Moisture-curable silicon polyolefin polymer and process

Abstract

The present disclosure provides a method. In certain embodiments, the process comprises performing a first melt blend on a first composition at a temperature of 80°C to 200°C. The first composition is composed of (i) an ethylene-SiH polymer, (ii) an auxiliary agent that is a monoketone, and (iii) a triarylborane. The process comprises forming a functionalized ethylene-Si polymer. The process further comprises performing a second melt blend on a second composition at a temperature of 80°C to 200°C. The second composition is composed of (iv) a functionalized ethylene-Si polymer and (v) a curing catalyst. The process comprises moisture-curing the second composition and forming a crosslinked ethylene-S polymer. The present disclosure also includes a functionalized ethylene-Si polymer composition produced from the process.

Description

Technical Field

[0001] The curing of polyolefin materials is often achieved by a) peroxide curing, b) platinum (Pt) - catalyzed hydrosilylation if hydrogenated silicon (SiH) or vinyl groups (C = C) are available, or c) moisture curing in the presence of a condensation catalyst if hydrolyzable groups such as alkoxysilane (-Si(OR)3) or hydridosilane (-SiHR2) are available. Both a) and b) require high temperatures to initiate the curing process. The application of b) is not preferred due to the high cost of Pt - based catalysts. In c), alkoxysilanes are often introduced onto polyolefins via a radical process, which follows polymerization and necessarily involves chain scission and hardening of the polymer backbone. Alternatively, alkoxysilane - functionalized polyolefins are synthesized by copolymerization of ethylene and unsaturated silanes (e.g., vinyltrimethoxysilane), which mainly limits the material selection to low - density polyethylene (LDPE). On the other hand, the high moisture sensitivity of alkoxysilanes requires a drying process to maintain a low moisture content in the components and prevent premature cross - linking. Compared with alkoxysilanes, the SiH groups on olefin / silane interpolymers exhibit higher hydrolysis stability, which results in improved storage stability but, on the other hand, leads to a slow curing rate even when exposed to high - temperature and high - humidity levels.

[0002] Therefore, in this technical field, there is a recognized need to devise new curing reactions for olefin - based polymers that are efficient and economically feasible. Furthermore, there is a need for a reaction that can introduce easily hydrolyzable groups into a wide range of polyolefin materials with little or no side reactions, where the hydrolyzable groups provide the ability to cure the functionalized polyolefin at ambient temperature (room temperature).

Summary of the Invention

[0003] The present disclosure provides a method. In certain embodiments, the process includes performing a first melt blend on a first composition at a temperature of 80°C to 200°C. The first composition is composed of (i) an ethylene-SiH polymer, (ii) an auxiliary agent that is a monoketone, and (iii) a triarylborane. The process includes forming a functionalized ethylene-Si polymer. The process further includes performing a second melt blend on a second composition at a temperature of 80°C to 200°C. The second composition is composed of (iv) a functionalized ethylene-Si polymer and (v) a curing catalyst. The process includes moisture-curing the second composition and forming a crosslinked ethylene-Si polymer.

[0004] The present disclosure provides a composition. In certain embodiments, the composition includes a functionalized ethylene-Si polymer having structure (1). Structure (1)

[0005] [Chemical formula] (wherein n is an integer from 4 to 6). Brief Description of the Drawings

[0006]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15

Figure 16

[0007] 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.

[0008] 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 specific definition disclosure (to the extent not inconsistent with any definition specifically provided in this disclosure) and general knowledge in the art.

[0009] The numerical ranges disclosed herein include all values (including the lower and upper values) from the lower value to the upper value. 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 of the explicit values is included (e.g., in the range of 1 - 7 above, the sub - ranges 1 - 2; 2 - 6; 5 - 7; 3 - 7; 5 - 6; etc. are included).

[0010] Unless otherwise stated, not implied from the context, or not customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

[0011] 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.

[0012] 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 include any additional additives, adjuvants, or compounds, whether polymeric or not, unless the contrary is stated. In contrast, the term "consisting essentially of" excludes from the scope of any preceding description any other components, steps, or procedures, except those that are not essential to the operability. 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.

[0013] "Dalton" is a unit of the molecular weight of a polymer, equivalent to the atomic mass unit, and its abbreviations are "Da" or "kDa" (kilodalton).

[0014] "Ethylene-based polymer" or "ethylene polymer" is a polymer that contains a majority amount of polymerized ethylene based on the weight of the polymer and may optionally contain at least one comonomer. Ethylene-based polymers typically contain at least 50 mole percent (mol%) of units derived from ethylene (based on the total amount of polymerizable monomers).

[0015] "Hydrocarbon" (or "hydrocarbyl", "hydrocarbyl group") is a compound that contains only hydrogen atoms and carbon atoms.

[0016] 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).

[0017] 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 term "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.

[0018] 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.

[0019] An "olefin 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 olefin polymers include ethylene polymers and propylene polymers. Representative polyolefins include polyethylene, polypropylene, polybutene, polyisoprene, and various interpolymers thereof.

[0020] "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 in and / or into the polymer. Also included are all forms of copolymers, such as random, block, etc. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" refer to the above-described copolymers prepared by polymerizing ethylene or propylene, respectively, and one or more additional polymerizable α-olefin monomers. Polymers are often referred to as being "made of", "based on", "containing" a particular monomer or type of monomer, etc., but in this context, it should be noted that the term "monomer" is understood to refer to the polymerized residue of a particular monomer and not to non-polymerized species. Generally, polymers herein are referred to as being based on "units" that are the polymerized form of the corresponding monomer.

[0021] "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).

[0022] As used herein, the terms "heat treating", "heat treatment", and similar terms refer to applying heat to a composition. The heat can be applied by conduction (e.g., heating coil), 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, the heat is applied by conduction or convection. Note that the temperature at which the heat treatment is performed refers to the internal temperature of the oven or other device used to cure (or crosslink) the interpolymer.

[0023] Test Methods Measure the density according to ASTM D792, Method B (g / cc or g / cm 3 ).

[0024] Differential Scanning Calorimetry (DSC). Use Differential Scanning Calorimetry (DSC) to measure the Tm, Tc, Tg, and crystallinity of the ethylene-based polymer sample. Weigh approximately 5 - 8 mg of the sample and place it in a DSC pan. Press the lid onto the pan to ensure a sealed atmosphere. Unless otherwise specified, place the sample pan in the DSC cell and then heat it to a temperature of 200 °C at a rate of approximately 10 °C / min. Hold the sample at this temperature for 3 minutes. Then cool the sample to -90 °C at a rate of 10 °C / min and maintain it isothermally at that temperature for 3 minutes. Next, heat the sample at a rate of 10 °C / min until it is 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. Record the peak heat flow temperature of Tm.

[0025] Dynamic Mechanical Analysis The oscillatory rheology test was performed using a strain-controlled rotational rheometer (ARES or ARES-G2, TA Instruments) with a rectangular torsion fixture geometry. A rectangular sample (thickness approximately 2 mm) was heated at a heating rate of 2 °C / min while applying a small oscillatory amplitude within the linear viscoelastic regime at an angular frequency of 1 rad / sec.

[0026] FTIR-ATR. The infrared spectrum was obtained using a Perkin Elmer Frontier Fourier transform infrared spectrometer (FT-IR) with an attenuated total reflection (ATR) accessory (single reflection diamond / ZnSe). The sample was cut with scissors to expose a clean internal surface, then placed in the accessory, held at a force where the peak absorbance was approximately 0.4, and 4 - 16 scans were collected depending on the spectral quality. The spectra were collected in at least triplicate to ensure representative sampling of the entire sample.

[0027] Following a procedure similar to that described in ASTM D2765, gel content analysis was performed using a Soxhlet extraction setup. A sample of known mass (m0) was placed in a pre-weighed glass fiber thimble (m t ) and extracted by boiling xylene (b.p. approximately 136 °C) for 15 hours under N2. The thimble was then dried at 50 °C under vacuum with any sample residue. The final masses of the thimble and residual sample were measured (m1), and the gel content was calculated using the following equation.

[0028]

Equation

[0029] For Polymers 2 - 5 in the Gel Permeation Chromatography Examples section, 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 to 160 °C and the column compartment was set to 150 °C. The columns were four AGILENT "Mixed A" 30 cm, 20 micron linear mixed bed columns. The chromatography solvent was 1,2,4-trichlorobenzene 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] The calibration of the GPC column set was carried out using 21 narrow molecular weight distribution polystyrene standards with molecular weights in the range of 580 to 8,400,000, prepared as six "cocktail" mixtures having at least a 10-fold interval between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared with a solvent of "0.025 grams in 50 milliliters" for molecular weights of 1,000,000 or more and a solvent of "0.05 grams in 50 milliliters" for molecular weights less than 1,000,000. The polystyrene standards were dissolved with gentle stirring at 80 degrees Celsius for 30 minutes. The peak molecular weight of the polystyrene standard was converted to polyethylene molecular weight using Equation 1 (EQ1) (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0031]

Number

[0032] A fifth-degree polynomial was used to fit each polyethylene equivalent calibration point. A slight adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band spreading effects so that a linear homopolymer polyethylene standard was obtained at 120,000 Mw. Decane (prepared with TCB "0.04 g in 50 milliliters" and dissolved for 20 minutes with gentle stirring) was used to measure the total plate count of the GPC column set. The number of theoretical plates (Equation 2, EQ2) and symmetry (Equation 3, EQ3) were measured with a 200 microliter injection using the following equations:

[0033]

Number

[0034]

Number

[0035] The sample was prepared semi-automatically using PolymerChar "Instrument Control" software, targeting a weight of 2 mg / mlwo, and a solvent (containing 200 ppm of BHT) was added via a PolymerChar high-temperature autosampler to a vial with a septum cap that had been sparged with nitrogen in advance. The sample was dissolved at 160 degrees Celsius for 2 hours under "low-speed" shaking.

[0036] 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 a 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 (EQ4 - EQ6) are as follows:

[0037]

Number

[0038]

Number

[0039]

Number

[0040] 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. Subsequently, any change in the time of the peak of the decane marker was assumed to be related to a linear shift in the flow rate of the entire run (effective flow rate). To facilitate the highest accuracy in RV measurements of the peak of the flow marker, a least-squares fitting routine was used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. Subsequently, the first derivative of the quadratic equation was used to solve for the true peak position. After calibrating the system based on the peak of the flow marker, the effective flow rate (with respect to the narrow standard calibration) was calculated as Equation 7: Effective flow rate = Apparent flow rate × (RV(FM calibrated) / RV(FM sample)) (Equation 7). The processing of the peak of the flow rate marker 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 should be.

[0041] For Polymer 1 in the Example section, 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 chromatography 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.

[0042] 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 to 6,570,000 g / mol. The individual spatulas were added to septum cap 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 7 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0043]

Equation

[0044] A third-degree polynomial was used to fit each polyethylene equivalent calibration point. A slight adjustment (approximately 0.375 - 0.445) was made to A, and the column resolution and band spreading effects were corrected so that the linear low-density polyethylene standard could be obtained at 120,000 Mw. The measurement of the total theoretical plates of the GPC column set was carried out using decane (3% v / v in TCB introduced via a micropump). The theoretical plate number measurement (Equation 2) and symmetry (Equation 3) were measured according to the following equations with a 200 microliter injection.

[0045]

Number

[0046]

Number

[0047] The sample was prepared semi-automatically using PolymerChar's "Instrument Control" software, with a target weight of 2 mg / ml for the sample. Solvent (containing 200 ppm of BHT) was added to vials with septum caps via a PolymerChar high-temperature autosampler. The sample was dissolved at 160 °C for 2 hours under high-speed shaking.

[0048] Mn (GPC) , Mw (GPC) and Mz (GPC) The calculations of, and were based on GPC results using PolymerChar's GPCOne (trademark) software, an IR chromatogram with the baseline subtracted at each equally spaced data collection point (i), and polyethylene equivalent molecular weights obtained from a narrow standard calibration curve for point (i) of Equation 1, using the internal IR5 detector (measurement channel) of a PolymerChar GPC-IR chromatograph, according to Equations 4 - 6. The equations 4 - 6 are as follows.

[0049]

Number

[0050]

Number

[0051]

Number

[0052] 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 peak of the decane marker was assumed to be related to a linear shift in the overall flow rate of the run (effective flow rate). To facilitate the highest accuracy in RV measurement of the peak of the flow marker, 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 peak of the flow marker, the effective flow rate (with respect to the narrow standard calibration) was calculated as Equation 7: effective flow rate = apparent flow rate × (RV(FM calibrated) / RV(FM sample)) (Equation 7). The processing of the peak of the flow rate marker 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 should be

[0053] The melt index (or "I2") of the melt index ethylene-based polymer is measured according to 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 the propylene-based polymer is measured according to ASTM D-1238, Condition 230 °C / 2.16 kg.

[0054] Nuclear Magnetic Resonance (NMR) Characterization of Terpolymers 13For the 13C NMR experiment, the sample was dissolved in tetrachloroethane-d2 (with or without 0.025 M Cr(acac)3) in a 10 mm NMR tube. The concentration was approximately 300 mg / 2.8 mL. Then each tube was heated in a heating block set at 110 °C. The sample tube was vortexed repeatedly and heated to obtain a homogeneous flowing fluid. 13 The 13C NMR spectra were obtained on a BRUKER AVANCE 600 MHz spectrometer equipped with a 10 mm C / H DUAL cryoprobe. The following acquisition parameters were used: a repetition delay of 60 seconds, a 90-degree pulse of 12.0 μs, and 256 scans. The spectral center was 100 ppm and the spectral width was 250 ppm. All measurements were carried out at 110 °C without rotating the sample. 13 The 13C NMR spectra were referenced to "74.5 ppm" for the resonance peak of the solvent. For the samples containing Cr, data were acquired with a "repetition delay of 7 seconds" and 1024 scans.

[0055] 1 For 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 tube was vortexed repeatedly and heated to obtain a homogeneous flowing fluid. 1 The 1H NMR spectra were obtained on a VARIAN 500 MHz spectrometer. A standard single-pulse 1 1H NMR experiment was performed. The following acquisition parameters were used: a repetition delay of 60 seconds and 16 - 32 scans. All measurements were carried out at 110 °C without rotating the sample. 1 The 1H NMR spectra were referenced to "5.99 ppm" for the resonance peak of the solvent (residual protonated tetrachloroethane). 1The polymerization SiH monomer content (wt%) in the ethylene-SiH polymer was determined using 1H NMR. "SiH monomer wt%" was calculated based on the integration of the SiMe proton resonance relative to the integration of the CH2 protons associated with ethylene units and the CH3 protons associated with octene units. "Octene (or other α-olefin) wt%" can be similarly determined by referring to the CH3 protons associated with octene units (or other α-olefins).

[0056] SiH conversion. The SiH conversion is measured by FTIR-ATR. See the FTIR-ATR test method. The SiH conversion percentage (%) is described in the section on the FTIR-ATR test method.

DETAILED DESCRIPTION OF THE INVENTION

[0057] The present disclosure provides a method. In one embodiment, the method includes performing a first melt blend at a temperature of 80°C to 200°C on a first composition comprising (i) an ethylene-SiH polymer, (ii) an auxiliary agent that is a monoketone, and (iii) a triarylborane to form a functionalized ethylene-Si polymer. The process further includes performing a second melt blend at a temperature of 80°C to 200°C on a second composition comprising (iv) the functionalized ethylene-SiH polymer and (v) a curing catalyst, and then curing the second composition to form a crosslinked ethylene-Si polymer.

[0058] The method includes performing a first melt blend at a temperature of 80°C to 200°C on a first composition comprising (i) an ethylene-SiH polymer, (ii) an auxiliary agent that is a monoketone, and (iii) a triarylborane. The ethylene-SiH polymer is composed of (1) ethylene monomer, (2) 0.1 wt% to 3.9 wt% of SiH comonomer, and (3) an optional C3-C 12 α-olefin or C4-C8 α-olefin terpolymer. As used herein, "SiH comonomer" (alternatively 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, where B and C may be the same or different, and further, B is a hydrocarbyl group, C is a hydrocarbyl group, and 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.

[0059] [Chemical formula] selected from.

[0060] In certain embodiments, the SiH comonomer is selected from allyldimethylsilane, hexenyldimethylsilane, octenyldimethylsilane, and hexenyltetramethyldisiloxane.

[0061] In certain embodiments, the ethylene-SiH polymer is an ethylene / α-olefin / SiH terpolymer. The α-olefin in the ethylene / α-olefin / SiH comonomer terpolymer can be a C3-C 12 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.

[0062] In certain embodiments, 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.

[0063] In one embodiment, the ethylene / α-olefin / SiH terpolymer is an ethylene / octene / SiH terpolymer. The ethylene / octene / SiH terpolymer contains 32% to 35% by weight of octene and 0.5% to 5% by weight, or 1.0% to 3.5% by weight of SiH comonomer, and has a density of 0.87 g / cc to 0.89 g / cc and an MI of 1 g / 10 min to 18 g / 10 min, or 2 g / 10 min to 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.

[0064] In one embodiment, the ethylene-SiH polymer is selected from an ethylene / octene / HDMS terpolymer and an ethylene / octene / ODMS terpolymer.

[0065] In one embodiment, the ethylene-based-SiH polymer is an ethylene / octene / interpolymer.

[0066] In one embodiment, the ethylene-SiH polymer is an ethylene / octene / ODMS terpolymer.

[0067] The first composition contains (ii) an auxiliary agent that is a monoketone (alternatively referred to as a "monoketone auxiliary agent"). As used herein, a "monoketone auxiliary agent" is a hydrocarbon containing a single carbonyl group. Non-limiting examples of suitable monoketone auxiliary agents include acetophenone, benzophenone, acetone, methyl ethyl ketone, and butanone. In one embodiment, the monoketone auxiliary agent is acetophenone.

[0068] The first composition contains (iii) a triarylborane. The three aryl groups 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.

[0069] (i) An ethylene-SiH polymer, (ii) a monoketone auxiliary, and (iii) a triarylborane are melt-blended (or a first melt-blend) at a temperature and for a time sufficient to fully homogenize the mixture, or are mixed by other means. The first melt-blend 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 first melt-blend initiates a hydrosilylation reaction between the Si-H moiety of the ethylene-SiH polymer and the carbonyl group of the monoketone auxiliary in the presence of a triarylborane catalyst, thereby grafting the monoketone auxiliary onto the ethylene-SiH polymer to form a functionalized ethylene-Si polymer. As used herein, "functionalized ethylene-Si polymer" is the reaction product between an ethylene-SiH polymer and a monoketone auxiliary, and the monoketone auxiliary is grafted onto the ethylene-SiH polymer at the silicon atom of the SiH moiety by an Si-O-C bond or is covalently bonded in other ways.

[0070] The functionalized ethylene-Si polymer has little or no crosslinking and has a gel content of less than 0% to 2.5%. In other words, the functionalized ethylene-Si polymer has a shear storage modulus (G') value of less than 1×10 6 Pa at 100 °C.

[0071] In certain embodiments, the crosslinked ethylene-Si polymer is the reaction product between an ethylene-SiH polymer and a monoketone auxiliary that is acetophenone, whereby acetophenone is grafted onto the ethylene-SiH polymer to form the following structure (1): Structure (1)

[0072]

Chemical formula

[0073] This method involves performing a second melt blend on a second composition comprising (iv) a functionalized ethylene-Si polymer and (v) a curing catalyst at a temperature of 80 °C to 200 °C. As used herein, "curing catalyst" is a compound that accelerates the reaction between pendant silane moieties of two or more olefin / silane interpolymer chains, e.g., -Si(R 1 )(R 2 )H, in the presence of moisture. Examples of curing catalysts include metal alkoxides, metal carboxylates, metal sulfonates, aryl sulfonic acids, and tris-aryl boranes. Metal alkoxides are typically represented by M(OR) n , where M is a metal, R is an alkyl group, and n ≧ 1. In certain embodiments, M is titanium (Ti) or tin (Sn).

[0074] Metal carboxylates are typically represented by M[O-C(O)-R] m , where M is a metal, R is alkyl, m ≧ 1, or (R’) n M[O-C(O)-R] m , where each of R’ and R is independently alkyl, M is a metal, and n ≧ 1 and m ≧ 1. In certain embodiments, M is Ti or Sn. In a further embodiment, M is Sn.

[0075] Metal sulfonates are typically represented by M[OS(O)2R] n , where M is a metal, R is a substituted or unsubstituted alkyl group, and n ≧ 1. For example, one or more hydrogen atoms on the alkyl group may be substituted with a halo group such as F. In certain embodiments, M is bismuth.

[0076] Aryl sulfonic acid contains at least one aryl group and at least one sulfonic acid group. Examples of aryl sulfonic acid are represented by Ar-S(O)2-OH, where Ar is an aryl group containing one or more alkyl groups. The aryl group can be bicyclic, tricyclic, etc. Examples of aryl sulfonic acid are described in International Publication No. WO 2002 / 12355, which is incorporated herein by reference.

[0077] Non-limiting examples of suitable curing catalysts include dibutyltin dilaurate, tetrabutyl titanate, dodecylbenzene sulfonic acid (DBSA), bismuth trifluoromethanesulfonate, and combinations thereof.

[0078] In certain embodiments, the curing catalyst is dodecylbenzene sulfonic acid (DBSA).

[0079] Component (iv) of the second composition, the functionalized ethylene-Si polymer, and (v) the curing catalyst are melt blended (or a second melt blend) or otherwise mixed at a temperature and for a time sufficient to completely homogenize the mixture. The second melt blend is carried out by batch mixing or continuous mixing 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.

[0080] In certain embodiments, the process includes forming or otherwise shaping the second composition into an article (prior to the moisture curing step). Non-limiting shaping procedures include pressing, rolling, molding, extrusion, compression, and combinations thereof to form non-limiting articles such as films, sheets, plaques, pellets, annular structures, and combinations thereof.

[0081] Once the second melt blend is complete, the second composition is moisture cured to form a crosslinked ethylene-Si polymer. As used herein, "moisture curing" refers to the curing or crosslinking of the second composition (after the second melt blend) when exposed to water. The water may be in the form of atmospheric moisture (moisture present in the air) or water in the form of a water bath. The rate and extent of moisture curing or crosslinking are functions of the amount of silane functionality in the second composition, the nature of the exposure to water (e.g., immersion in a water bath, relative humidity of the air, etc.), the duration of the exposure, and temperature. During moisture curing, the Si-0-C bonds in the functionalized ethylene-SiH polymer hydrolyze in the presence of moisture (water, air humidity, vapor) and a curing catalyst to form silanol groups. The silanol groups condense with each other in the presence of a curing catalyst to form Si-O-Si bonds, and the Si-O-Si bonds bond the individual chains of the ethylene-SiH polymer to each other or crosslink in other ways. As used herein, a "crosslinked ethylene-Si polymer" is a moisture curing reaction product in which Si-0-Si bonds crosslink or otherwise bond the individual polymer chains of a functionalized ethylene-SiH polymer to form a network structure of the bonded polymer chains together.

[0082] In certain embodiments, moisture curing includes exposing the second composition to air having a relative humidity (RH) of 10% to 70%, or 15% to 60%, and a temperature of 10°C to 60°C, or 10°C to 50°C, or 10°C to 25°C for 24 hours to 336 hours. Moisture curing forms a crosslinked ethylene-Si polymer.

[0083] In certain embodiments, moisture curing includes immersing the second composition in a water bath having a temperature of 20°C to 90°C, or 20°C to 60°C, or 20°C to 50°C for 24 hours to 168 hours. Moisture curing forms a crosslinked ethylene-Si polymer.

[0084] In certain embodiments, the crosslinked ethylene-Si polymer is the moisture curing reaction product between (i) a functionalized ethylene-Si polymer containing structure (1) and (ii) a curing catalyst DSBA, and this reaction product has the following structure (2): Structure (2)

[0085]

Chem.

[0086] In certain embodiments, the first melt blend and / or the second melt blend is performed by batch mixing in a batch mixer. In the first melt blend, (i) an ethylene-SiH polymer, (ii) a monoketone coagent, and (iii) a triarylborane are introduced into the batch mixer and melt blended or otherwise mixed 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. Non-limiting examples of suitable batch mixers include a BANBURY™ mixer, a BOLLING™ mixer, or a HAAKE™ mixer. The batch mixing forms a functionalized ethylene-Si polymer. In certain embodiments, the monoketone coagent is acetophenone and the batch mixing forms a functionalized ethylene-Si polymer having Structure (1).

[0087] In certain embodiments, the second melt blend is performed by batch mixing in a batch mixer. In the second melt blend, (iv) a functionalized ethylene-SiH polymer and (v) a curing catalyst are introduced into the batch mixer and melt blended or otherwise mixed 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. Non-limiting examples of suitable batch mixers include a BANBURY™ mixer, a BOLLING™ mixer, or a HAAKE™ mixer. The batch mixing forms a second composition that is subsequently moisture cured to form a crosslinked ethylene-Si polymer having Structure (2).

[0088] In certain embodiments, the first melt blend and / or the second melt blend are performed by continuous mixing in an extruder. In the first melt blend, (i) an ethylene-SiH polymer, (ii) a monoketone co - agent, and (iii) a triarylborane are introduced into the extruder and melt blended or otherwise mixed 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 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 a FARREL™ continuous mixer, a COPERION™ twin - screw extruder, or a BUSS™ kneading continuous extruder. The homogeneous composition exits the exit die of the extruder as an extrudate that is a functionalized ethylene - Si polymer. In certain embodiments, the monoketone co - agent is acetophenone, and the homogeneous composition exits the exit die of the extruder as an extrudate that is a functionalized ethylene - Si polymer having structure (1).

[0089] In certain embodiments, the second melt blend is performed by continuous mixing in an extruder. In the second melt blend, (iv) a functionalized ethylene - SiH polymer, and (v) a curing catalyst are introduced into the extruder and melt blended or otherwise mixed 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. The extruder can be a continuous single - screw extruder or a continuous twin - screw extruder. Non - limiting examples of suitable extruders include a FARREL™ continuous mixer, a COPERION™ twin - screw extruder, or a BUSS™ kneading continuous extruder. The homogeneous composition exits the exit die of the extruder as an extrudate composed of the second composition, and the extrudate is then moisture - cured to form a cross - linked ethylene - Si polymer having structure (2).

[0090] In one embodiment, the method includes providing a first composition comprising (i) an ethylene-SiH polymer, (ii) a monoketone coagent, and (iii) a triarylborane. The ethylene-SiH polymer contains Si atoms present in the SiH comonomer. The monoketone coagent contains a carbonyl moiety. As used herein, the “carbonyl:SiH molar ratio” is the ratio of the number of moles of carbonyl groups present in the monoketone coagent to the number of moles of Si atoms present in the ethylene-SiH polymer. This process includes components (i)-(iii) and provides a first composition having a carbonyl:SiH molar ratio of 0.25 to 2.5, or 0.5 to 2.0, or 0.50 to 1.5, and performing a first melt blend on the first composition at a temperature of 80° C. to 200° C. to form a functionalized ethylene-Si polymer. In one embodiment, the monoketone coagent is acetophenone and the functionalized ethylene-Si polymer has structure (1). The functionalized ethylene-Si polymer (having structure (1)) has a gel content of 0% or greater than 0% to less than 2.5%. This process further includes performing a second melt blend on a second composition of (iv) a functionalized ethylene-Si polymer (having structure (1) and having a gel content of 0% or greater than 0% to less than 2.5%) and (v) a curing catalyst, and then moisture-curing the second composition to form a crosslinked ethylene-Si polymer having structure (2).

[0091] In one embodiment, the process comprises (i) a first composition comprising 95 wt% to 98 wt% of an ethylene / α-olefin / -SiH terpolymer, (ii) 1 wt% to 10 wt%, or 3 wt% to 8 wt% of a monoketone aid which is acetophenone, and (iii) 5 ppm to 5000 ppm, or 10 ppm to 100 ppm of a trialkylborane, and performing a first melt blend 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 (the first composition having a carbonyl:SiH molar ratio of 0.25 to 2.5, or 0.5 to 2.0, or 0.5 to 1.5), to form a functionalized ethylene Si-H polymer having structure (1) and a gel content of from 0% or greater than 0% to less than 2.5%. The method further comprises (iv) performing a second melt blend on a second composition comprising the functionalized ethylene-Si polymer and (v) a curing catalyst which is DBSA, the second composition (after the second melt blend) being moisture-cured to form a crosslinked ethylene-Si polymer having structure (2).

[0092] The present disclosure provides a composition. In one embodiment, the composition comprises a functionalized ethylene-Si polymer having structure (1) Structure (1)

[0093]

Chemical formula

[0094] The crosslinked ethylene-Si polymer composition having structure (1) has the following properties: (i) a density of 0.86 g / cc to 0.88 g / cc, and / or (ii) 3000 ppm to 7000 ppm of silicon atoms, and / or (iii) one, some, or all of 1 ppm to 10 ppm of boron atoms.

[0095] The applicant has discovered a process for readily and predictably converting SiH groups to hydrolyzable groups such as alkoxysilanes and silyl esters by reacting the SiH moieties of an ethylene-SiH polymer with a carbonyl-containing co-agent, such as a monoketone co-agent, in the presence of a Lewis acid catalyst (e.g., triarylborane). This post-polymerization functionalization method can be applied not only to linear low density polyethylene (LLDPE), but also to low density polyethylene (LDPE) and high density polyethylene (HDPE). Further incorporation of a Bronsted acid catalyst (a curing catalyst such as DBSA) enables the resulting second composition to be curable when exposed to (atmospheric) moisture at ambient temperature to moderate temperatures (20 °C to 60 °C) and below the melting point of the ethylene-SiH polymer and / or below the melting point of the second composition. The ability of this method to enable ambient cure is unexpected and advantageous.

[0096] By way of example and not limitation, several embodiments of the present disclosure will now be described in detail in the following examples.

Examples

[0097] 1. Materials

[0098] The materials used in the comparative samples (CS) and the examples of the invention (IE) are provided in Table 1 below.

[0099]

Table 1

[0100] A. Synthesis and Properties of Polymers P1, P2, P3, P4, and P5 The ethylene / octene / silane copolymerization to produce Polymer 1 (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, by which the contents of the reactor were transferred to a dump pot to empty and released into the atmosphere. All the chemicals and the catalyst solution 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 the desired molar concentration solution. The solution was then diluted with ISOPAR-E or toluene to achieve the desired amount for the polymerization and drawn into a syringe for transfer to the catalyst shot tank.

[0101] In a typical polymerization, ISOPAR-E and 1-octene were loaded into the reactor via independent flow meters. The silane monomer was then added via a shot tank piped in 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. Ethylene was 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 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 at the time of catalyst injection, and thereafter, an exotherm and a decrease in reactor pressure were observed, indicating the success of the operation.

[0102] Next, ethylene was added using a pressure controller to maintain the reaction pressure set point in the reactor. The polymerization reaction was carried out over a set time or until ethylene uptake was complete. Then, 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 onto a tray, which was placed in a draft to allow the solvent to evaporate overnight. Next, 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.

[0103] Interpolymers 2 - 5 (ethylene - SiH polymers) were each prepared in a 1 - gallon polymerization reactor filled with hydraulic oil and operated under steady - state conditions. Detailed synthesis information is provided for some of the listed examples. The solvent was ISOPAR - E supplied by ExxonMobil Chemical Company. 5 - Hexenyldimethylsilane (HDMS) supplied by Gelest was used as the comonomer and was purified prior to use with AZ - 300 alumina supplied by UOP Honeywell. HDMS was fed to the reactor as a 22 wt% solution in ISOPAR - E. The reactor temperature was measured at or near the reactor outlet. The interpolymers were isolated and pelletized. The polymerization conditions are listed in Tables 1C - 1E and the catalysts are shown in Table 1B. The polymer properties for each ethylene - SiH polymer P1, P2, P3, P4, P5 are shown in Tables 2A and 2B.

[0104] [Table 2]

[0105] [Table 3]

[0106] [Table 4]

[0107]

Table 5

[0108]

Table 6

[0109]

Table 7

[0110]

Table 8

[0111] B. Melt Blend Moisture-curable material (IE1-13, CS1-2): (i) ethylene-SiH polymer, (ii) monoketone auxiliary, and (iii) FAB toluene solution (75 mg / mL) (the first composition) were sequentially fed into a torque rheometer (Haake™ Rheomix QC Lab Mixers or HAAKE™ Rheomix OS Lab Mixers, Thermal Scientific) equipped with a 20 mL or 50 mL bowl and two roller rotors at 100 °C. After the addition of each component, the sample (the first composition) was mixed at 60 rpm for 1 minute (min) (the first melt blend). The final blend was mixed for an additional 4 minutes (the first melt blend). Then, the hot melt was taken out of the blender to obtain a functionalized ethylene-Si polymer having structure (1). The SiH conversion rate of the functionalized Si-H polymer was analyzed using FTIR-ATR. (i) A second composition was prepared by blending the functionalized ethylene-Si polymer (having structure (1)), which was fed into the 20 mL bowl of the torque rheometer, melted at 100 °C, and mixed at 60 rpm for 1 minute (the second melt blend). Subsequently, the curing catalyst DBSA was added, and the blend was mixed for 5 minutes (the second melt blend) to obtain the second composition. The second composition was compression molded onto a torsion bar (thickness 1.7 mm) at 90 °C for 4 minutes under a force of 20,000 lbs.

[0112] Thermosetting material (CS3): Inside a sealable glass jar, POE pellets (98.2 wt%) were mixed with a curing additive (1.8 wt% dicumyl peroxide). The soaking process was carried out by shaking and absorbing for 4 hours until the liquid residue adhering to the glass jar was no longer visually observable. Then, the absorbed sample was melt blended in an RSI RS5000, RHEOMIX 600 mixer equipped with a CAM blade at 100 °C / 30 rpm for 6 minutes. The high-temperature sample was cooled in a Carver press (cooling platen) at 20,000 psi for 4 minutes to produce a "pancake sample" for further testing. The final sample was compression molded onto a plaque (thickness 1.7 mm) at 100 °C for 5 minutes under a force of 20,000 lbs.

[0113] C. Moisture Curing Moisture curing (IE1 - 13, CS1 - 2): The formed moisture - curable material (a 1.7 - mm - thick torsion bar made of the second composition) was subjected to different moisture - curing conditions: 1) 20°C, relative humidity (RH) 50%; 2) 25°C, 16 - 25% RH; 3) 50°C, 6 - 9% RH; 4) 50°C water bath; 5) 1% RH. Thermal curing (CS3): The formed thermosetting material was heated at 180°C for 10 minutes in a compression molding machine.

[0114] The amounts and ratios of components (i), (ii), (iii), (iv), and (v) in the obtained formulations CS1 - CS3 and IE1 - IE15 are shown in Table 3 below.

[0115]

Table 9

[0116]

Table 10

[0117] Figure 1 shows the temperature dependence of the storage modulus (G’) of the composition (IE2) using acetophenone as an auxiliary agent before and after moisture curing at 20°C and 50% RH. The G’ of the material increases with time, and the high - temperature plateau of the storage modulus suggests the formation of a cross - linked three - dimensional network structure after moisture curing, which is further confirmed by a gel content of 97%. FTIR - ATR shows the disappearance of the SiH peak at about 890 cm -1 and the disappearance of the SiH peak at about 890 cm -1As indicated by the appearance of the SiOC peak in, quantitative conversion of SiH in the functionalized ethylene-Si polymer to alkoxysilane was shown by mixing an ethylene-SiH polymer and acetophenone in the presence of FAB (Figure 2). The new peak at about 960 cm -1 can also be attributed to the resulting silyl ether structure. After exposure to moisture for 5 days (moisture curing), the peaks at 960 cm -1 and 1100 cm -1 both decreased significantly. On the other hand, a peak related to Si-O-Si appeared at about 1060 cm -1 , indicating the formation of siloxane crosslinks under ambient conditions.

[0118] Figures 3 to 13 show the temperature dependence of the storage modulus (G’) of different compositions (IE3 to 13) using acetophenone as an auxiliary before and after moisture curing under various conditions. In most cases, the G’ of the materials increased over time as a result of sample curing. The positive slope of the plateau storage modulus indicates that these materials formed a rubbery network. Despite the slower curing of IE7 containing 500 ppm of DBSA (Figure 7), IE7 still reached a gel content of 34% after 2 weeks.

[0119] Figure 14 shows the temperature dependence of the storage modulus (G’’) of the composition (CS1) without DBSA after exposure to moisture curing conditions. Little change was observed after 6 days, suggesting the need for the use of a Bronsted acid (curing catalyst) as a moisture curing catalyst.

[0120] Figure 15 shows the temperature dependence of the storage modulus (G’) of the composition (CS2) containing only SiH-POE and DBSA. Little change was observed after 7 days, suggesting that the conversion of SiH to silyl ether or silyl ester is essential for moisture curing to occur under ambient conditions.

[0121] Dicumyl peroxide (DCP) is commonly used to cure polyolefin elastomers by a radical mechanism. FIG. 16 shows the temperature dependence of the storage modulus (G’) of peroxide-cured POE, and its plateau G’ was much lower than that of the moisture-cured material due to a lower degree of chemical crosslinking.

[0122] 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 portions 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. It is a process, At temperatures between 80°C and 200°C, (i) Ethylene-SiH polymer and (ii) A monoketone as an adjuvant, (iii) A first melt blend is made with a first composition containing triarylborane, Forming a functionalized ethylene-Si polymer, At temperatures between 80°C and 200°C, (iv) The functionalized ethylene-Si polymer and (v) A second melt blend is performed on the second composition containing the curing catalyst, The above second composition is to be moisture-cured, A process comprising forming a crosslinked ethylene-Si polymer.

2. To provide a first composition having a carbonyl:SiH molar ratio of 0.25 to 2.5, The process according to claim 1, comprising forming a functionalized ethylene-SiH polymer having a gel content of 0% to less than 2.5%.

3. (i) 95% to 98% by weight of ethylene / α-olefin / -SiH terpolymer, (ii) 2% to 5% by weight of the above-mentioned auxiliary agent, The process according to claim 1, comprising providing a first composition comprising (iii) 5 ppm to 500 ppm of a trialkylborane.

4. The process according to claim 1, comprising forming a functionalized ethylene-SiH polymer having Si-O-C bonds.

5. Structure (1) 【Chemistry 1】 The process according to claim 1, comprising forming a functionalized ethylene-SiH polymer having (wherein n is an integer from 4 to 6).

6. (iv) 95% to 98% by weight of the functionalized ethylene / α-olefin / -SiH terpolymer, (v) To provide a second composition comprising a curing catalyst in a concentration of 100 ppm to 2000 ppm, The above second composition is to be moisture-cured, The process according to claim 1, comprising forming a crosslinked ethylene-Si polymer having Si-O-Si bonds.

7. Structure (2) 【Chemistry 2】 The process according to claim 6, comprising forming a crosslinked ethylene-SiH polymer having (wherein n is an integer from 4 to 6).

8. A composition, Structure (1) 【Transformation 3】 A composition comprising a functionalized ethylene-Si polymer having (wherein n is an integer between 4 and 6).

9. The composition according to claim 8, wherein the composition has a density of 0.86 g / cc to 0.88 g / cc.

10. The composition according to claim 8, comprising 3,000 ppm to 7,000 ppm of silicon atoms.

11. The composition according to any one of claims 8 to 10, comprising 1 ppm to 10 ppm of boron atoms.

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