Process and product for melt functionalizing a silicon hydride-containing polyolefin

Abstract

The present disclosure provides a process. In an embodiment, the process comprises melt blending (i) an olefin-SiH polymer with (ii) a monovinyl graft component having the structure (1) H2C=CH2-X in the presence of a platinum group metal catalyst, wherein X in structure (1) is a C4-C 20 heterohydrocarbyl group having one or more heteroatoms selected from the group consisting of O, N, and Si. The process includes grafting the monovinyl graft component onto the olefin-SiH polymer to form a functionalized olefin-Si polymer. The present disclosure also provides a functionalized olefin-Si polymer composition produced from the present process.

Description

Technical Field

[0001] Polyolefins have many advantages with respect to cost, mechanical robustness, chemical resistance, and composition range. However, polyolefins have limitations with respect to the functional groups they can contain. For example, the functionalization of ethylene-based polymers (polyethylene) is generally not compatible with solution-phase polyethylene synthesis. Radical high-pressure processes can produce polyethylene with polar functional groups, but this process is capital-intensive and has a limited composition range.

Background Art

[0002] Accordingly, there is a recognized need in the art for a process that can incorporate new functional groups into polyolefins, particularly polyethylene.

Summary of the Invention

[0003] The present disclosure provides a process. In an embodiment, the process includes melt-blending (i) an olefin-SiH polymer with (ii) a monovinyl graft component having structure (1) H2C=CH2-X in the presence of a platinum group metal catalyst, where X in structure (1) is a C4-C 20 heterohydrocarbyl group having one or more heteroatoms selected from the group consisting of O, N, and Si. The process includes grafting the monovinyl graft component onto the olefin-SiH polymer to form a functionalized olefin-Si polymer.

[0004] The present disclosure provides a composition. In an embodiment, the composition has structure (2):

[0005]

Chemical Formula

[0006] Definitions 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.

[0007] 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 disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.

[0008] 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).

[0009] 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.

[0010] 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.

[0011] 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 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.

[0012] "Dalton" is a unit of the molecular weight of a polymer, equal to the atomic mass unit, and is abbreviated as "Da" or "kDa" (kilodalton).

[0013] "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 contain 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).

[0014] "Hydrocarbon" (or "hydrocarbyl", "hydrocarbyl group") is a compound containing only hydrogen and carbon atoms.

[0015] 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).

[0016] 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 heterohydrocarbyl" or "substituted heterohydrocarbyl group") and similar terms, as used herein, refer to each heterohydrocarbon in which one or more hydrogen atoms are independently replaced by heteroatom groups.

[0017] 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.

[0018] An "olefinic polymer" or "polyolefin" is a polymer that contains (based on the total amount of polymerizable monomers) a majority mole percent 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.

[0019] "Polymer" is a polymeric compound prepared by polymerizing monomers, whether of the same kind or of different kinds. Thus, the general term "polymer" encompasses the term "homopolymer" (used to refer to a polymer prepared from only one kind of monomer, with the understanding that trace impurities may be incorporated into the polymer structure), and the term "interpolymer" as defined below herein. 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" each refer to the above-described copolymers prepared by polymerizing ethylene or propylene with one or more additional polymerizable α-olefin monomers. Polymers are often referred to as being "made of", "based on", "containing" a specific 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 specific 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.

[0020] "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).

[0021] Test Methods Density. Polymer plaques for density analysis were made using ASTM D4703. The density of each polymer was measured (g / cc or g / cm 3 ) using ASTM D792, Method B.

[0022] Differential Scanning Calorimetry (DSC). Differential Scanning Calorimetry (DSC) is used to measure the T m , T c , T g , and crystallinity of ethylene-based (PE) polymer samples and propylene-based (PP) polymer samples. Each sample (0.5 g) was compression molded into a film at 190 °C for 2 minutes at 5000 psi. A film sample of about 5 - 8 mg was weighed and placed in a DSC pan. The lid was crimped onto the pan to ensure a sealed atmosphere. Unless otherwise stated, the sample pan was placed in the DSC cell and then heated at a rate of 10 °C / min to a temperature of 180 °C for PE (230 °C for PP). The sample was held at this temperature for 3 minutes. Then, the sample was cooled at a rate of 10 °C / min to -90 °C for PE (-60 °C for PP) and held isothermally at that temperature for 3 minutes. Next, the sample was heated at a rate of 10 °C / min until completely melted (second heating). Unless otherwise stated, the melting point (T m ) and glass transition temperature (T g ) of each polymer were determined from the second heating curve, and the crystallization temperature (T c ) was determined from the first cooling curve. The peak temperature of each of T m and T c was recorded. The percent crystallinity can be calculated by dividing the heat of fusion (H f ) determined from the second heating curve by the theoretical heat of fusion of 292 J / g for PE (165 J / g for PP) and multiplying this amount by 100 (e.g., % crystallinity = (Hf / 292 J / g) × 100 for PE). In DSC measurements, it is common to observe multiple T m peaks, where the highest temperature peak is recorded as the T m of the polymer.

[0023] FTIR-ATR. The infrared spectrum was 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, then placed in the accessory and 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 in at least triplicate. SiH conversion rate. The SiH conversion rate is the mole % of SiH bonds in the ethylene-SiH polymer that become Si--C bonds ("SiC") as a result of the hydrosilylation reaction. The peak at 2920 cm -1 was normalized, and the SiH conversion rate was determined by setting the baseline to 0 at 942 cm -1 . Then, the conversion rate was determined using the Si-H peak at 887 cm -1 . %SiH conversion rate = 100 × (absorbance at 887 cm -1 after the hydrosilylation reaction) / (absorbance at 887 cm -1 before the hydrosilylation reaction).

[0024] Gel content analysis was performed using a Soxhlet extraction setup following a procedure similar to that described in ASTM D2765. A sample of known mass (m0) was placed in a pre-weighed glass fiber thimble (m t ) and extracted by boiling xylene (boiling point approximately 136 °C) under N2 for 15 hours. 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 formula.

[0025]

Equation

[0026] Gel permeation chromatography. For the P1 polymer, P2 polymer, and P3 polymer (in the 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 at 160 °C and the column compartment was set at 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.

[0027] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards with molecular weights in the range of 580 to 8,400,000 prepared in 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 at "0.025 grams in 50 milliliters" of solvent for molecular weights of 1,000,000 and above and at "0.05 grams in 50 milliliters" of solvent for molecular weights below 1,000,000. The polystyrene standards were dissolved with gentle stirring at 80 °C for 30 minutes. 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)):

[0028]

Equation

[0029] A fifth-degree polynomial was used to fit each polyethylene equivalent calibration point. Minor adjustments (approximately 0.375 - 0.445) were made to A to correct for column resolution and band broadening effects such that a linear homopolymer polyethylene standard would be obtained at 120,000 Mw. The total plate count of the GPC column set was performed using decane (prepared at "0.04 g in 50 milliliters" and dissolved for 20 minutes with gentle stirring). The plate count (Equation 2) and symmetry (Equation 3) were measured according to the following equations for a 200 microliter injection:

[0030]

Number

[0031]

Number

[0032] Samples were prepared in a semi - automatic mode using PolymerChar's "Instrument Control" software. The samples were weight - standardized at 2 mg / mL, and the solvent (containing 200 ppm of BHT) was added via a PolymerChar high - temperature autosampler to vials with septum caps that had been pre - sparged with nitrogen. The samples were dissolved at 160 °C for 2 hours under "low - speed" shaking.

[0033] Mn (GPC) 、Mw (GPC) 、and Mz (GPC) The calculations of Mn, Mw, and Mz 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, according to Equations 4 - 6, using the internal IR5 detector (measurement channel) of a PolymerChar GPC - IR chromatograph. Equations 4 - 6 are as follows:

[0034]

Number

[0035] 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 aligning 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 overall flow rate (effective flow rate) of the run. To facilitate the highest accuracy of the 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. Then, the first derivative of the quadratic equation was 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: effective flow rate = apparent flow rate × (RV(FM calibrated) / RV(FM sample)) (Equation 7). The processing of the flow marker peak was performed via PolymerChar GPCOne (trademark) software. For acceptable flow corrections, the effective flow rate should be within ±0.7% of the apparent flow rate.

[0036] For the P4 polymer (in the Examples chapter), 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 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 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.

[0037] 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-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 before 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)):

[0038]

Equation

[0039] A third-degree polynomial was used to fit each polyethylene equivalent calibration point. A slight adjustment was made to A (from approximately 0.375 to 0.445) to correct for column resolution and band broadening effects such 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:

[0040]

Equation

[0041]

Equation

[0042] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software to target sample weight of 2 mg / mL and add solvent (containing 200 ppm BHT) to septa-capped vials via the PolymerChar high temperature autosampler. Samples were dissolved at 160 degrees Celsius under "fast" shaking for 2 hours.

[0043] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation of was based on GPC results using the internal IR5 detector (measurement channel) of a PolymerChar GPC-IR chromatograph according to Equations 4-6 using PolymerChar's GPCOne™ software, baseline subtracted IR chromatograms 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. Equations 4-6 are as follows:

[0044]

number

[0045] 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 aligning 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 measurements 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. Then, the first derivative of the quadratic equation was 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)) (Equation 7). The processing of the flow marker peak was performed via PolymerChar GPCOne (trademark) software. For acceptable flow corrections, the effective flow rate should be within ±0.7% of the apparent flow rate.

[0046] For the P5 polymer (in the Examples chapter), 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 consisted of 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 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.

[0047] The GPC column set was calibrated 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 (about 5 mg) to obtain 20 molecular weight points in the range of about 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 before injecting into the chromatography system. The peak molecular weight of the polystyrene standards was converted to polypropylene molecular weight using Equation 8 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0048] [Number] (where M is the molecular weight, A has a value of 0.647, and B is equal to 1.0).

[0049] A third-degree polynomial was used to fit each polypropylene equivalent calibration point. The total plate count of the GPC column set was determined using decane (3% v / v in TCB introduced via a micropump). The plate count (Equation 9) and symmetry (Equation 3) were measured according to the following equations for a 200 microliter injection:

[0050]

Number

[0051]

Number

[0052] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / mL. A solvent (containing 200 ppm BHT) was added to vials with septum caps via a PolymerChar high-temperature autosampler. The samples were dissolved at 160 °C for 2 hours under "high-speed" shaking.

[0053] Mn (GPC) 、Mw (GPC) 、and Mz (GPC) were calculated using PolymerChar GPCOne™ 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, and were based on the GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph in accordance with Equations 10 - 12. Equations 10 - 12 are as follows.

[0054] [Number]

[0055] To monitor the deviation over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. Using this flow rate marker (FM), the RV (RV(FM sample)) of each decane peak in the sample was aligned with the RV (RV(FM calibrated)) of the decane peak within the narrow standard calibration, thereby linearly correcting the pump flow rate (apparent flow rate) of each sample. 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) for the entire run. To facilitate the highest accuracy of the 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. Then, the first derivative of the quadratic equation was 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)) (Equation 7). The processing of the flow marker peak was performed via PolymerChar GPCOne™ software. For an acceptable flow correction, the effective flow rate should be within ±0.7% of the apparent flow rate.

[0056] Melt Index. The melt index of the ethylene polymer (or "I2") is measured according to ASTM D-1238, Condition 190°C / 2.16 kg (melt index I10 at 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 polymer is measured according to ASTM D-1238, Condition 230°C / 2.16 kg.

[0057] Nuclear Magnetic Resonance (NMR) Characterization of Terpolymers. 13 For 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 repeatedly vortexed and heated to obtain a homogeneous flowing fluid. 13 The 13C NMR spectrum was obtained on a BRUKER AVANCE 600 MHz spectrometer equipped with a 10 mm C / H DUAL cryoprobe. The following acquisition parameters were used: a waiting time of 60 seconds, a 90-degree pulse of 12.0 μs, and 256 scans. The spectrum center was 100 ppm, and the spectrum width was 250 ppm. All measurements were performed without rotating the sample at 110°C. 13 The 13C NMR spectrum was referenced to "74.5 ppm" for the resonance peak of the solvent. For samples containing Cr, data were acquired with a "waiting time of 7 seconds" and 1024 scans.

[0058] 1For the 1H NMR experiments, each sample was dissolved in tetrachloroethane-d2 (with or without 0.001 M Cr(acac)3) in an 8 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 1H NMR spectra were obtained on a BRUKER AVANCE 600 MHz spectrometer equipped with a 10 mm C / H DUAL cryoprobe. Standard single pulse 1 1H NMR experiments were performed. The following acquisition parameters were used: a repetition delay of 70 s, a 90° pulse of 17.2 μs, and 32 scans. The spectral center was 1.3 ppm and the spectral width was 20 ppm. All measurements were performed without spinning the sample at 110 °C. 1 1H NMR spectra were referenced to "5.99 ppm" for the resonance peak of the solvent (residual protonated tetrachloroethane). For samples containing Cr, data were acquired with a "16 s delay" and 128 scans.

[0059] SiH conversion rate. See the FTIR-ATR test method. The (%) SiH conversion rate is described below the FTIR-ATR test method.

DETAILED DESCRIPTION OF THE INVENTION

[0060] The present disclosure provides a process. In an embodiment, the process includes melt blending (i) an olefin-SiH polymer with (ii) a monovinyl graft component having structure (1) H2C=CH2-X in the presence of a platinum group metal catalyst, where X in structure (1) is a heteroalkyl group containing a moiety selected from epoxide, ether, ester, alcohol, alkyl chain, amine, anhydride, ketone, phenol, and combinations thereof. The process includes grafting the monovinyl graft component onto the olefin-SiH polymer to form a functionalized olefin-Si polymer.

[0061] This process involves melt blending (i) an olefin-SiH polymer with (ii) a monovinyl graft component in the presence of a platinum group metal catalyst. The olefin-SiH polymer can be an ethylene-SiH polymer (ethylene-based polymer) or a propylene-SiH polymer (propylene-based polymer). In an embodiment, the olefin-SiH polymer is an ethylene-SiH polymer and is composed of (1) ethylene monomer, (2) 0.1 wt% to 3.9 wt% of SiH comonomer, and (3) optional C3-C 12 α-olefin ter monomer or C4-C8 α-olefin ter monomer.

[0062] In an embodiment, the olefin-SiH polymer is a propylene-SiH polymer and is composed of (1) propylene monomer, (2) 0.1 wt% to 3.9 wt% of SiH comonomer, and (3) optional C2 α-olefin (ethylene) or C4-C8 α-olefin ter monomer.

[0063] 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 and 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, and E and F may be the same or different. When E is a hydrocarbyl group, F is a hydrocarbyl group, and E and F may be the same hydrocarbyl group). Non-limiting samples 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:

[0064]

Chemical formula

[0065] In an embodiment, the SiH comonomer is selected from allyldimethylsilane, hexenyldimethylsilane, octenyldimethylsilane, and hexenyltetramethyldisiloxane.

[0066] In an 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 each ethylene / propylene SiH terpolymer, ethylene / butene / SiH terpolymer, ethylene / hexene / SiH terpolymer, ethylene / octene / SiH terpolymer, and ethylene / ethylidene norbornene / SiH terpolymer, respectively.

[0067] In an 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, ethylene / octene / allyldimethylsilane, and combinations thereof.

[0068] In an embodiment, the ethylene-SiH polymer is ethylene / octene / hexenyldimethylsilane.

[0069] In an embodiment, the ethylene-SiH polymer is an ethylene / octene / allyldimethylsilane (allyldimethylsilane, ADMS) terpolymer.

[0070] In an embodiment, the olefin-SiH polymer is a propylene / ethylene SiH polymer. In a further embodiment, the propylene / ethylene / SiH polymer (propylene-based polymer) is a propylene / ethylene / HDMS terpolymer.

[0071] The monovinyl graft component is melt blended with the ethylene-SiH polymer in the presence of a platinum group metal catalyst. The monovinyl monovinyl graft component has a single vinyl group and has the structure (1): Structure (1) H2C=CH2-X (In the formula, X of structure (1) is a C4-C heteroalkyl group having one or more heteroatoms selected from O, N, and Si.) 20 It has. In an embodiment, "X" of structure (1) is a C4-C heteroalkyl group containing a moiety selected from epoxide, ether, ester, alcohol, amine, anhydride, ketone, phenol, alkoxysilane, and combinations thereof. 20 It is a heteroalkyl group.

[0072] In an embodiment, the monovinyl graft component of structure (1) is a C4-C heteroalkyl group having one or more heteroatoms selected from O, N, and Si. 20 Or a C6-C heteroalkyl group. 18 It is a heteroalkyl group. In a further embodiment, structure (1) is selected from allyl glycidyl ether, 5-hexen-2-one, eugenol, methyl 10-undecenoate, vinyltriethoxysilane, N,N-diethylallylamine, 2,6-di-tert-butyl-4-vinylphenol, and tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate.

[0073] This process involves melt blending (i) an ethylene-SiH polymer with (ii) a monovinyl graft component in the presence of a platinum group metal catalyst. As used herein, "platinum group metal catalyst" is an organometallic compound containing a metal selected from iridium (Ir), palladium (Pd), platinum (Pt), rhodium (Rh), and ruthenium (Ru), and the organometallic compound accelerates the hydrosilylation reaction between the SiH moiety of the ethylene-SiH polymer and the vinyl group of the monovinyl graft component of structure (1).

[0074] In an embodiment, the platinum group metal catalyst contains a metal selected from Ir, Pt, and Rh. In a further embodiment, the platinum group metal catalyst contains platinum (Pt).

[0075] In an embodiment, the platinum group metal catalyst is (H3O)2(PtCl6)(H2O) in a solution of isopropyl alcohol x ("Speier catalyst") (wherein x is an integer from 0 to 6, or x is 0, or 1, or 2, or 3, or 4, or 5, or 6).

[0076] The ethylene-SiH polymer (or propylene-SiH polymer), the monofunctional monovinyl graft component, and the platinum group metal catalyst are melt blended or otherwise mixed at a temperature sufficient to completely homogenize the mixture for a sufficient length of time. The melt blending is carried out by batch mixing or continuous mixing at a temperature of 80°C to 160°C or 80°C to 120°C for 1 minute to 20 minutes, or 2 minutes to 15 minutes, or 3 minutes to 10 minutes. The melt blending initiates a hydrosilylation reaction between the Si-H moiety of the ethylene-SiH polymer (or propylene-SiH polymer) and the vinyl group of the monovinyl graft component in the presence of the platinum group metal catalyst, thereby grafting the monovinyl graft component onto the ethylene-SiH polymer (or propylene-SiH polymer) to form a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer). As used herein, "functionalized ethylene-Si polymer" is the reaction product between an ethylene-SiH polymer and a monovinyl graft component, whereby the monovinyl graft component is grafted onto the ethylene-SiH polymer at the silicon atom of the Si-H moiety by an Si-C-C-Y bond (wherein "Y" is a C4 to C 20 heterohydrocarbyl group or a C6 to C 18 heterohydrocarbyl group) or otherwise covalently bonded. In an embodiment, "Y" is a C4 to C 20 heterohydrocarbyl group and contains a moiety selected from epoxide, ether, ester, alcohol, amine, anhydride, ketone, phenol, and combinations thereof.

[0077] As used herein, "functionalized propylene-Si polymer" is the reaction product between a propylene-SiH polymer and a monovinyl graft component, whereby the monovinyl graft component is grafted to the propylene-SiH polymer at the silicon atom of the SiH moiety by means of an Si-C-C-Y bond (wherein "Y" is a C4-C 20 heterohydrocarbyl group or a C6-C 18 heterohydrocarbyl group) or otherwise covalently bonded. In embodiments, "Y" is a C4-C 20 heterohydrocarbyl group and contains a moiety selected from the group consisting of epoxides, ethers, esters, alcohols, amines, anhydrides, ketones, phenols, and combinations thereof.

[0078] In embodiments, the process comprises the following structure (2):

[0079]

Chemical formula

[0080]

Chemical formula

[0081] In an embodiment, the melt blend is carried out by batch mixing in a batch mixer. The ethylene-SiH polymer (or propylene-Si polymer), the monovinyl graft component, and the platinum group metal catalyst are added to the batch mixer and melt blended at a temperature of 80°C to 160°C or 100°C to 140°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 functionalized ethylene-Si polymer (or propylene-Si polymer) having structure (2) is formed.

[0082] In an embodiment, the melt blend is carried out by continuous mixing or extrusion in an extruder. The extruder can be a continuous single-screw extruder or a continuous twin-screw extruder. The ethylene-SiH polymer (or propylene-Si polymer), the monovinyl graft component, and the platinum group metal catalyst are introduced into the extruder and melt blended at a temperature of 80°C to 160°C or 100°C to 140°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. Non-limiting examples of suitable extruders include FARREL (trademark) 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 that is a functionalized ethylene-Si polymer (or propylene-Si polymer) having structure (2).

[0083] In an embodiment, the process comprises (i) 50 wt% to 98 wt% of ethylene / C3-C 12An ethylene-SiH polymer, which is an α-olefin / SiH terpolymer, is melt blended with (ii) 50 wt% to 2 wt% of a monovinyl graft component of structure (1) (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) in the presence of a platinum group metal catalyst of 1 ppm to 60 ppm or 2 ppm to 50 ppm to form a functionalized ethylene-Si polymer having structure (2).

[0084] In an embodiment, the process includes forming a functionalized ethylene-Si polymer (having structure 2) having a gel content of less than 0% to 2.5%. The gel content is measured according to ASTM D2765-16.

[0085] In an embodiment, the process includes (i) 50 wt% to 98 wt% of ethylene / C3-C 12 An ethylene-SiH polymer, which is an α-olefin / SiH terpolymer, is melt blended with (ii) 50 wt% to 2 wt% of a monovinyl graft component of structure (1) (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) in the presence of a platinum group metal catalyst of 1 ppm to 60 ppm or 2 ppm to 50 ppm at a temperature of 80 °C to 120 °C for 1 minute to 20 minutes to convert more than 90%, or more than 93%, or more than 95%, or more than 95% to 99% of SiH to SiC to form a functionalized ethylene-Si polymer having structure (2).

[0086] In an embodiment, the process is carried out (i) in the absence of a solvent, (ii) in the absence of a peroxide, and (iii) in a combination of (i) and (ii). As used herein, "solvent" is a liquid comprising water, hydrocarbons, alcohols, ketones, esters, acids, bases, and combinations thereof that is present in an amount sufficient to dissolve an ethylene-SiH polymer (or propylene-Si polymer) at a temperature higher than the melting temperature of the (2) ethylene-SiH polymer (or propylene-Si polymer). Since the ethylene-SiH polymer (or propylene-Si polymer) is not soluble in isopropanol, it is understood that the carrier liquid (isopropanol) for the Speier catalyst is not a solvent as defined herein. Even if soluble, the amount of isopropanol is very small so that the ethylene-SiH polymer (or propylene-Si polymer) does not dissolve, and since the boiling point of isopropanol is 82.5 °C, isopropanol evaporates at the melting temperature of the ethylene-SiH polymer (or propylene-Si polymer).

[0087] In an embodiment, the process comprises melt blending (i) an ethylene / C3-C 12 α-olefin / SiH terpolymer ethylene-SiH polymer that is 50 wt% to 98 wt% and (ii) a monovinyl graft component of structure (1) that is 50 wt% to 2 wt% (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) in the presence of a platinum group metal catalyst of 1 ppm to 60 ppm or 2 ppm to 50 ppm at a temperature of 80 °C to 120 °C for 1 minute to 20 minutes. The monovinyl graft component is selected from allyl glycidyl ester, 5-hexen-2-one, eugenol, methyl 10-undecenoate, vinyltriethoxysilane, and 2,6-di-tert-butyl-4-vinylphenol, triethylamine, and combinations thereof. The process comprises forming a functionalized ethylene-Si polymer having structure (2).

[0088] In an embodiment, the process includes melt blending (i) 50 wt% to 98 wt% of an ethylene-SiH polymer that is an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer and (ii) 50 wt% to 2 wt% of a monovinyl graft component of structure (1) that is an allyl glycidyl ester (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) in the presence of a platinum group metal catalyst of 1 ppm to 60 ppm or 2 ppm to 50 ppm at a temperature of 80°C to 120°C for 1 minute to 20 minutes. The process includes forming a functionalized ethylene-Si polymer having structure (3).

[0089]

Chemical formula

[0090] In an embodiment, the process includes melt blending (i) 50 wt% to 98 wt% of an ethylene-SiH polymer that is an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer and (ii) 50 wt% to 2 wt% of a monovinyl graft component of structure (1) that is 5-hexen-2-one (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) in the presence of a platinum group metal catalyst of 1 ppm to 60 ppm or 2 ppm to 50 ppm at a temperature of 80°C to 120°C for 1 minute to 20 minutes. The process includes forming a functionalized ethylene-Si polymer having structure (4).

[0091]

Chemical formula

[0092] In an embodiment, the process includes melt blending (i) 50 wt% to 98 wt% of an ethylene-SiH polymer, which is an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, and (ii) 50 wt% to 2 wt% of a monovinyl graft component of structure (1), which is eugenol (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component), at a temperature of 80°C to 120°C for 1 minute to 20 minutes in the presence of a platinum group metal catalyst of 1 ppm to 60 ppm or 2 ppm to 50 ppm. The process includes forming a functionalized ethylene-Si polymer having structure (5).

[0093]

Chemical formula

[0094] In an embodiment, the process includes melt blending (i) 50 wt% to 98 wt% of an ethylene-SiH polymer, which is an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, and (ii) 50 wt% to 2 wt% of a monovinyl graft component of structure (1), which is methyl 10-undecenoate (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component), at a temperature of 80°C to 120°C for 1 minute to 20 minutes in the presence of a platinum group metal catalyst of 1 ppm to 60 ppm or 2 ppm to 50 ppm. The process includes forming a functionalized ethylene-Si polymer having structure (6).

[0095]

Chemical formula

[0096] In an embodiment, the process includes melt blending (i) 50 wt% to 98 wt% of an ethylene-SiH polymer that is an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer and (ii) 50 wt% to 2 wt% of a monovinyl graft component of structure (1) that is vinyltriethoxysilane (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst at a temperature of 80°C to 120°C for 1 minute to 20 minutes. The process includes forming a functionalized ethylene-Si polymer having structure (7).

[0097]

Chemical formula

[0098] In an embodiment, the process includes melt blending (i) 50 wt% to 98 wt% of an ethylene-SiH polymer that is an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer and (ii) 50 wt% to 2 wt% of a monovinyl graft component of structure (1) that is 2,6-di-tert-butyl-4-vinylphenol (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst at a temperature of 80°C to 120°C for 1 minute to 20 minutes. The process includes forming a functionalized ethylene-Si polymer having structure (8).

[0099]

Chemical formula

[0100] In an embodiment, the process includes melt blending (i) 50 wt% to 98 wt% of an ethylene-SiH polymer, which is an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, and (ii) 50 wt% to 2 wt% of a monovinyl graft component of structure (1), which is diethylallylamine (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component), at a temperature of 80°C to 120°C for 1 minute to 20 minutes in the presence of a platinum group metal catalyst of 1 ppm to 60 ppm or 2 ppm to 50 ppm. The process includes forming a functionalized ethylene-Si polymer having structure (9).

[0101]

Chemical formula

[0102] In an embodiment, the process includes melt blending (i) 50 wt% to 98 wt% of an ethylene-SiH polymer, which is an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, and (ii) 50 wt% to 2 wt% of a monovinyl graft component of structure (1), which is diethylallylamine (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component), at a temperature of 80°C to 120°C for 1 minute to 20 minutes in the presence of a platinum group metal catalyst of 1 ppm to 60 ppm or 2 ppm to 50 ppm. The process includes forming a functionalized ethylene-Si polymer having structure (9).

[0103]

Chemical formula

[0104] In an embodiment, the process comprises melt blending (i) an ethylene-SiH polymer that is a 50 wt% to 98 wt% ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, and (ii) a monovinyl graft component of structure (1) that is tert-butyl bicyclo[2.2.1]hepta-5-ene-2-carboxylate (weight percent based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) in the presence of a platinum group metal catalyst of 1 ppm to 60 ppm or 2 ppm to 50 ppm at a temperature of 80 °C to 120 °C for 1 minute to 20 minutes. The process comprises forming a functionalized ethylene-Si polymer having structure (10).

[0105] Applicants have unexpectedly found that the monovinyl graft component does not undergo crosslinking during hydrosilylation. The resulting functionalized ethylene-Si polymer of structure (2) has little or no gel content, i.e., a gel content of 0% to less than 2.5%. Applicants have found a process for producing a functionalized polyolefin (functionalized polyethylene) without using a solvent (solvent-free process), without using a peroxide (peroxide-free process), and without using / requiring an inhibitor or antioxidant (antioxidant-free process). This process advantageously reduces production costs. In this process, for example, monomer grafts are obtained as opposed to oligo / polymer grafts in solvent-based free radical grafting of polyethylene. It is unexpected that monomer grafts can be obtained in polyethylene by this process.

[0106] The present disclosure provides a composition. In an embodiment, the composition comprises a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (2),

[0107]

Chemical formula

[0108]

Chemical formula

[0109] In an embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (3):

[0110]

Chemical formula

[0111] In an embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (4):

[0112]

Chemical formula

[0113] In an embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (5):

[0114]

Chemical formula

[0115] In an embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (6):

[0116]

Chemical formula

[0117] In an embodiment, the composition has structure (7):

[0118]

Chemical formula

[0119] In an embodiment, the composition has structure (8):

[0120]

Chemical formula

[0121] In an embodiment, the composition has structure (9):

[0122]

Chemical formula

[0123] In an embodiment, the composition has structure (10):

[0124]

Chemical formula

[0125] By way of example and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples.

Example

[0126] A. Synthesis and Properties of Polymers P1, P2, P3, P4, and P5 Ethylene / propylene / silane copolymerization to produce P5 (propylene-SiH polymer) was carried out in a batch reactor designed for homopolymerization and copolymerization of ethylene. 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, which transferred the contents of the reactor to a dump pot to empty it and release it into the atmosphere. All chemicals and catalyst solutions used in the polymerization were passed through a purification column before use. ISOPAR-E, propylene, 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 tallow 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.

[0127] In a typical polymerization, ISOPAR-E and propylene were loaded into the reactor via independent flow meters. Subsequently, the silane monomer was added via a shot tank piped therein through an adjacent glove box. After adding 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, after which an exotherm and a decrease in reactor pressure were observed, indicating the success of the operation.

[0128] Then, ethylene was added using a pressure controller to maintain the reaction pressure set point inside the reactor. The polymerization reaction was carried out over 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 onto a tray, which was placed in a draft to evaporate the solvent overnight. Then, 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.

[0129] Interpolymers P1, P2, and P3 (ethylene-SiH polymers) were each prepared in a 1-gallon polymerization reactor filled with hydraulic pressure and operated under steady-state conditions. The solvent was ISOPAR-E supplied by ExxonMobil Chemical Company. 5-Hexenyl dimethylsilane (HDMS) supplied by Gelest was used as the comonomer and was purified with AZ-300 alumina supplied by UOP Honeywell before use. 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 to 1E, and the catalysts are shown in Table 1B. The polymer properties of each ethylene / octene / silane interpolymer (SiH-POE) and ethylene / octene interpolymer (POE) are shown in Tables 2A and 2B.

[0130] Interpolymer P4 (ethylene-SiH polymer) was prepared in a 100 mL polymerization reactor filled with hydraulic pressure and operated under steady-state conditions. The solvent was ISOPAR-E supplied by ExxonMobil Chemical Company. Allyl dimethylsilane (ADMS) was used as the comonomer and was purified with AZ-300 alumina supplied by UOP Honeywell before use. The ADMS synthesis is described below. ADMS was fed to the reactor as a 250 g / L solution in ISOPAR-E. The reactor temperature was measured at or near the reactor outlet. The polymer solution was collected in a tray, placed in a draft, and the solvent was evaporated overnight. The tray containing the remaining polymer was then 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. The polymerization conditions are listed in Tables 1C to 1E, and the catalysts are shown in Table 1B. The polymer properties of each olefin-SiH polymer are shown in Tables 2A and 2B.

[0131] B. ADMS Synthesis A nitrogen-purged, dried, 30-gallon glass-lined steel reactor was charged with 35 kg of dry toluene (obtained from Sigma-Aldrich (>99%) and dried to less than 5 ppmw water via an alumina column). Next, 20.2 L of 1 M allylmagnesium bromide in diethyl ether (Sigma-Aldrich) was added to the reactor and stirred at 25 °C and 120 rpm. 2 L of dimethylchlorosilane (DOWSIL™ Z-1219) was added to obtain 1.8 kg of allyldimethylsilane (ADMS) in toluene and diethyl ether. The mixture was then transferred to a 20-gallon glass-lined steel reactor, and the volatiles were overhead distilled at a jacket temperature of 110–140 °C and 800 torr. The ADMS mixture was further distilled using a 12-L batch still (4 feet × 2 inches) packed column to obtain approximately 1.2 kg of ADMS.

[0132]

Table 1

[0133]

Table 2

[0134]

Table 3

[0135]

Table 4

[0136]

Table 5

[0137] [Table 6] * Silane mol% determined by 13C NMR (P1, P2, P3, and P5) and 1H NMR (P4) based on the total moles of monomers in the polymer. ** Silane weight% calculated from the mol% and based on the weight of the interpolymer.

[0138] [Table 7]

[0139] C. Process 1. Materials The materials used in the comparative sample (CS) and the examples of the present invention (IE) are provided in Table 3 below.

[0140] [Table 8]

[0141] Olefin-SiH polymers are listed in Table 4. Monovinyl graft components 1-8 were obtained from Sigma-Aldrich or Oakwood Chemical and used without further modification. The synthesis of monovinyl graft component 7 is provided in the literature (Org. Lett. 2005, 3721). Monovinyl graft component 8 was obtained from TCI America.

[0142] [Table 9]

[0143] Examples 1 to 5 of the present invention For Examples (IE) 1 to 5 of the present invention, 30 to 35 g (shown in Table 5) of an olefin-SiH polymer was added to a Haake mixer (Haake mixer equipped with a 50 cc mixing bowl) preheated at a specific temperature (shown in Table 5) at a blending speed of 100 rpm. Mixing was continued until the polymer became homogeneous. A monovinyl graft component was added and mixing was continued for 1 to 5 minutes. Then, a catalyst was added (shown in Table 5 below) and the hydrosilylation reaction was allowed to proceed for 10 minutes. At the end of the hydrosilylation reaction, the functionalized polymer was recovered. Purification was carried out by precipitation from hot toluene into methanol. The obtained substance was characterized by proton NMR spectroscopy in 1,1,2,2-tetrachloroethane-d2. The characteristics of the obtained functionalized polymer are provided in Table 5 below.

[0144] Examples 11 to 12 of the present invention For IE11 and IE12, 35 to 50 g (shown in Table 5) of a silane polymer was added to a heating jar equipped with an overhead stirrer in a nitrogen-filled glove box at a specific temperature (shown in Table 5) at a blending speed of 100 rpm. Mixing was continued until the polymer became homogeneous. A monovinyl graft component (5 molar equivalents relative to the silane) was added and mixing was continued for 1 to 5 minutes. Then, a catalyst was added (shown in Table 5 below) and the hydrosilylation reaction was allowed to proceed for 10 minutes.

[0145] Examples 13 to 16 of the present invention For IE13 - IE16, the ethylene - SiH polymer was processed in a Thermo Fisher Scientific Process 11 twin - screw extruder (TSE) with a 11 - mm diameter held within the chemical draft. This is a small - scale parallel co - rotating TSE with a clam - shell barrel. The extruder length is 44 L / D, including a 40 L / D barrel and a 4 L / D extension. The barrel has six multi - functional barrel ports for reagent injection or vacuum and eight separate heating zones along the barrel. To facilitate feeding, the polymer was ground to a particle size of less than 2 mm before use. A MovaColor MCBALANCE single - screw gravimetric feeder was used to supply the polymer to the extruder at a rate of 180 g / h. A 1000D ISCO pump was used at barrel position #4 to inject the Speier catalyst solution in allyl glycidyl ether into the extruder. To achieve the desired loadings of allyl glycidyl ether and catalyst, a solution with a concentration of 0.18 - 0.50 mg Speier catalyst / mL allyl glycidyl ether was formed. A residence time of 2.5 minutes was used. Generally, the extruder was run for about 5 minutes for equilibration and then about 10 - 20 g of sample was collected for analysis.

[0146] Purification was carried out by precipitating the functionalized polymer from hot toluene into methanol. The resulting purified functionalized polymer was characterized by proton NMR spectroscopy in 1,1,2,2 - tetrachloroethane - d2.

[0147]

Table 10

[0148] Comparative Samples 1 - 2 For Comparative Samples (CS) 1 - 2, 35 g of the silane polymer (shown in Table 5) was added to a Haake mixer preheated to 100 °C (Haake mixer equipped with a 50 cc mixing bowl) at a blending speed of 100 rpm. Mixing was continued until the silane polymer became homogeneous. The monovinyl graft component was added and mixing was continued for 1 - 5 minutes. Then, the catalyst was added (shown in Table 5) and the hydrosilylation reaction was allowed to proceed for 10 minutes. At the end of the hydrosilylation reaction, the functionalized polymer was recovered. Purification was performed by precipitation from hot toluene into methanol. The resulting material was characterized by proton NMR spectroscopy in 1,1,2,2 - tetrachloroethane - d2. The properties of the resulting functionalized polymers are provided in Table 4 below.

[0149] CS1 provides a material with an unacceptable level of gel content (13%) when the Karstedt catalyst is applied to a polymer with high molecular weight (P1 polymer Mw 100 kDa), whereas IE6 (P3 polymer Mw 50 kDa) demonstrates an acceptable gel content (1%).

[0150] IE16 demonstrates that with a catalyst loading lower limit of 3 ppm Pt, it can produce a functionalized ethylene - Si polymer with a gel content of 0% or greater than 0% to 3% (IE16 - 2% gel content) and a desired product of greater than 75% (IE16 79% desired product).

[0151] The Applicant has found it unexpected that a functionalized ethylene-Si polymer can be produced by melt blending an ethylene-SiH polymer with a monovinyl graft component of structure (1) at a temperature of 80 °C to 120 °C, obtaining a SiH conversion rate of over 95% and a gel content of 0% to 3% (as shown in IE1 to 16). The use of non-radical chemistry enables the grafting of functional groups that would otherwise react undesirably in the presence of a radical initiator. In particular, antioxidant (hindered phenol) functional groups and amine functional groups have undesirable reactivity in the presence of a radical initiator. The present process and its use of non-radical grafting are beneficial for introducing antioxidant (hindered phenol) functional groups and amine functional groups, such as those in structures 8 and 9 for example.

[0152] The present disclosure is not limited to the embodiments and examples contained herein, and it is particularly intended to include modified forms of those embodiments, including parts of embodiments and combinations of elements of different embodiments, to the extent that they fall within the scope of the following claims.

Claims

1. A process comprising: In the presence of a platinum group metal catalyst, (i) an olefin-SiH polymer, (ii) Structure (1): Structure (1) H ２ C=CH ２ -X wherein X in structure (1) is a C group having one or more heteroatoms selected from the group consisting of O, N, and Si. ４ ~C ２０ a monovinyl graft component having a heterohydrocarbyl group; grafting said monovinyl graft component onto said olefin-SiH polymer to form a functionalized olefin-Si polymer; A process involving:

2. The process of claim 1, wherein the olefin-SiH polymer is selected from the group consisting of ethylene-SiH polymers and propylene-SiH polymers.

3. C of the structure (1) ４ ~C ２０ 10. The process of claim 1, wherein the heterohydrocarbyl group comprises a moiety selected from the group consisting of epoxides, ethers, esters, alcohols, amines, anhydrides, ketones, phenols, and combinations thereof.

4. 10. The process of claim 1, wherein the functionalized olefin-SiH polymer has a gel content of 0% to less than 2.5% as measured according to ASTM D2765-16.

5. melt blending at a temperature of 80°C to 120°C for 1 minute to 20 minutes; converting greater than 90% of the SiH to SiC; 2. The process of claim 1, comprising:

6. 10. The process of claim 1 conducted (i) in the absence of a solvent, (ii) in the absence of a peroxide, and (iii) a combination of (i) and (ii).

7. 2. The process of claim 1, wherein the monovinyl graft component of structure (1) is selected from the group consisting of allyl glycidyl ester, 5-hexen-2-one, eugenol, methyl 10-undecenoate, vinyltriethoxysilane, 2,6-di-tert-butyl-4-vinylphenol, N,N-diethylallylamine, and 2,6-tert-butylbicyclo[2.2.1]hept-5-ene-2-carboxylate.

8. The functionalized olefin-Si polymer has a —Si—C—C—Y bond, Si is a silicon atom, C is a carbon atom Y is a C group having one or more heteroatoms selected from the group consisting of O, N, and Si. ４ ~C ２０ The process of any one of claims 1 to 7, comprising:

9. Structure (2): Structure (2) 【Chemistry 1】 (In the formula, R is selected from the group consisting of a hexyl group, a methyl group, a hydrogen atom, and combinations thereof; R' is -CH ２ - and - (CH ２ ) ４ - selected from the group consisting of R'' is CH ３ and 9. The process of claim 8, comprising forming a functionalized olefin-Si polymer having a moiety selected from the group consisting of epoxides, ethers, esters, alcohols, alkyl chains, amines, anhydrides, ketones, phenols, and combinations thereof.

10. 1. A composition comprising: Structure (2): Structure (2) 【Chemistry 2】 (In the formula, R is selected from the group consisting of a hexyl group, a methyl group, a hydrogen atom, and combinations thereof; R' is -CH ２ - and - (CH ２ ) ４ - selected from the group consisting of R'' is CH ３ and Y is a heterohydrocarbonyl group having a moiety selected from the group consisting of epoxides, ethers, esters, alcohols, alkyl chains, amines, anhydrides, ketones, phenols, and combinations thereof.

11. The composition of claim 10, wherein the functionalized olefin-Si polymer is a functionalized ethylene-Si polymer.

12. The composition of claim 10, wherein the functionalized olefin-Si polymer is a functionalized propylene-Si polymer.

13. The composition according to any one of claims 10 to 12, wherein Y is a compound selected from the group consisting of the following s17) to s24): 【Transformation 3】

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