Auxiliary-assisted formation of crosslinked silicon-polyolefin interpolymers using crosslinking agents

Abstract

The present disclosure provides a process. In one embodiment, the process comprises melt blending a composition composed of (i) an ethylene-SiH polymer, (ii) a crosslinking agent which is 1,3-dibenzoylpropane, (iii) a triarylborane, and (iv) an alkylamine inhibitor at a temperature of 80 °C to 200 °C. The process further comprises forming a crosslinked ethylene-Si polymer. The present disclosure also provides a crosslinked ethylene-Si polymer composition composed of this process.

Description

Technical Field

[0001] Crosslinked polyolefins (e.g., crosslinked polyethylene) are known to have excellent mechanical properties compared to their non-crosslinked counterparts, which results in improved performance in their end uses.

[0002] One common approach for crosslinking polyolefins involves a processing step for functionalizing the polyolefin. The functionalized polyolefin is then subjected to a crosslinking step that requires an initiator such as a peroxide or a condensation catalyst.

[0003] Another common approach for curing polyolefin materials (e.g., polyethylene) is moisture curing. Moisture curing involves introducing a hydrolyzable functional group such as vinyltrimethoxysilane (VTMS) onto the polyethylene and subsequently exposing the functionalized polyethylene to moisture. However, curing of such materials requires penetration of moisture into the material, which can limit the curing rate and cause non-uniform curing across the thickness of the material. On the other hand, moisture curing often requires a specific setup such as a humidity chamber or a sauna chamber. Moisture curing of polyolefin materials typically occurs over several days or weeks. When the curing process depends on diffusion of moisture, it often results in non-uniform curing across the thickness of the material, making it difficult to fully cure thick parts.

[0004] Considering the continuing growth in the use of crosslinked polyolefins, there is a recognized continuing need in the art for new processes for crosslinking polyethylene and for forming crosslinked polyethylene that is degradable and / or recyclable.

Summary of the Invention

[0005] The present disclosure provides a process. In one embodiment, the process includes melt blending a composition consisting of (i) an ethylene-SiH polymer, (ii) a crosslinking agent that is 1,3-dibenzoylpropane, (iii) a triarylborane, and (iv) an alkylamine inhibitor at a temperature between 80° C. and 200° C. The process further includes forming a crosslinked ethylene-Si polymer.

[0006] The present disclosure provides a composition. In one embodiment, the composition comprises a compound having the structure (1):

[0007] [ka] The crosslinked ethylene-Si polymer comprises

[0008] Applicant has discovered that upon heating, the alkylamine inhibitor decomposes and releases triarylborane as a catalyst, which reacts with the ethylene-SiH polymer and the crosslinker (which is a bifunctional crosslinker) to produce a crosslinked network. Without the alkylamine inhibitor, the crosslinking reaction is uncontrollable, resulting in loss of processability, which is detrimental to the manufacture of finished parts. The resulting Si-OC bonds are degradable, making it possible to recycle the crosslinked ethylene-Si polymer. Applicant has further discovered that the temperature at which crosslinking occurs can be adjusted based on the identity of the alkylamine inhibitor used. [Brief description of the drawings]

[0009]

Figure 1(a)

Figure 1(b)

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Figure 8

Figure 9(a)

Figure 9(b)

Figure 10

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Figure 12

[0010] Definition Any reference to the Periodic Table of the Elements is a reference to the Periodic Table of the Elements published by CRC Press, Inc., in 1990 - 1991. References to groups of elements in this table are by the new notation for numbering the groups.

[0011] For the purposes of U.S. patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or an equivalent U.S. version is so incorporated by reference) with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the relevant art.

[0012] The numerical ranges disclosed herein include all values from the lower limit to the upper limit (including the lower and upper limits). In the case of ranges containing explicit values (e.g., 1 or 2, or 3 - 5, or 6, or 7), any sub - range between any two explicit values is included (e.g., in the range 1 - 7 above, sub - ranges such as 1 - 2, 2 - 6, 5 - 7, 3 - 7, 5 - 6, etc. are included).

[0013] Unless otherwise stated, not implied from the context, or not customary in the relevant art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0014] The term "composition" refers to a mixture of materials that make up the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0015] The terms "comprising", "including", "having", and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. To avoid any ambiguity, all compositions claimed through the use of the term "comprising" may, unless otherwise stated, include any additional additives, adjuvants, or compounds, whether polymeric or not. In contrast, the term "consisting essentially of" excludes any other components, steps, or procedures from the scope of any preceding description, except for those that are not essential to the operation. The term "consisting of" excludes any component, step, or procedure not specifically depicted or enumerated. The term "or" refers to the listed members individually and in any combination, unless otherwise specified. The use of the singular includes the use of the plural, and vice versa.

[0016] "Dalton" is a unit of the molecular weight of a polymer, equivalent to the atomic mass unit, and is abbreviated as "Da" or "kDa" (kilodalton).

[0017] "Ethylene polymer" or "ethylene-based polymer" is a polymer that contains a majority amount of polymerized ethylene based on the weight of the polymer and may optionally include at least one comonomer. Ethylene polymers typically contain at least 50 mole percent (mol%) of units derived from ethylene (based on the total amount of polymerizable monomers).

[0018] "Hydrocarbon" (or "hydrocarbyl", "hydrocarbyl group") is a compound containing only hydrogen and carbon atoms.

[0019] The term "heterohydrocarbon" ("heterohydrocarbyl" or "heterohydrocarbyl group") and similar terms, as used herein, refer to each hydrocarbon in which at least one carbon atom is substituted with a heteroatom group (e.g., Si, O, N, or P).

[0020] The term "substituted hydrocarbon" (or "substituted hydrocarbyl" or "substituted hydrocarbyl group") refers to a hydrocarbon in which one or more hydrogen atoms are independently replaced by heteroatom groups. The terms "substituted heterohydrocarbon" ("substituted hetero hydrocarbyl" or "substituted hetero hydrocarbyl group") and similar terms, as used herein, refer to each heterohydrocarbon in which one or more hydrogen atoms are independently replaced by heteroatom groups.

[0021] An "interpolymer" is a polymer prepared by the polymerization of at least two different types of monomers. Thus, the general term "interpolymer" includes copolymers (used to refer to polymers prepared from two different types of monomers), and polymers prepared from three or more different types of monomers.

[0022] An "olefinic polymer" or "polyolefin" is a polymer that contains (based on the total amount of polymerizable monomers) a majority molar percentage of polymerized olefin monomers and optionally may contain at least one comonomer. Non-limiting examples of olefinic polymers include ethylene-based polymers and propylene-based polymers. Representative polyolefins include polyethylene, polypropylene, polybutene, polyisoprene, and various interpolymers thereof.

[0023] "Polymer" is a polymeric compound prepared by polymerizing monomers, whether of the same or different types. Thus, the general term "polymer" encompasses the term "homopolymer" (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace impurities may be incorporated into the polymer structure), and the term "interpolymer" as defined hereinafter in this specification. Trace impurities, such as catalyst residues, may be incorporated into and / or within the polymer. It also encompasses all forms of copolymers, such as random, block, etc. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" refer to the above-mentioned copolymers prepared by polymerizing ethylene or propylene, respectively, with one or more additional polymerizable α-olefin monomers. Polymers are often referred to as being "made of", "based on", "containing" a specific monomer content of one or more specific monomers, etc., but in this context, it should be noted that the term "monomer" is understood to refer to the polymerized residue of a specific monomer and not to non-polymerized species. Generally, polymers herein are referred to as being based on "units" that are the polymerized forms of the corresponding monomers.

[0024] "Propylene-based polymer" is a polymer that contains a majority amount of polymerized propylene based on the weight of the polymer and optionally may contain at least one comonomer. Propylene-based polymers typically contain at least 50 mole percent (mol%) of units derived from propylene (based on the total amount of polymerizable monomers).

[0025] Test Methods Density is measured in accordance with ASTM D792, Method B (g / cc or g / cm 3 )).

[0026] Differential Scanning Calorimetry (DSC). Differential Scanning Calorimetry (DSC) was used to measure the Tm, Tc, Tg, and crystallinity of the ethylene-based polymer samples. Samples of approximately 5 - 8 mg were weighed and placed in DSC pans. The lid was crimped onto the pan to ensure a sealed atmosphere. Unless otherwise specified, the sample pans were placed in the DSC cell and then heated to a temperature of 200 °C at a rate of approximately 10 °C / min. The sample was held at this temperature for 3 minutes. Next, the sample was cooled to -90 °C at a rate of 10 °C / min and maintained isothermally at that temperature for 3 minutes. Then, the sample was heated at a rate of 10 °C / min until completely melted (second heating). Unless otherwise specified, the melting point (Tm) and glass transition temperature (Tg) of each polymer were determined from the second heating curve. The peak heat flow temperature of Tm was recorded.

[0027] FTIR-ATR. Infrared spectra were collected using a Perkin Elmer Frontier Fourier transform infrared spectrometer (FT-IR) equipped with an attenuated total reflection (ATR) accessory (single bounce diamond / ZnSe). The sample was cut with scissors to expose a clean internal surface and then placed in the accessory, held with a force such that the peak absorbance was approximately 0.4, and 4 - 16 scans were collected depending on the spectral quality. To ensure representative sampling of the entire sample, spectra were collected at least 3 times. SiH conversion rate. The SiH conversion rate is the mole percentage of SiH bonds in the ethylene-SiH polymer that have been converted to Si-C bonds ("SiC") as a result of the hydrosilylation reaction. The SiH conversion rate was determined by normalizing the peak at 2920 cm -1 and setting the baseline to 0 at 942 cm -1 , and then using the Si-H peak at 887 cm -1 to determine the conversion rate. %SiH conversion rate = 100 * (Absorbance at 887 cm -1 after the hydrosilylation reaction) / (Absorbance at 887 cm -1 before the hydrosilylation reaction).

[0028] The gel content is measured by hot extraction with xylene overnight according to ASTM D2765-16.

[0029] Gel Permeation Chromatography. The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set at 160 °C and the column compartment was set at 150 °C. The columns were one Agilent PLgel MIXED 7.5×50 mm, 20 μm linear mixed-bed guard column, followed by four Agilent PLgel MIXED-A 7.5×300 mm, 20 micron linear mixed-bed columns. The chromatograph solvent was 1,2,4-trichlorobenzene (TCB) containing 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters and the flow rate was 1.0 milliliter / minute.

[0030] Calibration of the GPC column set was performed using Agilent EasiCal polystyrene standards (EasiCal PS-1 and EasiCal PS-2). Each EasiCal system consisted of two different spatulas that supported a mixture of five polymer standards (approx. 5 mg) to obtain 20 molecular weight points in the range of approximately 580 - 6,570,000 g / mol. The individual spatulas were added to septum-capped vials, sealed, and loaded into the PolymerChar autosampler. Using the PolymerChar Instrument Control Software, 8 mL of solvent was added to each vial and the standards were dissolved at 160 °C for 15 minutes under high-speed shaking prior to injection into the chromatography system. The peak molecular weight of the polystyrene standards was converted to polyethylene molecular weight using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M ポリエチレン =A×(M ポリスチレン )B (EQ1), where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0031] A third-degree polynomial was used to fit each polyethylene equivalent calibration point. Slight adjustments (approximately 0.375 - 0.445) were made to A, and the column resolution and band broadening effects were corrected so that the linear low-density polyethylene standard was obtained at 120,000 Mw. The total plate count of the GPC column set was performed using decane (3% v / v in TCB introduced via a micropump). The plate count (Equation 2) and symmetry (Equation 3) were measured according to the following equations for a 200 microliter injection.

[0032]

Number

[0033]

Number

[0034] The samples were prepared semi-automatically using PolymerChar's "Instrument Control" software, weight-standardized at 2 mg / ml, and the solvent (containing 200 ppm of BHT) was added to the septum-capped vials via a PolymerChar high-temperature autosampler. The samples were dissolved at 160 °C for 2 hours under high-speed shaking.

[0035] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculations of were based on the GPC results using PolymerChar's GPCOne (trademark) software, the IR chromatogram with the baseline subtracted at each equally spaced data collection point (i), and the polyethylene equivalent molecular weights obtained from the narrow standard calibration curve for point (i) of Equation 1, according to Equations 4 - 6, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph. Equations 4 - 6 are as follows:

[0036]

Equation

[0037] To monitor the deviation over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. Using this flow rate marker (FM), the pump flow rate (apparent flow rate) of each sample was linearly corrected by matching the RV (RV(FM sample)) of each decane peak in the sample with the RV (RV(FM calibrated)) of the decane peak within a narrow standard calibration. Then, any change in the time of the decane marker peak was assumed to be related to a linear shift in the flow rate (effective flow rate) of the entire run. To facilitate the highest accuracy in RV measurement of the flow marker peak, a least-squares fitting routine was used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. 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 (with respect to the narrow standard calibration) was calculated as Equation 7: Flow rate (effective) = Flow rate (apparent) × (RV(FM calibrated) / RV(FM sample)) (EQ7). The processing of the flow rate marker peak was performed via PolymerChar GPCOne (trademark) software. For acceptable flow rate correction, the effective flow rate should be within ±0.7% of the apparent flow rate.

[0038] Moving die rheometer (MDR). The cure evaluation of the samples was carried out at a specified temperature for 30 minutes at an arc of 0.5° using an Alpha Technologies Advanced Polymer Analyzer (APA 2000) in accordance with ASTM D5289-12, Standard Test Method for Rubber Property-Vulcanization Using Rotorless Cure Meters. The test was conducted at a frequency of 100 cycles per minute (cpm). The minimum measured torque value is shown as "ML" expressed in deciNewton-meter (dN-m). As curing or crosslinking progresses, the measured torque value increases and finally reaches the maximum torque value. The maximum or highest measured torque value is shown as "MH" expressed in dN-m. When all other conditions are equal, the greater the MH torque value, the greater the degree of crosslinking. The T90 cure time is determined as the time (in minutes) required to achieve a torque value equal to 90% of the difference between MH and ML, i.e., 90% of the distance from ML to MH. The shorter the T90 cure time, i.e., the earlier the torque value reaches 90% of the distance from ML to MH, the faster the cure rate of the test sample. Conversely, the longer the T90 cure time, i.e., the more time it takes for the torque value to reach 90% of the distance from ML to MH, the slower the cure rate of the test sample.

[0039] Melt index. The melt index (or "I2") of ethylene-based polymers is measured in accordance with ASTM D-1238, Condition 190°C / 2.16 kg (the melt index (I10) is 190°C / 10.0 kg). I 10 / I2 is calculated from the ratio of I 10 to I2. The melt flow rate MFR of propylene-based polymers is measured in accordance with ASTM D-1238, Condition 230°C / 2.16 kg.

[0040] Nuclear magnetic resonance (NMR) characterization of terpolymers 1For the 1H NMR experiment, each sample was dissolved in tetrachloroethane-d2 in a 5 mm NMR tube. The concentration was approximately 100 mg / 1.8 mL. Then, each tube was heated in a heating block set at 110 °C. The sample tubes were vortexed repeatedly and heated to obtain a homogeneous flowing fluid. 1 The 1H NMR spectra were obtained using a VARIAN 500 MHz spectrometer. Standard single pulse 1 1H NMR experiments were performed. The following acquisition parameters were used, namely, a relaxation delay of 60 seconds and 16 - 32 scans. All measurements were performed without rotating the sample at 110 °C. 1 The 1H NMR spectra were referenced to "5.99 ppm" for the resonance peak of the solvent (residual protonated tetrachloroethane). 1 1H NMR was used to determine the polymerized SiH comonomer content (wt%) in the ethylene-SiH polymer. "Weight % of SiH monomer" was calculated based on the integration of the SiMe proton resonance relative to the integration of the CH2 protons related to ethylene units and the CH3 protons related to octene units. "Weight % of octene (or other α-olefin)" can be similarly determined by referencing the CH3 protons related to octene units (or other α-olefins).

[0041] SiH conversion rate. The SiH conversion rate is measured by FTIR-ATR. See the FTIR-ATR test method. The SiH conversion rate (%) is described under the FTIR-ATR test method.

Mode for Carrying Out the Invention

[0042] The present disclosure provides a process. In one embodiment, the process comprises melt blending a composition composed of (i) an ethylene-SiH polymer, (ii) a crosslinking agent which is 1,3-dibenzoylpropane, (iii) a triarylborane, and (iv) an alkylamine inhibitor at a temperature of 80 °C to 200 °C. The process further comprises forming a crosslinked ethylene-Si polymer.

[0043] The process includes melt-blending a composition composed of (i) an ethylene-SiH polymer, (ii) a crosslinking agent which is 1,3-dibenzoylpropane, (iii) a triarylborane, and (iv) an alkylamine inhibitor at a temperature of 80°C to 200°C. The ethylene-SiH polymer is composed of (1) an ethylene monomer, (2) 0.1 wt% to 3.9 wt% of a SiH comonomer, and (3) an optional C3 to C 12 α-olefin or a C4 to C8 α-olefin ter monomer. As used herein, "SiH comonomer" (also interchangeably referred to as "SiH") is a silane monomer of Formula 1. (Formula 1) A-(SiBC-O) x -Si-EFH (wherein A is an alkenyl group, B is a hydrocarbyl group or hydrogen, C is a hydrocarbyl group or hydrogen, B and C may be the same or different, and further, B is a hydrocarbyl group, C is a hydrocarbyl group, and further B and C are the same, H is hydrogen, x≥0, E is a hydrocarbyl group or hydrogen F is a hydrocarbyl group or hydrogen, E and F may be the same or different, and when E is a hydrocarbyl group, F is a hydrocarbyl group, and E and F may be the same hydrocarbyl group). Non-limiting examples of suitable SiH comonomers of Formula 1 include the following compounds, s1) (allyldimethylsilane), s2) (propenyldimethylsilane), s3) (butenyldimethylsilane), s4) (hexenyldimethylsilane), s5) (octenyldimethylsilane), s6), (decenyldimethylsilane), s7) norbornylethyldimethylsilane, s8) octahydrodimethanonaphthalenylethyldimethylsilane, s9) vinyltetramethyldisiloxane, s10) allyltetramethyldisiloxane, s11) butenyltetramethyldisiloxane, s12) hexenyltetramethyldisiloxane, s13) octenyltetramethyldisiloxane, s14) decenyltetramethyldisiloxane, s15) norbornylethyltetramethyldisiloxane, s16) octahydrodimethanonaphthalenylethyltetramethyldisiloxane, that is,

[0044] [Chemical formula] selected from.

[0045] In one embodiment, the SiH comonomer is selected from allyldimethylsilane, hexenyldimethylsilane, octenyldimethylsilane, and hexenyltetramethyldisiloxane.

[0046] In one embodiment, the ethylene-SiH polymer is an ethylene / α-olefin / SiH terpolymer. The α-olefin in the ethylene / α-olefin / SiH comonomer terpolymer is C3-C 12It can be an α-olefin or a C4-C8 α-olefin. Non-limiting examples of suitable α-olefins include propylene, butene, hexene, octene, and ethylidene norbornene for ethylene / propylene / SiH terpolymer, ethylene / butene / SiH terpolymer, ethylene / hexene / SiH terpolymer, ethylene / octene / SiH terpolymer, and ethylene / ethylidene norbornene / SiH terpolymer, respectively.

[0047] In one embodiment, the ethylene / α-olefin / SiH terpolymer is an ethylene / octene / SiH terpolymer. Non-limiting examples of suitable ethylene / octene / SiH terpolymers include ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, ethylene / octene / octenyldimethylsilane (ODMS) terpolymer, and combinations thereof.

[0048] In one embodiment, the ethylene / α-olefin / SiH terpolymer is an ethylene / octene / SiH terpolymer. The ethylene / octene / SiH terpolymer contains 30 wt% - 41 wt% octene and 0.5 wt% - 5 wt%, or 1.0 wt% - 3.5 wt% SiH comonomer, has a density of 0.87 g / cc - 0.89 g / cc, and an MI of 1 g / 10 min - 18 g / 10 min, or 2 g / 10 min - 12 g / 10 min. Non-limiting examples of suitable ethylene / octene / SiH terpolymers include ethylene / octene / allyldimethylsilane (ADMS) terpolymer, ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, and ethylene / octene / octenyldimethylsilane (ODMS) terpolymer.

[0049] In one embodiment, the ethylene-SiH polymer is ethylene / octene / hexenyldimethylsilane.

[0050] In one embodiment, the ethylene-SiH polymer is an ethylene / octene / ODMS terpolymer.

[0051] The composition contains a crosslinking agent. The crosslinking agent is 1,3-dibenzoylpropane.

[0052] The composition contains a triarylborane. The three aryl groups of the triarylborane may be the same or different. Each of the three aryl groups may independently contain one, or two, or three, or four, or five substituents selected from hydrogen, chlorine, fluorine, trifluoromethyl group, and combinations thereof. The triarylborane is a Lewis acid catalyst and promotes the hydrosilylation reaction between the SiH monomer of the ethylene-SiH polymer and the carbonyl group of 1,3-dibenzoylpropane. Non-limiting examples of suitable triarylboranes include tris(pentafluorophenyl)borane (FAB), tris(3,5-bis(trifluoromethyl)phenyl)borane; bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6-trifluorophenyl)borane; bis(3,5-bis(trifluoromethyl)phenyl)(2,5-bis(trifluoromethyl)phenyl)borane; bis(3,5-bis(trifluoromethyl)phenyl)(4-trifluoromethylphenyl)borane, bis(3,5-bis(trifluoromethyl)phenyl)(2,6-difluorophenyl)borane, tris(2,5-bis(trifluoromethyl)phenyl)borane, and combinations thereof.

[0053] The composition contains an alkylamine inhibitor. The alkylamine inhibitor is a C2-C 16 alkylamine or a C3-C 12 alkylamine. The alkylamine inhibitor may have a linear alkylamine, branched alkylamine, or cyclic alkylamine structure. The alkylamine inhibitor binds to the borane catalyst and prevents the borane catalyst from interacting with Si-H, thereby rendering the borane catalytically inactive. Upon heating, the amine-borane complex decomposes and releases free borane that can catalyze the reaction. Suitable C2-C 16Non-limiting examples of alkylamine inhibitors include triethylamine, diisopropylamine, di-n-propylamine, tert-octylamine, n-octylamine, 2-amino-2,4,4-trimethylpentane, 2-aminoheptane, piperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, and combinations thereof.

[0054] (i) An ethylene-SiH polymer, (ii) a crosslinking agent that is 1,3-dibenzoylpropane, (iii) a triarylborane, and (iv) an alkylamine inhibitor are melt blended or otherwise mixed at a temperature and for a time sufficient to completely homogenize the mixture. The melt blending is carried out at a temperature of 80°C to 200°C, or 90°C to 150°C, or 100°C to 120°C for 1 minute to 20 minutes, or 2 minutes to 15 minutes, or 3 minutes to 10 minutes, by batch mixing or continuous mixing. The melt blending initiates a hydrosilylation reaction between the Si-H moiety of the ethylene-SiH polymer and the carbonyl of 1,3-dibenzoylpropane in the presence of the triarylborane catalyst, thereby bonding or otherwise crosslinking the polymer chains of the ethylene-SiH polymer with 1,3-dibenzoylpropane bonds to form a crosslinked ethylene-Si polymer. The alkylamine inhibitor binds to the borane catalyst and prevents the borane catalyst from interacting with Si-H, thereby rendering the borane catalytically inactive. Upon heating, the amine-borane complex decomposes and releases free borane that can catalyze the reaction. As used herein, "crosslinked ethylene-Si polymer" is the reaction product between an ethylene-SiH polymer and 1-3-dibenzoylpropane, whereby Si-O-C bonds crosslink or bond the individual chains of the ethylene-SiH polymer to each other.

[0055] In one embodiment, the crosslinked ethylene-Si polymer is the reaction product between an ethylene-SiH polymer and 1-3-dibenzoylpropane, whereby structure (1) is a link that crosslinks or bonds the individual chains of the ethylene-SiH polymer to each other:

[0056] [Chemical formula]

[0057] In one embodiment, the crosslinked ethylene-Si polymer contains the link of structure (1) and has the following structure (2)

[0058] [Chemical formula] (wherein the term "polymer" in structure (2) refers to an individual chain of the ethylene-SiH polymer) to form a crosslinked polymer network.

[0059] In one embodiment, the melt blend is carried out by batch mixing in a batch mixer. (i) An ethylene-SiH polymer, (ii) A crosslinking agent which is 1,3-dibenzoylpropane, (iii) A triarylborane, and (iv) An alkylamine inhibitor are put into the batch mixer and melt blended at a temperature of 80°C to 200°C, or 90°C to 150°C, or 100°C to 120°C for 1 minute to 20 minutes, or 2 minutes to 15 minutes, or 3 minutes to 10 minutes, or mixed by other methods. Non-limiting examples of suitable batch mixers include BANBURY (trademark) mixer, BOLLING (trademark) mixer, or HAAKE (trademark) mixer. By batch mixing, a crosslinked ethylene-Si polymer having structure (1) and / or structure (2) is formed.

[0060] In one embodiment, the melt blend is carried out by continuous mixing in an extruder. (i) An ethylene-SiH polymer, (ii) a crosslinking agent which is 1,3-dibenzoylpropane, (iii) a triarylborane, and (iv) an alkylamine inhibitor are introduced into the extruder and melt blended at a temperature of 80°C to 200°C, or 90°C to 150°C, or 100°C to 120°C for 1 minute to 20 minutes, or 2 minutes to 15 minutes, or 3 minutes to 10 minutes, or mixed by other methods to form a homogeneous composition. The extruder can be a continuous single-screw extruder or a continuous twin-screw extruder. Non-limiting examples of suitable extruders include FARREL (trademark), TM continuous mixer, COPERION (trademark) twin-screw extruder, or BUSS (trademark) kneading continuous extruder. The homogeneous composition exits the exit die of the extruder as an extrudate which is a functionalized ethylene-Si polymer having structure (1) and / or structure (2).

[0061] In one embodiment, the process comprises a composition composed of (i) an ethylene-SiH polymer, (ii) a crosslinking agent which is 1,3-dibenzoylpropane, (iii) a triarylborane, and (iv) an alkylamine inhibitor. The ethylene-SiH polymer contains Si atoms present in the SiH comonomer. 1,3-dibenzoylpropane contains a carbonyl moiety. As used herein, the "molar ratio of Si:carbonyl" refers to the ratio of the number of moles of Si atoms in the ethylene-SiH polymer to the number of moles of carbonyl groups in 1,3-dibenzoylpropane. The process includes preparing a composition containing components (i) to (iv) and having a molar ratio of Si:carbonyl of 0.75:1 to 1:1 to 1.25:1, and melt blending the composition at a temperature of 80°C to 200°C to form a crosslinked ethylene-Si polymer. The crosslinked ethylene-Si polymer has structure (1) and / or structure (2).

[0062] In one embodiment, the process comprises a composition composed of (i) an ethylene-SiH polymer, (ii) a crosslinking agent which is 1,3-dibenzoylpropane, (iii) a triarylborane, and (iv) an alkylamine inhibitor. As used herein, the "molar ratio of alkylamine:triarylborane" is the ratio of the number of moles of the alkylamine inhibitor to the number of moles of the triarylborane in the composition. The process comprises preparing (either alone or in combination with preparing a composition containing components (i)-(iv) and having a Si:carbonyl molar ratio of 0.75:1 to 1:1 to 1.25:1 (Si:carbonyl molar ratio 1.0 + / - 0.25)) a composition containing components (i)-(iv) having an alkylamine:triarylborane ratio of 1:1 to 2:1, melt-blending the composition at a temperature of 80°C to 200°C, and forming a crosslinked ethylene-Si polymer. The crosslinked ethylene-Si polymer has structure (1) and / or structure (2).

[0063] In one embodiment, the process comprises melt-blending, at a temperature of 80°C to 200°C, or 90°C to 150°C, or 100°C to 120°C, for 1 minute to 20 minutes, or 2 minutes to 15 minutes, or 3 minutes to 10 minutes, a composition composed of (i) a 93 wt% to 98 wt% ethylene / α-olefin / -SiH terpolymer, (ii) a crosslinking agent which is 1 wt% to 10 wt%, or 3 wt% to 8 wt% of 1,3-dibenzoylpropane, (iii) a 5 ppm to 5000 ppm, or 50 ppm to 500 ppm trialkylborane, and (iv) a 5 ppm to 500 ppm, or 10 ppm to 200 ppm alkylamine, the composition having a Si:carbonyl molar ratio of 0.75:1 to 1:1 to 1.25:1 (Si:carbonyl molar ratio 1.0 + / - 0.25) and an alkylamine:triarylborane ratio of 1:1 to 2:1. The weight percentages are based on the total weight of the composition. The process further comprises forming a crosslinked ethylene-Si polymer. The crosslinked ethylene-Si polymer has structure (1) and / or structure (2).

[0064] The present disclosure provides a composition. In one embodiment, the composition comprises a crosslinked ethylene-Si polymer having structure (1)

[0065] [Chemical formula] and includes a crosslinked ethylene-Si polymer having structure (1).

[0066] The crosslinked ethylene-Si polymer comprising structure (1) has the following properties, namely (i) a density of 0.86 g / cc to 0.88 g / cc, and / or (ii) an M * -M * of 1 dN H m to 3.5 dN L m, and / or (iii) 3500 ppm to 5100 ppm of silicon atoms, and / or (iv) 1 ppm to 10 ppm of boron atoms, having one, some, or all of these.

[0067] In one embodiment, the composition comprises a crosslinked ethylene-Si polymer having structure (2)

[0068] [Chemical formula] (wherein the term "polymer" in structure (2) refers to an individual chain of an ethylene-SiH polymer) and includes a crosslinked ethylene-Si polymer having structure (2).

[0069] The applicant has discovered that upon heating, the alkylamine inhibitor decomposes, releasing triarylborane as a catalyst, which reacts with the ethylene-SiH polymer and the crosslinking agent (a difunctional crosslinking agent) to form a crosslinked network. In the absence of the alkylamine inhibitor, the crosslinking reaction becomes uncontrollable, impairing processability, which is detrimental to the manufacture of finished parts. The applicant has further discovered that the temperature at which crosslinking is generated can be adjusted based on the type of alkylamine inhibitor used.

[0070] Rather than being limiting, and by way of example, several embodiments of the present disclosure will now be described in detail in the following examples.

Example

[0071] A. Synthesis and Properties of Polymers P1, P2, and P3 Ethylene / octene / silane copolymerization to produce a polymer (ethylene-SiH polymer) was carried out in a batch reactor designed for ethylene homopolymerization and copolymerization. The reactor was equipped with an electric heating band and an internal cooling coil containing cooling glycol. Both the reactor and the heating / cooling system were controlled and monitored by a process computer. A dump valve was attached to the bottom of the reactor, and by this, the contents of the reactor were transferred to a dump pot to empty it and released into the atmosphere. All chemicals and catalyst solutions used in the polymerization were passed through a purification column before use. ISOPAR-E, 1-octene, ethylene, and silane monomer were also passed through the column. Ultra-high purity grade nitrogen (Airgas) and hydrogen (Airgas) were used. The catalyst cocktail was prepared in an inert glove box by mixing a scavenger (MMAO), an activator (bis(hydrogenated tar alkyl)methyltetrakis(pentafluorophenyl)borate(1<->)amine), and a catalyst with an appropriate amount of toluene to achieve a desired molar concentration solution. The solution was then diluted with ISOPAR-E or toluene to achieve the desired amount for polymerization and drawn into a syringe for transfer to the catalyst shot tank.

[0072] In a typical polymerization, ISOPAR-E and 1-octene were loaded into the reactor via independent flow meters. Subsequently, the silane monomer was added via a shot tank connected therein by a pipe through an adjacent glove box. After the addition of the solvent / comonomer, hydrogen (if necessary) was added while heating the reactor to the polymerization set point of 120 °C. Then, ethylene was added to the reactor via a flow meter at the desired reaction temperature to maintain a predetermined reaction pressure set point. The catalyst solution was transferred to the shot tank via a syringe and then added to the reactor via a high-pressure nitrogen stream after the reactor pressure set point was reached. The operation timer was started upon catalyst injection, and thereafter, an exotherm and a decrease in reactor pressure were observed, indicating the success of the operation.

[0073] Subsequently, ethylene was added using a pressure controller to maintain the reaction pressure set point inside the reactor. The polymerization reaction was carried out for a set time or until ethylene uptake was complete, after which the stirrer was stopped and the bottom dump valve was opened to transfer the contents of the reactor to a dump pot. The contents of the pot were poured into a tray, which was placed inside a draft to allow the solvent to evaporate overnight. Subsequently, the tray containing the remaining polymer was transferred to a vacuum oven and heated to 100 °C under reduced pressure to remove any remaining solvent. After cooling to ambient temperature, the polymer was weighed for yield / efficiency, transferred to a container for storage, and subjected to analytical tests.

[0074]

Table 1

[0075]

Table 2

[0076]

Table 3

[0077] [Table 4]

[0078] 1. Materials The materials used in the Comparative Sample (CS) and the Examples of the Invention (IE) are shown in Table 2 below.

[0079] [Table 5]

[0080] B. Melt Blend (i) An ethylene - SiH polymer, (ii) 1,3 - dibenzoylpropane (1,3 - DBP), and (iii - iv) a solution of a FAB - alkylamine inhibitor in toluene were sequentially fed at 100 °C to a torque rheometer (Haake PolyLab QC, Thermal Scientific) equipped with a 20 mL bowl and two roller rotors. After the addition of each component, the sample was mixed at 60 RPM for 1 minute. The final blend was mixed for an additional 4 minutes (t mix = 4 + 1 = 5 minutes). Then, for further testing, the hot melt was removed from the blender.

[0081] The amounts and ratios of components (i) - (iv) in the resulting formulation are shown in Table 3 below.

[0082] [Table 6]

[0083] [Table 7]

[0084] Figures 1(a) and 1(b). MDR profiles of each 1,3-DBP sample containing 100 ppm of FAB (IE1) in Fig. 1(a) and 50 ppm of FAB (IE2) in Fig. 1(b), inhibited by 1.2 equivalents of NEt3 at different temperatures. Both samples were compounded at 100 °C for 5 minutes.

[0085] Fig. 1(a) shows the curing profiles at different temperatures of the sample inhibited by NEt3 with 100 ppm of FAB (IE1). The minimum torque (M L ) of the sample decreases with the increase in curing temperature, and a larger torque increase (M H - M L ) is recorded at a lower curing temperature.

[0086] In Fig. 1(b), when the FAB addition is reduced to 50 ppm (IE2), M L is significantly reduced at a specific temperature compared to the sample in Fig. 1(a) containing 100 ppm of FAB, which reflects a lower curing level that occurred during the compounding process. Overall, the M H - M L of the sample showed the same temperature dependence as that of the 100 ppm FAB-NEt3 sample. At 150 °C and 180 °C, the curing time of the 50 ppm FAB-NEt3 sample (Fig. 1b) was the same as that of the 100 ppm FAB-NEt3 sample (Fig. 1a). On the other hand, the M H - M L (Fig. 1(b)) of the 50 ppm FAB-NEt3 sample was smaller at each temperature, probably because there was less catalyst available for the curing reaction under these conditions. Interestingly, at 120 °C, the torque increase of the 50 ppm FAB-NEt3 sample within 30 minutes (Fig. 1(b)) was larger than that of the 100 ppm FAB-NEt3 sample (Fig. 1(a)), and the curing reaction did not show signs of completion.

[0087] As shown in FIGS. 1(a) and 1(b), an embodiment of the present process is carried out at a temperature of 120° C. to 180° C. or 120° C., and comprises melt blending a composition composed of (i) an ethylene / octene / ODMS terpolymer, (ii) a crosslinking agent which is 1,3-dibenzoylpropane, (iii) 100 ppm to 50 ppm of tris(pentafluorophenyl)borane, and (iv) 12 ppm to 24 ppm of triethylamine, to form a crosslinked ethylene-Si polymer having a M * of 1 dN * m to 3 dN H -M L . This process comprises forming a crosslinked ethylene-Si polymer having a M * of 1 dN H -M L when the composition contains 100 ppm of FAB and 24 ppm of triethylamine and is melt blended at a temperature of 120° C. This process comprises forming a crosslinked ethylene-Si polymer having a M * of 3 dN H -M L when the composition contains 50 ppm of FAB and 12 ppm of triethylamine and is melt blended at a temperature of 120° C.

[0088] FIG. 2. SiH conversion rates of 1,3-DBP samples containing no FAB, 100 ppm of FAB (IE1) and 50 ppm of FAB (IE2), inhibited by 1.2 equivalents of NEt3, at different curing temperatures after 30 minutes. The data points at 100° C. represent the SiH conversion rates in the compounded-as-blended samples blended at 100° C. for 5 minutes. FIG. 2 shows that the SiH conversion rates of the FAB-NEt3 samples IE1 and IE2 were maximum when they were cured at 120° C., and it is further confirmed that the M H -M L difference of the FAB-NEt3 samples observed at different temperatures was mainly due to the difference in the curing level.

[0089] Figures 3-4. MDR profiles of 1,3-DBP samples containing 100 ppm FAB inhibited by 1.2 equivalents of iPr2NH (IE3) at different temperatures. Figure 4. SiH conversion rates of 1,3-DBP samples containing 100 ppm FAB inhibited by 1.2 equivalents of iPr2NH (IE3) at different temperatures. The data points at 100 °C represent the SiH conversion rates in the compounded-as-received samples blended at 100 °C for 5 minutes. The M of the FAB-iPr2NH samples L was significantly increased compared to that of the FAB-Pr2NH samples (Figure 3). Nevertheless, the M of the FAB-iPr2NH samples H -M L and both the final SiH conversion rates (Figure 4) were higher than those of the FAB-Pr2NH samples at the same temperature.

[0090] As shown in Figures 3-4, iPr2NH is an effective inhibitor that can cure from M H -M L 1 dN * m to M H -M L 3 dN * m in the melt blend temperature range of 120 °C to 180 °C, and potential curing is observed at all temperatures from 120 °C to 180 °C, providing the highest curing at 120 °C. Embodiments of this process include melt blending a composition consisting of (i) an ethylene / octene / ODMS terpolymer, (ii) a crosslinking agent that is 1,3-dibenzoylpropane, (iii) 100 ppm of tris(pentafluorophenyl)borane, and (iv) 24 ppm of diisopropylamine at a temperature of 120 °C to 180 °C or 120 °C to form a crosslinked ethylene-Si polymer having an M * from 1 dN * m to 3 dN H -M L . This process involves forming a crosslinked ethylene-Si polymer having an M * from 1 dN H -M Lincluding forming a crosslinked ethylene-Si polymer having. This process, when the composition contains 100 ppm of FAB and 24 ppm of diisopropylamine and is melt blended at a temperature of 150 °C, results in 2 dN * m of M H -M L including forming a crosslinked ethylene-Si polymer having. This process, when the composition contains 100 ppm of FAB and 24 ppm of diisopropylamine and is melt blended at a temperature of 120 °C, results in 3 dN * m of M H -M L including forming a crosslinked ethylene-Si polymer having.

[0091] Figure 5. MDR profiles of 1,3-DBP samples containing 100 ppm of FAB inhibited by 1.2 equivalents of Pr2NH at different temperatures. Figure 6. SiH conversion rates of 1,3-DBP samples containing 100 ppm of FAB inhibited by 1.2 equivalents of Pr2NH at different temperatures. The data points at 100 °C represent the SiH conversion rates in the compounded-as-received samples blended at 100 °C for 5 minutes. As shown in Figures 5 and 6, the samples inhibited by Pr2NH (IE4) showed the same curing profile and temperature dependence of SiH conversion rate as the FAB-NEt3 samples (IE1 - IE2). The M L of the samples decreased, and a stronger inhibition of FAB provided by Pr2NH compared to NEt3 was confirmed, and the torque increase was significantly higher than that of the FAB-NEt3 samples, especially at 150 °C and 180 °C. An embodiment of this process is to melt blend a composition composed of (i) an ethylene / octene / ODMS terpolymer, (ii) a crosslinking agent which is 1,3-dibenzoylpropane, (iii) 100 ppm of tris(pentafluorophenyl)borane, and (iv) 24 ppm of diisopropylamine at a temperature of 180 °C, and 0.5 dN * m of M H -M Lcomprises forming a crosslinked ethylene-Si polymer having. This process has a melt blend at a temperature of 150 ° C when the composition contains 100 ppm of FAB and 24 ppm of diisopropylamine, 1.5 dN * m of M H -M L comprises forming a crosslinked ethylene-Si polymer having. This process has a melt blend at a temperature of 120 ° C when the composition contains 100 ppm of FAB and 24 ppm of diisopropylamine, 3.0 dN * m of M H -M L comprises forming a crosslinked ethylene-Si polymer having.

[0092] Figure 7. MDR profiles of 1,3-DBP samples containing 100 ppm of FAB inhibited by 1.2 equivalents of tOA (IE5) at different temperatures. Figure 8. SiH conversion rates of 1,3-DBP samples containing 100 ppm of FAB inhibited by 1.2 equivalents of tOA (IE5) after 30 minutes at different temperatures. The data points at 100 ° C represent the SiH conversion rates in the compounded samples blended at 100 ° C for 5 minutes. With the addition of 100 ppm of FAB-tOA, the M L is lower than that of the 100 ppm FAB-NEt3 and 100 ppm FAB-iPr2NH samples, and M H -M L is higher than that of the 100 ppm FAB-Pr2NH sample (Figure 7). Similarly, M H -M L and the SiH conversion rate decreased with increasing curing temperature (Figure 8). Embodiments of this process are at a temperature of 120 ° C to 180 ° C, (i) an ethylene / octene / ODMS terpolymer, (ii) a crosslinking agent which is 1,3-dibenzoylpropane, (iii) 100 ppm of tris (pentafluorophenyl) borane, (iv) 30 ppm of tert-octylamine, and the resulting composition is melt blended, 1.5 dN * m to 3.5 dN * m of M H -M LIncluding forming a crosslinked ethylene-Si polymer having. This process, when the composition contains 100 ppm of FAB and 30 ppm of tert-octylamine and is melt blended at a temperature of 180 °C, has a 1.5 dN * m of M H -M L Including forming a crosslinked ethylene-Si polymer having. This process, when the composition contains 100 ppm of FAB and 30 ppm of tert-octylamine and is melt blended at a temperature of 150 °C, has a 2.5 dN * m of M H -M L Including forming a crosslinked ethylene-Si polymer having. This process, when the composition contains 100 ppm of FAB and 30 ppm of tert-octylamine and is melt blended at a temperature of 120 °C, has a 3.5 dN * m of M H -M L Including forming a crosslinked ethylene-Si polymer having.

[0093] Figure 9. MDR profiles of 1,3-DBP samples containing 100 ppm of FAB (IE6) in Fig. 9(a) and 500 ppm of FAB (IE7) in Fig. 9(b), inhibited by 1.2 equivalents of nOA at different temperatures. The low M L of the 100 ppm FAB-nOA samples at various temperatures showed little curing of the samples in the compounding step (Fig. 9(a)), suggesting strong FAB inhibition. Correspondingly, the curing rate of the samples inhibited by nOA was relatively slow, i.e., the samples underwent minimal thermal curing under the test conditions (30 minutes at 120 °C to 180 °C). Fig. 9(b) shows the curing profile of the 500 ppm FAB-nOA samples, indicating that there is little additional sample curing in the compounding step compared to the case of 100 ppm FAB-nOA. The curing reaction was almost complete within 30 minutes at 200 °C. In particular, the curing rate increased with temperature, and the curing level (M H -M L ) increased accordingly. The IR results also show that the SiH conversion rate increased with the curing temperature (Fig. 10).

[0094] Embodiments of this process involve melt blending a composition consisting of (i) an ethylene / octene / ODMS terpolymer, (ii) a crosslinking agent which is 1,3-dibenzoylpropane, (iii) 100 ppm of tris(pentafluorophenyl)borane, and (iv) 30 ppm of n-octylamine at a temperature of 120 °C to 200 °C, and 1.5 dN * m to 3.0 dN * m of M H -M L to form a crosslinked ethylene-Si polymer. This process involves forming a crosslinked ethylene-Si polymer having 1.5 dN * m of M H -M L when the composition contains 100 ppm of FAB and 30 ppm of n-octylamine and is melt blended at a temperature of 180 °C. This process involves forming a crosslinked ethylene-Si polymer having 1.5 dN * m of M H -M L when the composition contains 100 ppm of FAB and 30 ppm of n-octylamine and is melt blended at a temperature of 150 °C. This process involves forming a crosslinked ethylene-Si polymer having 3.0 dN * m of M H -M L when the composition contains 100 ppm of FAB and 30 ppm of n-octylamine and is melt blended at a temperature of 200 °C.

[0095] Figure 11. MDR profile of a 1,3-DBP sample containing 100 ppm of FAB inhibited by 1.2 equivalents of Pip(CS2), TMP(CS4), and DMP(CS3) at 180 °C. When piperidine (Pip), 2,6-dimethylpiperidine (DMP), and 2,2,6,6-tetramethylpiperidine (TMP) were used as FAB inhibitors, no thermal curing was observed, as suggested by the very low M L and torque increase being zero (Figure 11).

[0096] Figure 12. MDR profiles of 1,3-DBP samples containing 100 ppm FAB inhibited by 1.2 equivalents of 2-AH (CS5) at different temperatures. When 2-AH was used as the FAB inhibitor, no curing occurred even when the samples were heated at 120 °C and 180 °C for 30 minutes.

[0097] The present disclosure is not limited to the embodiments and examples contained herein, and is particularly intended to include modified forms of those embodiments, including parts of the embodiments and combinations of elements of different embodiments, to the extent that they fall within the scope of the following claims.

Claims

1. The mixture is melted and blended at a temperature of 80°C to 200°C. (i) Ethylene-SiH polymer and (ii) A crosslinking agent which is 1,3-dibenzoylpropane, (iii) Triarylborane and (iv) Alkylamine inhibitors and A composition containing the above is melt-blended, A process comprising forming a cross-linked ethylene-Si polymer.

2. The process according to claim 1, comprising preparing a composition having a Si:carbonyl molar ratio of 0.75:1 to 1:1 to 1.25:

1.

3. The process according to claim 1, comprising preparing a composition having a molar ratio of alkylamine:triarylborane of 1:1 to 2:

1.

4. (i) 90% to 99% by weight of ethylene / α-olefin / -SiH terpolymer, (ii) The crosslinking agent, which is 1,3-dibenzoylpropane in an amount of 1% to 10% by weight, (iii) Triarylborane in concentrations of 5 ppm to 5000 ppm, (iv) To prepare a composition comprising 5 to 500 ppm of the alkylamine, wherein the molar equivalent ratio of the alkylamine to borane is 1:1 to 2:

1. The process according to claim 1, comprising forming a crosslinked ethylene-Si polymer.

5. The process according to claim 1, comprising forming a crosslinked ethylene-Si polymer having Si-O-C bonds.

6. Structure (1) The process according to claim 1, comprising forming a crosslinked ethylene-Si polymer having 【Chemistry 1】

7. (i) Ethylene / octene / ODMS terpolymer and (ii) A crosslinking agent which is 1,3-dibenzoylpropane, (iii) 100 ppm to 50 ppm of tris(pentafluorophenyl)borane, (iv) 12 ppm to 24 ppm of triethylamine, The composition containing the above is melt-blended at a temperature of 120°C. 1 dN ＊ m to 3dN ＊ m of M Ｈ -M Ｌ The process according to claim 1, comprising forming a crosslinked ethylene-Si polymer having

8. (i) Ethylene / octene / ODMS terpolymer and (ii) A crosslinking agent which is 1,3-dibenzoylpropane, (iii) 100 ppm tris(pentafluorophenyl)borane and (iv) A composition containing 24 ppm diisopropylamine is melt-blended at a temperature of 120°C to 180°C. 1 dN ＊ m to 3dN ＊ m of M Ｈ -M Ｌ The process according to claim 1, comprising forming a crosslinked ethylene-Si polymer having

9. (i) Ethylene / octene / ODMS terpolymer and (ii) A crosslinking agent which is 1,3-dibenzoylpropane, (iii) 100 ppm tris(pentafluorophenyl)borane and (iv) A composition containing 30 ppm diisopropylamine is melt-blended at a temperature of 120°C to 180°C. 1.5 dN ＊ m to 3.5 dN ＊ m of M Ｈ -M Ｌ forming a crosslinked ethylene-Si polymer having -M, and the process according to claim 1, comprising.

10. (i) Ethylene / octene / ODMS terpolymer and (ii) A crosslinking agent which is 1,3-dibenzoylpropane, (iii) 100 ppm tris(pentafluorophenyl)borane and (iv) A composition containing 30 ppm n-octylamine is melt-blended at a temperature of 120°C to 200°C. 1.5 dN ＊ m to 3.5 dN ＊ m of M Ｈ -M Ｌ The process according to claim 1, comprising forming a crosslinked ethylene-Si polymer having

11. Structure (1) A composition comprising a crosslinked ethylene-Si polymer having the following properties. 【Chemistry 2】

12. The composition according to claim 11, having a density of 0.86 g / cc to 0.88 g / cc.

13. 1 dN ＊ m to 5 dN ＊ m of M Ｈ -M Ｌ The composition according to claim 11, having the following characteristics.

14. The composition according to claim 11, comprising 1,000 ppm to 6,000 ppm of silicon atoms.

15. The composition according to claim 11, comprising 0.1 ppm to 100 ppm of boron atoms.

16. The composition according to any one of claims 11 to 15, wherein the crosslinked ethylene-Si polymer has structure (2). 【Transformation 3】

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