiene contains ≥80 mol%, ≥85 mol% or ≥90 mol% of 1,2 vinyl groups based on the total vinyl content, and has a melt viscosity of 30 cP to 500 cP, or 30 cP to 400 cP, or 30 cP to 300 cP, or 30 cP to 200 cP, or 30 cP to 150 cP, or 30 cP to 100 cP at 45°C.

[0196] Q3] The composition according to any one of H3] to P3] above, wherein the composition further comprises component d: a curing inhibitor.

[0197] R3] A composition according to Q3] above, wherein the curing inhibitor of component d is selected from the following:

[0198]

[0199] If ViD4 is not used as component c.

[0200] S3] A composition according to Q3] or R3] above, wherein the curing inhibitor of component d is IRGAFOS 168.

[0201] T3] A composition according to any one of Q3] to S3] above, wherein the curing inhibitor of component d is added in an amount required to increase the temperature at which crosslinking begins to occur (as measured by DMA (see the experimental part below)) by ≥20°C, or ≥30°C, or ≥40°C, or ≥50°C, compared to the same composition without component d.

[0202] U3] A composition according to any one of H3] to T3] above, wherein the composition further comprises a component e selected from the following: IRGANOX 1010, IRGANOX 1076 or a combination thereof.

[0203] V3] A composition according to U3] above, wherein component e is added in an amount required to reduce the temperature at which crosslinking begins (as measured by DMA (see below)) by ≤10°C, or ≤15°C, or ≤20°C compared to the same composition without component e.

[0204] W3] A composition according to any one of H3] to V3] above, wherein the composition also contains a filler, and the filler is further present in an amount of 1.0 wt%, or 2.0 wt%, or 5.0 wt% to 10 wt%, or 15 wt%, or 20 wt%, wherein each weight percentage is based on the weight of the composition.

[0205] X3] A composition according to any one of H3] to W3] above, wherein the composition is heat treated at a temperature of ≥40°C, or ≥45°C, or ≥50°C, or ≥55°C, or ≥60°C, or ≥65°C, or ≥70°C.

[0206] Y3] A composition according to any one of H3] to X3] above, wherein the composition is heat treated at a temperature of ≤200°C, or ≤180°C, or ≤160°C, or ≤140°C, or ≤120°C, or ≤100°C.

[0207] Z3] A composition according to any one of H3] to Y3] above, further comprising adding component c to component a before or simultaneously with adding component b to component a before heat treating the composition comprising components ac.

[0208] A4] The composition according to Z3] above, further comprising adding component c to component a before adding component b to component a.

[0209] B4] The composition according to Z3] above, further comprising adding component c to component a before or simultaneously with adding component b to component a.

[0210] C4] A composition according to any one of H3] to B4] above, wherein component b is present in an amount of 5 ppm to 200 ppm, or 10 ppm to 100 ppm, based on the weight of the composition.

[0211] D4] A composition according to any one of H3] to C4] above, wherein the weight ratio of the curing catalyst (component b) to the vinyl compound (component c) is ≥ 0.0005, or ≥ 0.0050 or ≥ 0.0100.

[0212] E4] The composition according to any one of H3] to D4] above, wherein the weight ratio of the curing catalyst (component b) to the vinyl compound (component c) is ≤10, or ≤8.0 or ≤6.0.

[0213] F4] A composition according to any one of H3] to E4] above, wherein based on the weight of the composition, the composition comprises ≥50.0 wt.%, or ≥55.0 wt.%, or ≥60.0 wt.%, or ≥65.0 wt.%, or ≥70.0 wt.%, or ≥75.0 wt.%, or ≥80.0 wt.%, or ≥85.0 wt.%, or ≥90.0 wt.% of component a.

[0214] G4] A composition according to any one of H3] to F4] above, wherein the composition comprises ≤99.9 wt%, or ≤99.5 wt%, or ≤99.0 wt%, or ≤98.5 wt%, or ≤98.0 wt% of component a based on the weight of the composition.

[0215] H4] A composition according to H3] to G4] above, wherein the composition has a weight ratio of component a to component c of ≥2.00, or ≥2.50, or ≥3.00, or ≥3.50, or ≥4.00.

[0216] I4] A composition according to any one of H3] to H4] above, wherein the composition has a weight ratio of component a to component c of ≤100, or ≤95, or ≤90, or ≤85, or ≤80.

[0217] J4] A composition according to any one of H3] to I4] above, wherein based on the weight of the composition, the composition comprises ≥0.20 wt%, or ≥0.30 wt%, or ≥0.40 wt%, or ≥0.50 wt%, or ≥0.60 wt%, or ≥0.70 wt%, or ≥0.80 wt%, or ≥0.90 wt%, or ≥1.00 wt% of component c.

[0218] K4] A composition according to any one of H3] to J4] above, wherein the composition comprises ≤50.0 wt%, or ≤40.0 wt%, or ≤30.0 wt%, or ≤20.0 wt%, or ≤10.0 wt%, or ≤5.0 wt% of component c, based on the weight of the composition.

[0219] L4] A composition according to any one of H3] to K4] above, wherein the composition comprises ≥0 wt%, or ≥0.005 wt%, or ≥0.01 wt%, or ≥0.02 wt%, or ≥0.04 wt%, or ≥0.06 wt%, or ≥0.08 wt% of component d, based on the weight of the composition.

[0220] M4] A composition according to any one of H3] to L4] above, wherein based on the weight of the composition, the composition contains ≤20.0 wt%, or ≤15.0 wt%, or ≤10.0 wt%, or ≤5.0 wt%, or ≤2.0 wt%, or ≤1.0 wt%, or ≤0.80 wt%, or ≤0.60 wt%, or ≤0.40 wt%, or ≤0.20 wt% or ≤0.10 wt% of component d.

[0221] N4] A composition according to any one of H3] to M4] above, wherein the composition further comprises a solvent.

[0222] O4] A composition according to any one of H3] to N4] above, wherein the composition comprises ≤1.0 wt%, or ≤0.5 wt%, or ≤0.05 wt%, or ≤0.01 wt% of solvent based on the weight of the composition.

[0223] P4] A composition according to any one of H3] to M4] above, wherein the composition does not contain a solvent.

[0224] Q4] A composition according to any one of H3] to P4] above, wherein the copolymer of component a comprises ≥0.20 wt%, or ≥0.40 wt%, or ≥0.60 wt%, or ≥0.80 wt%, or ≥1.00 wt%, or ≥1.20 wt% of silane (monomer) in polymerized form, based on the weight of the copolymer.

[0225] R4] A composition according to any one of H3] to Q4] above, wherein the copolymer of component a comprises, in polymerized form, ≤10 wt%, or ≤5.0 wt%, or ≤4.0 wt%, or ≤3.8 wt%, or ≤3.6 wt%, or ≤3.4 wt%, or ≤3.2 wt%, or ≤3.0 wt% of silane (monomer), based on the weight of the copolymer.

[0226] S4] A composition according to any one of H3] to R4] above, wherein the copolymer of component a comprises ≥20 wt%, or ≥22 wt%, or ≥24 wt%, or ≥26 wt%, or ≥28 wt%, or ≥30 wt% of α-olefin in polymerized form, based on the weight of the copolymer.

[0227] T4] A composition according to any one of H3] to S4] above, wherein the copolymer of component a comprises ≤60 wt%, or ≤58 wt%, or ≤56 wt%, or ≤54 wt%, or ≤52 wt%, or ≤50 wt% of α-olefin in polymerized form, based on the weight of the copolymer.

[0228] U4] A composition according to any one of H3] to T4] above, wherein the interpolymer of component a has a molecular weight distribution (MWD = Mw / Mn) of ≥ 1.6, or ≥ 1.8, or ≥ 1.9, or ≥ 2.0.

[0229] V4] A composition according to any one of H3] to U4] above, wherein the interpolymer of component a has a molecular weight distribution MWD of ≤3.0, or ≤2.9, or ≤2.8, or ≤2.7, or ≤2.6.

[0230] W4] A composition according to any one of H3] to V4] above, wherein the copolymer of component a has a number average molecular weight (Mn) of ≥10,000 g / mol, or ≥12,000 g / mol, or ≥14,000 g / mol, or ≥16,000 g / mol.

[0231] X4] A composition according to any one of H3] to W4] above, wherein the copolymer of component a has a number average molecular weight (Mn) of ≤100,000 g / mol, or ≤95,000 g / mol, or ≤90,000 g / mol, or ≤85,000 g / mol, or ≤80,000 g / mol, or ≤75,000 g / mol, or ≤70,000 g / mol.

[0232] Y4] A composition according to any one of H3] to X4] above, wherein the copolymer of component a has a weight average molecular weight (Mw) of ≥30,000 g / mol, or ≥35,000 g / mol, or ≥40,000 g / mol, or ≥45,000 g / mol, or ≥50,000 g / mol, or ≥55,000 g / mol, or ≥60,000 g / mol.

[0233] Z4] A composition according to any one of H3] to Y4] above, wherein the copolymer of component a has a weight average molecular weight (Mw) of ≤200,000 g / mol, or ≤190,000 g / mol, or ≤180,000 g / mol, or ≤170,000 g / mol, or ≤160,000 g / mol, or ≤155,000 g / mol.

[0234] A5] The composition according to any one of items H3] to Z4] above, wherein the melting temperature Tm of the copolymer of component a is ≥40°C, or ≥45°C, or ≥50°C, or ≥55°C, or ≥60°C.

[0235] B5] A composition according to any one of H3] to A5] above, wherein the melting temperature Tm of the interpolymer of component a is ≤ 120°C, or ≤ 115°C, or ≤ 110°C, or ≤ 105°C, or ≤ 100°C.

[0236] C5] A composition according to any one of H3] to B5] above, wherein the interpolymer of component a has a % crystallinity of ≥1.8%, or ≥2.0%, or ≥2.1%, or ≥2.2%, or ≥2.3%, or ≥2.4%.

[0237] D5] A composition according to any one of H3] to C5] above, wherein the interpolymer of component a has a crystallinity % of ≤22%, ≤20%, or ≤18%, ≤16%, or ≤14%, or ≤13%, or ≤12%.

[0238] E5] A cross-linked composition, which is formed from the composition according to any one of H3] to D5] above.

[0239] F5] A crosslinked composition according to E5] above, wherein the crosslinked composition comprises a crosslinked olefin / silane interpolymer comprising linking groups selected from L1 to L5, each as described above, as crosslinks between interpolymer molecules:

[0240] G5] A crosslinked composition according to F5] above, wherein the crosslinked olefin / silane interpolymer comprises a linking group selected from L1 as described above as the crosslink between the interpolymer molecules.

[0241] H5] The cross-linked composition according to G5] above, wherein "-CH 2 -CH 2 -R3-CH 2 -CH 2 The "-" portion is derived from dodecadiene or divinylbenzene.

[0242] I5] A crosslinked composition according to F5] above, wherein the crosslinked olefin / silane interpolymer comprises a linking group selected from L2 as described above as the crosslink between the interpolymer molecules.

[0243] J5] According to the cross-linked composition described in I5] above, wherein "-CH 2 -CH 2 -CH(CH 3 )-[CH 2 CH(CH=CH 2 )] n -CH 2 -CH 2 The "-" portion is derived from a polybutadiene comprising ≥80 mol%, ≥85 mol%, or ≥90 mol% of 1,2 vinyl groups based on the total vinyl content and having a melt viscosity at 45°C of 30 cP to 500 cP, or 30 cP to 400 cP, or 30 cP to 300 cP, or 30 cP to 200 cP, or 30 cP to 150 cP, or 30 cP to 100 cP.

[0244] K5] A crosslinked composition according to F5] above, wherein the cured olefin / silane interpolymer comprises a linking group selected from L3 or L4 as described above, each as a crosslink between interpolymer molecules.

[0245] L5] The cross-linking composition according to K5] above, wherein for the linking group L3, "-CH 2 -CH 2 -C(O)-OR 4 -C(CH 2 -CH 3 )[R 4 -OC(O)-CH=CH 2 ]-R 4 -OC(O)-CH 2 -CH 2 The "-" portion is derived from trimethylolpropane triacrylate (TMPTA).

[0246] M5] The cross-linking composition according to K5] above, wherein for the linking group L4, the trivalent "containing -R4-C(CH 2 -CH 3 The )(R4-)(R4-)" portion is derived from trimethylolpropane triacrylate (TMPTA).

[0247] N5] A crosslinked composition according to F5] above, wherein the cured olefin / silane interpolymer comprises a linking group selected from L5 as described above as crosslinks between interpolymer molecules.

[0248] O5] An article comprising at least one component formed from the composition described in any one of X2] to N5] above.

[0249] P5] The article according to O5], wherein the article is an automobile part, a building material or a computer part.

[0250] Test Method

[0251] 1H NMR Characterization of Interpolymers

[0252] For 1H NMR experiments, each polymer sample was dissolved in tetrachloroethane-d2 (with or without 0.001 M Cr(acac)) in an 8 mm NMR tube. 3 ). The concentration was about 100 mg / 1.8 mL. The tube was then heated in a heating block set at 110°C. The sample tube was repeatedly vortexed and heated to obtain a uniformly flowing fluid. 1H NMR spectra were acquired on a BRUKER AVANCE 600MHz spectrometer equipped with a 10mm C / H DUAL cryoprobe. Standard single-pulse 1H NMR experiments were performed. The following acquisition parameters were used: 70 second relaxation delay, 90 degree pulse of 17.2 μs, 32 scans. The spectrum was centered at "1.3 ppm" and the spectrum width was 20 ppm. All measurements were performed at 110°C without sample rotation. The resonance peak of the solvent (residual protonated tetrachloroethane) in the 1H NMR spectrum was located at "5.99 ppm". For each sample with Cr, data was acquired with a 16 second relaxation delay and 128 scans. 1H NMR is used to determine the polymerized silane monomer content (wt%) in olefin / silane interpolymers, such as wt% ODMS. The "weight % silane monomer" is calculated based on the integration of the SiMe proton resonance relative to the integration of the CH2 protons associated with the ethylene unit and the CH3 protons associated with the octene unit. The "weight % octene (or other α-olefin)" can be similarly determined by reference to the CH3 protons associated with the octene unit (or other α-olefin).

[0253] 13C NMR Characterization of Interpolymers

[0254] For 13C NMR experiments, each polymer sample was dissolved in tetrachloroethane-d2 (with or without 0.025 M Cr(acac)) in a 10 mm NMR tube. 3). The concentration was about 300 mg / 2.8 mL. The tube was then heated in a heating block set at 110° C. The sample tube was repeatedly vortexed and heated to obtain a uniformly flowing fluid. 13C NMR spectra were acquired on a BRUKER AVANCE 600MHz spectrometer equipped with a 10mm C / H DUAL cryoprobe. The following acquisition parameters were used: 60 seconds relaxation delay, 90 degree pulse of 12.0 μs, and 256 scans. The spectrum was centered at "100 ppm" and the spectrum width was 250 ppm. All measurements were performed at 110° C without sample rotation. The resonance peak of the solvent in the 13C NMR spectrum is located at "74.5 ppm". For samples with Cr, data was acquired with a 7 second relaxation delay and 1024 scans. "Weight % silane monomer" was calculated based on the integral of the SiMe carbon resonance relative to the integral of the CH2 carbon associated with the ethylene unit and the CH / CH3 carbon associated with the octene unit. "Weight % octene (or other α-olefin)" can be similarly determined by reference to the CH / CH3 carbons associated with the octene units (or other α-olefins).

[0255] Gel Permeation Chromatography

[0256] The chromatographic system consists of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven chamber is set to 160 degrees Celsius, and the column chamber is set to 150 degrees Celsius. The columns are four AGILENT "Mixed A" 30cm 20 micron linear mixed bed columns. The chromatographic solvent is 1,2,4-trichlorobenzene, which contains "200ppm" of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0257] The GPC column set was calibrated using 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 molecular weights and arranged in six "cocktail" mixtures with at least ten times the interval between individual molecular weights. The standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, "0.025 grams" of polystyrene standards were prepared in 50 milliliters of solvent, and for molecular weights less than 1,000,000, "0.05 grams" of polystyrene standards were prepared in 50 milliliters of solvent. The polystyrene standards were dissolved by gentle stirring at 80°C for 30 minutes. The peak molecular weight of the polystyrene standards was converted to polyethylene molecular weight (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)) using Equation 1. 聚乙烯 =A×(M 聚苯乙烯 ) B (Equation 1), where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0258] A fifth order polynomial was used to fit the calibration points to the corresponding polyethylene equivalents.A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band broadening effects such that a linear homopolymer polyethylene standard was obtained at 120,000 Mw.

[0259] Total plate counts for the GPC column set were performed using decane (prepared as 0.04 g in 50 mL TCB and dissolved for 20 minutes with slow stirring). Plate counts (Equation 2) and symmetry (Equation 3) were measured at 200 μL injection according to the following equations:

[0260] wherein RV is the retention volume in milliliters, peak width is in milliliters, peak maximum is the maximum height of the peak, and 1 / 2 height is 1 / 2 the height of the peak maximum; and

[0261] Where RV is the retention volume in milliliters, and the peak width is in milliliters, the peak maximum is the peak maximum position, the tenth height is 1 / 10 the height of the peak maximum, and wherein the post-peak refers to the peak tail at a later retention volume than the peak maximum, and wherein the pre-peak refers to the peak front at an earlier retention volume than the peak maximum. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22. The samples were prepared in a semi-automatic manner using the PolymerChar "Instrument Control" software, wherein the target weight of the sample was set to "2 mg / ml", and the solvent (containing 200 ppm BHT) was added to a vial covered with a septum that was previously bubbled with nitrogen by a PolymerChar high temperature autosampler. The samples were dissolved at 160°C for two hours under "slow" shaking.

[0262] Based on the GPC results, the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer was used, according to Equations 4-6, using the PolymerChar GPCOne TM The software, the baseline-subtracted IR chromatogram at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1 were used to determine Mn. (GPC) 、Mw (GPC) and Mz (GPC) Calculation of. Equation 4-6 is as follows:

[0263] and

[0264]

[0265] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (flow rate (nominal)) for each sample by comparing the RV of the corresponding decane peak in the sample (RV (FM sample)) with the RV of the decane peak in the narrow standard calibration (RV (FM calibrated)). It was then assumed that any changes in the time of the decane marker peak were related to linear changes in the flow rate (flow rate (effective)) for the entire run. In order to facilitate the highest accuracy of the RV measurement of the flow marker peak, the peak of the flow marker concentration chromatogram was fit to a quadratic equation using a least squares fitting procedure. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated using Equation 7: Flow rate (effective) = flow rate (nominal) * (RV (FM calibration) / RV (FM sample)) (Equation 7). By PolymerChar GPCOne TM The software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.7% of the nominal flow rate.

[0266] Melt Index

[0267] The melt index I2 of the ethylene-based polymer is measured according to ASTM D-1238 at 190°C / 2.16kg. The melt flow rate (MFR) of the propylene-based polymer is measured according to ASTM D-1238 at 230°C / 2.16kg.

[0268] density

[0269] ASTM D4703 was used to prepare polymer plaques for density analysis. ASTM D792, Method B was used to measure the density of each polymer.

[0270] Differential Scanning Calorimetry (DSC) – Polymers

[0271] Differential scanning calorimetry (DSC) is used to measure Tm, Tc, Tg and crystallinity in ethylene-based polymer samples. About 5 mg to 8 mg sample is weighed and placed in a DSC pan. The lid is screwed on the pan to ensure a closed atmosphere. Unless otherwise stated, the sample pan is placed in a DSC unit and then heated to a temperature of 200 ° C at a rate of 10 ° C / minute. The sample is kept at this temperature for three minutes. The sample is then cooled to -90 ° C at a rate of 10 ° C / minute, and isothermally maintained at this temperature for three minutes. The sample is then heated at a rate of 10 ° C / minute until fully melted (second heating). Unless otherwise stated, the melting point (Tm) and glass transition temperature (Tg) of each polymer are determined by the second heating curve. Record the peak heat flow temperature of Tm.

[0272] Dynamic Mechanical Analysis (DMA)

[0273] The mechanical properties of the molded discs as a function of temperature or time were characterized by dynamic mechanical analysis (DMA) using an ARES rheometer equipped with 25 mm parallel plates (disposable aluminum) and operated in oscillatory shear mode at a frequency of 1 rad / s and a strain amplitude of <0.1%. After loading the sample disc, a preload of 100 g force was used to ensure good contact with the plate. At the start of the run, the environment was cooled and stabilized at 25 ° C. Unless otherwise specified, the temperature was started and the sample was heated from 25 ° C to 200 ° C at a rate of 2 ° C / min using heated N2 gas while measuring the complex viscosity or shear storage modulus.

[0274] Soxhlet extraction

[0275] Each Soxhlet extraction was performed according to ASTM D2765-16.

[0276] Melt viscosity

[0277] The melt viscosity of low viscosity polybutadiene and other low viscosity polydienes can be measured at 45°C using a Brookfield viscometer and spindle LV-1.

[0278] experiment

[0279] Commercially available polymers and additives

[0280] Karstedt catalyst (platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution) containing 2 wt% Pt in xylene (Sigma Aldrich) hereinafter referred to as Karstedt catalyst.

[0281] Very low molecular weight polybutadiene (Sigma Aldrich, melt viscosity 30 cP-100 cP at 45° C.) contains 90 mol % of 1,2 vinyl content based on the total vinyl content in the polybutadiene, hereinafter referred to as “polybutadiene”.

[0282] Bis(2-ethylhexyl) maleate was purchased from Sigma Aldrich.

[0283] 1-Ethynyl-1-cyclohexanol, "ETCH", 99%, was purchased from Sigma Aldrich.

[0284] Surfynol-61 was purchased from Sigma Aldrich.

[0285] Tetravinyltetramethylcyclotetrasiloxane (ViD4) was purchased from Sigma Aldrich.

[0286] polymerization

[0287] Ethylene / octene / silane copolymerizations were carried out in an autoclave batch reactor designed for ethylene homopolymerization and copolymerization. The reactor was equipped with electric heating bands and internal cooling coils containing cooling glycol. Both the reactor and the heating / cooling system were controlled and monitored by a process computer. The bottom of the reactor was equipped with a dump valve that emptied the reactor contents into a dump pan connected to the atmosphere.

[0288] All chemicals and catalyst solutions used for polymerization were passed through a purification column before use. ISOPAR-E, 1-octene, ethylene and silane monomers were also passed through the column. Ultra-high purity grades of nitrogen (Airgas) and hydrogen (Airgas) were used. The catalyst mixture was prepared by mixing the scavenger (MMAO), activator (bis(hydrogenated tallow alkyl) methylamine tetra(pentafluorophenyl) borate (1<->)) and catalyst with an appropriate amount of toluene in an inert glove box to obtain a solution of the desired molar concentration. The solution was then diluted with ISOPAR-E or toluene to achieve the amount required for polymerization and drawn into a syringe for transfer to the catalyst injection tank.

[0289] In a typical polymerization, ISOPAR-E and 1-octene are loaded into the reactor via separate flow meters. The silane monomer is then added via an injection tank input through an adjacent glove box. After the solvent / comonomer addition, hydrogen is added (if necessary) while the reactor is heated to a polymerization set point of 120°C. Ethylene is then added to the reactor via a flow meter at the desired reaction temperature to maintain a predetermined reaction pressure set point. The catalyst solution is transferred to an injection tank via a syringe and then added to the reactor via a high pressure nitrogen stream after the reactor pressure set point is reached. The run timer is started upon injection of the catalyst, after which an exotherm and a decrease in reactor pressure are observed to indicate a successful run.

[0290] Ethylene is then added using a pressure controller to maintain the reaction pressure set point in the reactor. The polymerization reaction is set for a set time or ethylene absorption, after which the agitator is stopped and the bottom dump valve is opened to empty the reactor contents into a dump tank. The tank contents are poured into a tray placed in a fume hood, and the solvent is allowed to evaporate overnight. The tray containing the remaining polymer is then transferred to a vacuum oven and heated to 100 ° C under reduced pressure to remove any residual solvent. After cooling to ambient temperature, the polymer is weighed to obtain a yield / efficiency, transferred to a container for storage and submitted for analysis and testing. See Table 1A, Table 1B and Table 1C.

[0291] Table 1A: Polymerization conditions

[0292] Terpolymer catalyst Reactor pressure (psi) Reactor size (L) Reaction end point (min) 1 3 115.5 2 8.1 2 1 108.1 3.79 10 3 1 123.5 2 7.4 4 1 107.4 3.79 10 5 1 125.4 2 11.9 6 1 132.7 2 8.5

[0293] Table 1B: Polymerization conditions

[0294]

[0295]

[0296] Table 1C: Catalysts

[0297]

[0298] Study 1: DSC of solution-prepared Pt sulfidable formulations

[0299] Terpolymer 1 (3.0 wt% octenyldimethylsilane (ODMS, 1H NMR), 31.6 wt% octene (1H NMR), the remainder ethylene; dissolved in toluene at a loading of "0.80 g terpolymer / 15 g toluene" at 50°C. Terpolymer 1 has Mn=17,000 g / mol and Mw=41,000 g / mol, a peak melting temperature of 95.4°C, and an integrated melting enthalpy of 33.4 J / g (equivalent to 11.4% crystallinity, assuming a pure crystal melting enthalpy of 293 J / g, measured by differential scanning calorimetry (DSC) at a heating rate of 10°C / min). This solution is Solution A.

[0300] Prepare a separate solution B containing 10.0 g toluene and 0.20 g polybutadiene. Heat the solution to 50°C under shaking to dissolve the viscous liquid polymer in the solvent. Dilute the Karstedt catalyst to 0.01 wt % Pt (based on the total weight of the catalyst and toluene) by adding toluene. Add a small amount (0.20 g) of this diluted catalyst solution (containing 0.01 wt % Pt) to solution B.

[0301] Sealed glass vials of solutions A and B were heated to 60°C in a hot water bath, respectively, to obtain a clear, homogeneous fluid. Solutions A and B were combined and mixed by shaking to obtain a clear fluid containing 20 ppm Pt (based on the mass of the terpolymer and polybutadiene). The mixed solution was poured into a PTFE mold (10 cm x 10 cm x 0.5 cm), and the filled mold was dried overnight in a laboratory fume hood to evaporate the toluene. The soft, gel-like sheet of the formulated terpolymer was peeled off and scraped off from the mold and further dried in a laboratory fume hood for another 24 hours or more.

[0302] After drying for 48 hours, approximately 7 mg of the formulated terpolymer was loaded into a sealed DSC pan and scanned in a TA Instruments Q1000 DSC apparatus. The results are shown in Figure 2 Multiple consecutive scans were performed in which the sample was equilibrated at -50°C, heated from -50°C to 250°C at 10°C / min, and then cooled from 250°C to -50°C at -10°C / min. In the first scan, the sample showed a broad multimodal melting endotherm extending from 38°C to 99°C, with the highest peak melting temperature at 92.6°C. The integrated melting enthalpy was 26.9 J / g (9.0% crystalline; 80% of the value measured for the pure terpolymer).

[0303] During the second scan, the sample exhibited a broad melting endotherm extending from 38°C to 101°C, but exhibited only one peak with a melting temperature of 82.0°C. The integrated melting enthalpy decreased to 16.55 J / g, corresponding to a crystallinity of only 5.65%. The significant decrease in peak melting temperature and integrated enthalpy after the first scan indicates that heating above the melting point during the first scan induced hydrosilylation-based crosslinks in the terpolymer. These crosslinks inhibited polymer chain mobility during the cooling period between the first and second scans, significantly limiting the ability of the chains to crystallize and resulting in the observed decrease in percent crystallinity and peak melting temperature.

[0304] Study 2: Shear Rheology of Solution-Prepared Pt Curable Formulations with Inhibitors

[0305] Terpolymer 1 was dissolved in toluene at 50°C at a loading of "1.0 g polymer / 15 g toluene". After the dissolution of the terpolymer was complete, 0.10 g of a 0.1 wt% solution of bis(2-ethylhexyl)maleate in toluene was added to the solution of the terpolymer in toluene. This solution was Solution A.

[0306] Prepare a separate solution B containing 5.0 g toluene and 0.020 g polybutadiene. Heat the solution to 50°C under shaking to dissolve the polybutadiene in the solvent. Dilute the Karstedt catalyst to 0.01 wt % Pt (based on the total weight of the catalyst and toluene) by adding toluene. Add a small amount (0.10 g) of this diluted catalyst solution (containing 0.01 wt % Pt) to solution B.

[0307] Sealed glass vials of solutions A and B were heated separately to 60° C. in a hot water bath to obtain a clear, homogeneous fluid. Solutions A and B were combined and mixed by shaking to obtain a clear fluid containing 10 ppm Pt (based on the total weight of the terpolymer and polybutadiene) and 100 ppm bis(2-ethylhexyl) maleate (based on the weight of the terpolymer). The mixed solution was poured into a PTFE mold (10 cm×10 cm×0.5 cm), and the filled mold was dried overnight in a laboratory fume hood to evaporate the toluene. The cloudy elastomeric film was peeled off the mold, turned over in the mold, and dried for another 24 hours in a laboratory fume hood.

[0308] The resulting film was cut into pieces and 0.70 g was placed in a flat plate mold (25 mm diameter × 2 mm deep) and sandwiched between steel plates with PTFE film liners. The assembly was placed between the platens of a Carver press, thermostatically controlled at 120°C. The assembly was first preheated for two minutes without pressure. It was then pressurized to 13800 kPa (2000 psig) and held under pressure for 30 seconds. The pressure was released and the assembly was cooled between water-cooled platens for two minutes. An opaque white disk with a flat, smooth top and bottom surface was recovered and a small amount of burrs around the outside were trimmed with scissors.

[0309] The mechanical properties of the molded discs were characterized by dynamic mechanical analysis (DMA) as a function of temperature. Figure 3 Shown is the response plotted as |η*| (Pa·s), the magnitude of the complex viscosity versus temperature (°C). Figure 3 The curve in shows four distinct regions. At low temperatures (0°C–70°C), the sample exhibits solid-like behavior, where the magnitude of the complex viscosity is high and decreases slowly with increasing temperature. At slightly higher temperatures (70°C–95°C), the viscosity decreases rapidly with increasing temperature as the terpolymer crystallites melt. At temperatures in the range of 95°C to about 140°C, the viscosity is low (liquid-like) and nearly constant with temperature. Finally, at higher temperatures (140°C-200°C), the viscosity increases significantly with increasing temperature, again reaching values ​​consistent with solid-like behavior and indicating crosslinking.

[0310] Comparative study 1: Shear rheology of formulations prepared from solutions without Pt and without polyvinyl compounds

[0311] DMA disks (25 mm diameter x 2 mm thick) were compression molded from terpolymer 2 containing 1.3 wt % octenyldimethylsilane (ODMS, 1H NMR, 13C NMR), 41.9 wt % octene (1H NMR, 13C NMR), the balance ethylene as described in Study 2. Terpolymer 2 had Mn = 43,000 g / mol and Mw = 91,000 g / mol, a peak melting point of 60.2°C and a percent crystallinity of 2.6% at a heating rate of 10°C / min by differential scanning calorimetry (DSC).

[0312] The mechanical properties of the molded discs were characterized by dynamic mechanical analysis (DMA) as a function of temperature. Figure 4 Shown is the response plotted as |η*| (Pa·s), the magnitude of the complex viscosity versus temperature (°C). Figure 4 The curve in shows that the viscosity gradually decreases with increasing temperature. There are no obvious regions of fairly constant viscosity or increasing viscosity in the thermal scan data. This indicates that in the absence of polyvinyl compounds and catalysts, the hydrosilylation responsible for crosslinking the polyolefin does not occur.

[0313] Study 3: Shear Rheology of Solution-Prepared Pt Curable Formulations

[0314] Terpolymer 2 was dissolved in toluene at 50°C at a loading of "2.0 g polymer / 20 g toluene". This solution was Solution A. Polybutadiene was dissolved in toluene at 50°C at a loading of "0.023 g polymer / 10 g toluene". A small amount (0.22 g) of diluted Karstedt catalyst (containing 0.01 wt% Pt) was added to the "polybutadiene solution" - Solution B.

[0315] Solutions A and B were combined to obtain a clear fluid containing a 99 / 1 weight ratio of terpolymer 2 / polybutadiene and 10 ppm Pt (based on the total weight of the terpolymer and polybutadiene). The mixed solution was poured into a PTFE mold (10 cm×10 cm×0.5 cm), and the filled mold was dried overnight in a laboratory fume hood. The cloudy elastomeric film was peeled off the mold, turned over in the mold, and dried for another 24 hours in a laboratory fume hood.

[0316] The resulting films were cut into sheets and compression molded (as described in Study 2) to yield "25 mm diameter x 2 mm thick" DMA disks. Figure 5 Shown is the response plotted as |η*| (Pa·s), the magnitude of the complex viscosity versus temperature (°C). Figure 5 The curve in shows three different regions. At low temperatures (0°C-70°C), the sample shows a stable, monotonically decreasing magnitude of complex viscosity with increasing temperature. At higher temperatures, the rate of viscosity decrease slows significantly, and the value is almost constant in the temperature range of 70°C-150°C. At higher temperatures (150°C-200°C), the viscosity increases significantly with increasing temperature, indicating that the crosslinking reaction based on hydrosilylation is ongoing.

[0317] Study 4: Shear Rheology of Melt-Prepared Pt Curable Formulations

[0318] Terpolymer 3 (15 g) containing 2.1 wt % octenyldimethylsilane (ODMS, 1H NMR), 47.9 wt % octene (1H NMR) and the balance ethylene was melted using a HAAKE melt blender set at 90°C at a blade speed of 60 rpm. Terpolymer 3 had Mn=53,000 g / mol and Mw=136,000 g / mol. Polybutadiene (2 wt %, based on the total weight of the terpolymer and polybutadiene) was then added to the melt blender as a polyvinyl compound. After three minutes of fluxing, 100 ppm Pt from Karstedt Catalyst (based on the total weight of the terpolymer and polybutadiene) was added to the mixer and fluxed for one minute until homogenized. DMA disks (25 mm diameter × 2 mm thick) were compression molded using a Carver press (20,000 lbs of force, 80°C, 1 minute) and immediately cooled between water-cooled press plates for two minutes. The resulting samples were then tested using a series of isothermal time sweeps (T = 120°C, 180°C, 200°C) using an ARES rheometer (25 mm disposable aluminum parallel plates, 1.0% strain amplitude, 1 rad / sec frequency, tested under N2 gas). The data from these tests are shown in Figure 6 These data demonstrate the ability to melt blend a silane terpolymer, a polyvinyl compound, and a Pt catalyst in a solvent-free process to form a vulcanizable formulation. The data also indicate that the vulcanization process follows Arrhenius-like kinetics as increased temperature results in faster shear storage modulus growth, which is directly related to the crosslink density. Samples tested at 120°C showed minimal crosslinking during the testing period. The higher temperature isotherms show significantly higher crosslinking over a shorter period of time. It was also found that the order of addition of the components (terpolymer, then polyvinyl compound, then Pt catalyst) is important for maintaining catalyst stability in the polymer melt. If the catalyst is added before the polyvinyl compound, there is visual instability of the Pt complex in the terpolymer formulation, as seen by irregular spots of various sizes within the DMA disk.

[0319] Study 5: Shear Rheology of Melt-Prepared Pt Curable Formulations Adjustable by Catalyst Addition

[0320] Terpolymer 3 (15 g) was melted at a blade speed of 60 rpm using a HAAKE melt blender set at 90°C. Polybutadiene (2 wt %, based on the total weight of the terpolymer and polybutadiene) was then added to the melt blender as a polyvinyl compound. After three minutes of fluxing, 10 ppm or 100 ppm of Pt (based on the total weight of the terpolymer and polybutadiene) from Karstedt catalyst (2 wt %, in xylene) was added to the mixer, and the resulting composition was fluxed for one minute until homogenized. A DMA disk (25 mm diameter × 2 mm thick) was compression molded using a Carver press (20,000 lbs of force, 80°C, 1 minute) and then immediately cooled between water-cooled press plates for two minutes. The resulting sample was then tested using an ARES rheometer (25 mm disposable aluminum parallel plate, 1.0% strain amplitude, 1 rad / sec frequency, tested under N2 gas). The data from these tests are shown in Figure 7 These data demonstrate the ability to control the crosslinking rate by adding different amounts of Pt catalyst to a vulcanizable formulation in a solvent-free process. It has been found that the crosslink density growth rate is controlled by both catalyst loading and vulcanization temperature. The data show that catalyst loading is a more sensitive process for regulating modulus growth.

[0321] Study 6: Shear Rheology of Melt-Prepared Pt Curable Formulations with Inhibitor Adjustable

[0322] Terpolymer 4 (15 g) containing 1.6 wt% octenyldimethylsilane (ODMS, 1H NMR, 13C NMR), 44.4 wt% octene (1HNMR, 13C NMR) and the balance ethylene was melted using a HAAKE melt blender set at 90°C at a blade speed of 60 rpm. Terpolymer 4 had Mn=66,000 g / mol and Mw=142,000 g / mol. Polybutadiene (2 wt%, based on the total weight of the terpolymer and the polybutadiene) was then added to the melt blender as the polyvinyl compound. After three minutes of fluxing, 0 ppm or 10 ppm of Pt from Karstedt's catalyst (based on the total weight of the terpolymer and the polybutadiene) was added to the mixer, and the resulting composition was fluxed for one minute until homogenized. In one of the samples, 1000 ppm (based on the total weight of the terpolymer and polybutadiene) of an inhibitor (1-ethynyl-1-cyclohexanol, "ETCH", 99%, Sigma) was added before the addition of the Pt catalyst.

[0323] Dynamic mechanical analysis (DMA) disks (25 mm diameter x 2 mm thick) were compression molded using a Carver press (20,000 lbs force, 80°C, 1 minute) and then immediately cooled between water-cooled platens for two minutes. The resulting samples were then tested using an ARES rheometer (25 mm disposable aluminum parallel plates, 1.0% strain amplitude, 1 rad / sec frequency, tested under N2 gas) using a DMA program (2°C / min ramp rate, 25°C–200°C temperature range). The data are shown in Figure 8 The data indicate that when no Pt catalyst (0 ppm) is added to the formulation, the shear storage modulus of the sample decreases monotonically with increasing temperature during DMA. No crosslinking was observed in this sample. When 10 ppm Pt was added to the sample (without added inhibitor), crosslinking was observed. The DMA trace can be divided into a warming region (25°C–60°C), a melting region (60°C–90°C), and a crosslinking region (90°C–200°C). The warming region exhibits some stress relaxation through expansion of the sample, which can result in a small increase in storage modulus with temperature. The melting region is characterized by a decrease in storage modulus as the increased thermal energy allows individual polymer chains to become more mobile.

[0324] The crosslinked region is characterized by an increase in shear storage modulus. This is due to the progression of the hydrosilylation reaction, creating covalent crosslinks between the silane and the polyvinyl compound, as it is catalyzed by Pt. When examining the sample containing 10 ppm Pt and 1000 ppm ETCH inhibitor, the temperature range shifts. In this sample, the rising temperature region continues to be observed from 25°C–60°C, however the melt region temperature range now extends from 60°C–150°C. This is due to the temporary complexation of the ETCH inhibitor with the vinyl groups in the Pt catalyst, inhibiting the occurrence of the hydrosilylation reaction. As the temperature of the system increases, the thermal energy eventually added is sufficient to cause dissociation between the ETCH inhibitor and the Pt complex. The Pt is now considered active, and the crosslinked region begins (150°C–200°C). This demonstrates the ability to melt blend the polyvinyl compound, inhibitor, and precious metal catalyst complex to form a rate-controlled vulcanizable formulation. This suppressed catalytic effect can better allow for controlled processability of these formulations.

[0325] Study 7: Shear Rheology of Melt-Prepared Pt Curable Formulations Adjustable with Additional Classes of Inhibitors

[0326] Terpolymer 5 (15 g) containing 2.4 wt% hexenyldimethylsilane (HDMS, 1H NMR), 48.3 wt% octene (1H NMR) and the balance ethylene was melted using a HAAKE melt blender set at 90°C with a blade speed of 60 rpm. Terpolymer 4 had Mn=54,000 g / mol and Mw=141,000 g / mol. Polybutadiene (2 wt%, based on the total weight of the terpolymer and polybutadiene) was then added as the polyvinyl compound to the melt blender. After three minutes of fluxing, 1000 ppm (based on the total weight of the terpolymer and polybutadiene) of an inhibitor (ETCHA, Surfynol-61 or ViD4) was added and the formulation was fluxed for another three minutes. After homogenization, 100 ppm of Pt from Karstedt's catalyst (based on the total weight of the terpolymer and polybutadiene) was added to the mixer and the resulting composition was fluxed for one minute until homogenized.

[0327] Dynamic mechanical analysis (DMA) disks (25 mm diameter x 2 mm thick) were compression molded using a Carver press (20,000 lbs force, 80°C, 1 minute) and then immediately cooled between water-cooled platens for two minutes. The resulting samples were then tested using an ARES rheometer (25 mm disposable aluminum parallel plates, 1.0% strain amplitude, 1 rad / sec frequency, tested under N2 gas) using an isothermal time sweep (T = 180°C). The data from these tests are shown in Fig. 9 . The data show that adding the same weight percent loading of various inhibitors to the polymer system results in different shear storage modulus plateaus. The rate at which the storage modulus plateau is reached varies depending on the type of inhibitor used. These data show that the system with "added ViD4" is the most strongly inhibited, with minimal crosslinking observed. The systems using ETCHA and Surfynol-61 have lower binding strength to the Pt complex, resulting in higher reactivity at elevated temperatures and in a shorter amount of time. These data suggest that different types of inhibitors can be used to adjust reactivity based on the expected processing conditions. It should also be noted that the control sample was filled with 10 wt % talc (based on the weight of the terpolymer, polybutadiene and talc), indicating that these systems can accommodate inorganic non-reactive fillers without greatly affecting the cure properties. Further examination (using 1000 ppm of ETCHA and Surfynol-61) used two different isothermal time scans (T=120°C, 180°C) to look for further differences, such as Fig.10 The lower temperature isotherm (120 °C) shows a small difference in the degree of inhibition, and the higher temperature isotherm (180 °C) begins to show that ETCHA binds less strongly to the Pt complex than Surfynol-61.

[0328] Study 8: Shear Rheology of Melt-Prepared Pt Curable Formulations with Common Antioxidants

[0329] Terpolymer 6 (15 g) containing 1.7 wt % octenyldimethylsilane (ODMS, 1H NMR), 42.1 wt % octene (1H NMR) and the balance ethylene was melted using a HAAKE melt blender set at 90° C. at a blade speed of 60 rpm. Terpolymer 6 had Mn=59,000 g / mol and Mw=153,000 g / mol. Polybutadiene (2 wt %, based on the total weight of the terpolymer and polybutadiene) was then added to the melt blender as a polyvinyl compound. After three minutes of fluxing, varying amounts of IRGANOX 1010 (750 ppm or 1500 ppm), IRGANOX 1076 (200 ppm or 1500 ppm) or IRGAFOS 1680 (750 ppm or 1500 ppm; similar to IRGAFOS 168) were added as a 10 wt % solution dissolved in 100 uL toluene. Each "ppm" amount is based on the total weight of the terpolymer and polybutadiene. The formulation was fluxed for an additional three minutes after which 100 ppm Pt (based on the total weight of the terpolymer and polybutadiene) of Karstedt's catalyst was added to the mixer and fluxed for one minute until homogenized.

[0330] Dynamic mechanical analysis (DMA) disks (25 mm diameter x 2 mm thick) were compression molded using a Carver press (20,000 lbs force, 80°C, 1 minute) and then immediately cooled between water-cooled platens for two minutes. The resulting samples were then tested using an ARES rheometer (25 mm disposable aluminum parallel plates, 1.0% strain amplitude, 1 rad / sec frequency, tested under N2 gas) using a DMA program (2°C / min ramp rate, 25°C–200°C temperature range). The data are shown in Fig.11 The data show that IRGAFOS 1680 (a phosphite-based antioxidant) can be used to inhibit the Pt hydrosilylation reaction. Both cases of "addition of IRGAFOS 168" show significantly higher starting temperatures in the crosslinked region of the DMA trace (about 180°C) compared to the uninhibited control case (about 120°C for this sample). The IRGANOX 1010 and IRGANOX 1076 formulations show that the crosslinking rate can be accelerated due to the addition of these hindered phenolic antioxidants. The crosslinking starting point observed for each formulation is closer to 100°C, and the shear storage modulus always increases at an accelerated rate regardless of the antioxidant loading. This is attributed to the reaction between the carbonyl or alcohol groups in these IRGANOX antioxidants and the silane in the terpolymer, which is catalyzed by Pt. The data show that antioxidant loading is less important for Pt inhibition than the type of antioxidant and the temperature at which antioxidant dissociation occurs.

Claims

1. A method of forming a crosslinked composition, the method comprising heat treating a composition comprising: a) an olefin / silane interpolymer, wherein the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of: 2 C=CH-R1-Si(R)(R')-H, wherein R1 is an alkylene group, and R and R' are each independently an alkyl group, and R and R' can be the same or different, b) a curing catalyst, and c) Polyvinyl compounds.

2. The method of claim 1, wherein the olefin / silane interpolymer of component a is an ethylene / α-olefin / silane interpolymer.

3. The method of claim 1, wherein the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of: Where R 2 It is an alkylene group.

4. The method of claim 2, wherein the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of: Where R 2 It is an alkylene group.

5. The method according to any one of claims 1 to 4, wherein the curing catalyst of component b comprises platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

6. The method according to any one of claims 1 to 4, wherein the polyvinyl compound of component c is selected from the following i) to iv): i) Wherein R3 is selected from alkylene or arylene; ii) a polydiene comprising at least one of the following structures: (CR1R2-CR3=CR4-CR5R6) n -(CR7R8-CR9(CR10=CR11R12)) m -, wherein each of R1 to R12 is independently hydrogen (H) or an alkyl group, and n≥1 and m≥1; iii) H 3 C-CH 2 -C[R4-OC(O)-CH=CH 2 ] 3 , wherein R4 is an alkylene group or an arylene group; or iv) has the following structure – [Si(CH=CH 2 )(R5)-O] n - a cyclic siloxane wherein R5 is an alkyl group and n is 3 to 6.

7. The method according to any one of claims 1 to 4, wherein the polyvinyl compound of component c is selected from the following: dodecadiene, divinylbenzene, tetravinyltetramethylcyclotetrasiloxane (ViD4), trimethylolpropane triacrylate (TMPTA), or polybutadiene, the polybutadiene containing ≥80 mol % of 1,2 vinyl groups and having a melt viscosity at 45°C of 30 cP to 500 cP.

8. The method according to any one of claims 1 to 4, wherein the composition further comprises component d: a curing inhibitor.

9. A composition comprising the following components: a) an olefin / silane interpolymer, wherein the silane of the olefin / silane interpolymer is derived from a compound selected from the group consisting of: 2 C=CH-R1-Si(R)(R')-H, wherein R1 is an alkylene group, and R and R' are each independently an alkyl group, and R and R' can be the same or different, b) a curing catalyst, and c) Polyvinyl compounds.

10. The composition of claim 9, wherein the olefin / silane interpolymer of component a is an ethylene / α-olefin / silane interpolymer.

11. The composition according to claim 9, wherein the vinyl compound of component c is selected from the following i)-iv): i) Wherein R3 is selected from alkylene or arylene; ii) a polydiene comprising at least one of the following structures: (CR1R2-CR3=CR4-CR5R6) n -(CR7R8-CR9(CR10=CR11R12)) m -, wherein each of R1 to R12 is independently hydrogen (H) or an alkyl group, and n≥1 and m≥1; iii) H 3 C-CH 2 -C[R4-OC(O)-CH=CH 2 ] 3 , wherein R4 is an alkylene group or an arylene group; or iv) has the following structure – [Si(CH=CH 2 )(R5)-O] n - a cyclic siloxane wherein R5 is an alkyl group and n is 3 to 6.

12. The composition according to claim 10, wherein the vinyl compound of component c is selected from the following i)-iv): i) Wherein R3 is selected from alkylene or arylene; ii) a polydiene comprising at least one of the following structures: (CR1R2-CR3=CR4-CR5R6) n -(CR7R8-CR9(CR10=CR11R12)) m -, wherein each of R1 to R12 is independently hydrogen (H) or an alkyl group, and n≥1 and m≥1; iii) H 3 C-CH 2 -C[R4-OC(O)-CH=CH 2 ] 3 , wherein R4 is an alkylene group or an arylene group; or iv) has the following structure – [Si(CH=CH 2 )(R5)-O] n - a cyclic siloxane wherein R5 is an alkyl group and n is 3 to 6.

13. The composition according to any one of claims 9 to 12, wherein the composition further comprises component d: a curing inhibitor.

14. A cross-linked composition formed from the composition according to any one of claims 9 to 13.

15. An article comprising at least one component formed from the composition of any one of claims 9 to 13.

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