Method and product for melt functionalization of hydrogenated silicon-containing polyolefins

Abstract

The present disclosure provides a method. In one embodiment, the method 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 of structure (1) is a C4-C20 heterohydrocarbyl group having one or more heteroatoms selected from O, N, and Si. The method includes grafting a monovinyl grafting component onto an olefin-SiH polymer to form a functionalized olefin-Si polymer. The present disclosure also provides a functionalized olefin-Si polymer composition produced by the present process.

Description

Background Art

[0001] Polyolefins have many advantages in terms of cost, mechanical robustness, chemical resistance and composition range. However, polyolefins have limitations in terms of the functional groups they may contain. For example, the functionalization of vinyl polymers (polyethylene) is usually incompatible with solution phase polyethylene synthesis. Free radical high pressure processes can produce polyethylene with polar functional groups, but the method is capital intensive and has a limited composition range.

[0002] There is therefore a recognized need in the art for methods that can introduce new functional groups into polyolefins, particularly polyethylene. Summary of the invention

[0003] The present disclosure provides a method. In one embodiment, the method comprises melt blending (i) an olefin-SiH polymer with (ii) a monovinyl graft component having the structure (1) H2C=CH2-X, wherein X of the structure (1) is a C4-C ... 20 The method comprises grafting a monovinyl grafting component onto an olefin-SiH polymer to form a functionalized olefin-Si polymer.

[0004] The present disclosure provides a composition. In one embodiment, the composition comprises a functionalized olefin-Si polymer having structure (2)

[0005] Structure (2)

[0006]

[0007] in

[0008] R is selected from hexyl, methyl, hydrogen atom and their combination,

[0009] R' is selected from -CH2- and -(CH2)4-,

[0010] R″ is CH3, and

[0011] Y is a heteroalkyl group having a moiety selected from the group consisting of epoxides, ethers, esters, alcohols, alkyl chains, amines, anhydrides, ketones, phenols, and combinations thereof.

[0012] definition

[0013] Any reference to the Periodic Table of the Elements is to the Periodic Table as published by CRC Press, Inc., 1990-1991. Groups of elements in this table are referred to by a new notation for numbering the groups.

[0014] For purposes of U.S. patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or their equivalent U.S. versions are so incorporated by reference), especially with respect to definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and common general knowledge in the art.

[0015] Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit, and include the lower limit and the upper limit. For ranges containing exact values ​​(e.g., 1 or 2, or 3 to 5, or 6, or 7), any sub-range between any two exact values ​​is included (e.g., the above ranges 1 to 7 include 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6, etc.).

[0016] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure.

[0017] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0018] 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 these components, steps or procedures are specifically disclosed. For the avoidance of any doubt, all compositions claimed through the use of the term "comprising" may include any additional additives, adjuvants or compounds, whether in polymeric form or otherwise, unless stated to the contrary. Conversely, the term "consisting essentially of excludes any other components, steps or procedures (except those that are not essential to operability) from the scope of any subsequent statements. The term "consisting of..." excludes any components, steps or procedures that are not specifically described or listed. Unless otherwise stated, the term "or" refers to the listed members individually and in any combination. The use of the singular includes the use of the plural, and vice versa.

[0019] "Dalton" is a unit of polymer molecular weight, equivalent to the atomic mass unit, abbreviated "Da" or "kDa" (kilodalton).

[0020] "Ethylene-based polymers" or "ethylene polymers" are polymers that contain a majority amount of polymerized ethylene, based on the weight of the polymer, and optionally may contain at least one comonomer. Ethylene-based polymers typically contain at least 50 mole percent (mol%) units derived from ethylene (based on the total amount of polymerizable monomers).

[0021] A "hydrocarbon" (or "hydrocarbyl" or "hydrocarbyl group") is a compound containing only hydrogen and carbon atoms.

[0022] As used herein, the term "heterohydrocarbon" ("heteroalkyl" or "heteroalkyl group") and similar terms refer to the corresponding hydrocarbon in which at least one carbon atom is replaced by a heteroatom group (eg, Si, O, N, or P).

[0023] 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 a heteroatom group. The term "substituted heterohydrocarbyl" ("substituted heterohydrocarbyl" or "substituted heterohydrocarbyl group") and similar terms as used herein refer to the corresponding heterohydrocarbyl in which one or more hydrogen atoms are independently replaced by a heteroatom group.

[0024] "Interpolymers" are polymers prepared by polymerizing at least two different types of monomers. The generic term interpolymer thus includes copolymers (employed to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0025] "Olefin-based polymers" or "polyolefins" are polymers that contain a majority mole % of polymerized olefin monomers (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Non-limiting examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers. Representative polyolefins include polyethylene, polypropylene, polybutene, polyisoprene, and various interpolymers thereof.

[0026] "Polymer" is a polymeric compound prepared by polymerizing monomers (whether of the same type or different types). Thus, the generic term polymer encompasses the term "homopolymer" (used to refer to polymers prepared from only one type of monomer, it being understood that trace impurities may be incorporated into the polymer structure) and the term "interpolymer" as defined below. Trace impurities (e.g., catalyst residues) may be incorporated into and / or within the polymer. It also encompasses all forms of copolymers, such as random copolymers, block copolymers, and the like. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" refer to copolymers prepared by polymerizing ethylene or propylene and one or more additional polymerizable α-olefin monomers, respectively, as described above. It should be noted that although polymers are often referred to as "made of" one or more specified monomers", "based on" a specified monomer or monomer type, "containing" a specified monomer content, etc., in this context, the term "monomer" is understood to refer to the polymerized residue of the specified monomer rather than unpolymerized material. Generally speaking, polymers are referred to herein as "units" based on the polymerized form of the corresponding monomer.

[0027] "Propylene-based polymers" are polymers that contain a majority amount of polymerized propylene, based on the weight of the polymer, and optionally may include at least one comonomer. Propylene-based polymers typically contain at least 50 mole percent (mol%) units derived from propylene (based on the total amount of polymerizable monomers).

[0028] Test Method

[0029] density Polymer plaques were prepared for density analysis using ASTM D4703. Density (g / cc or g / cm2) of each polymer was measured using ASTM D792, Method B. 3 ).

[0030] Differential scanning calorimetry (DSC). Differential Scanning Calorimetry (DSC) was used to measure the T m , T c , T g And crystallinity. Each sample (0.5g) was compressed into a film at 5000psi, 190°C for two minutes. About 5mg to 8mg of the film sample was weighed and placed in a DSC pan. The lid was screwed on the pan to ensure a closed atmosphere. Unless otherwise stated, the sample pan was placed in a DSC unit and then heated to a temperature of 180°C for PE at a rate of 10°C / min (for PP, heated to 230°C). The sample was kept at this temperature for three minutes. Then, for PE, the sample was cooled to -90°C (for PP, cooled to -60°C) at a rate of 10°C / min, and isothermally kept at this temperature for three minutes. The sample was then heated at a rate of 10°C / min until completely melted (second heating). Unless otherwise stated, the melting point (T m ) and the glass transition temperature (Tg) are determined from the second heating curve, and the crystallization temperature (T c ) is determined by the first cooling curve. Record T m and T c The corresponding peak temperature can be determined by the heat of fusion (H f ) divided by the theoretical heat of fusion of 292 J / g for PE (165 J / g for PP) and multiplying this number by 100 to calculate the percent crystallinity (e.g., % crystallinity = (Hf / 292 J / g) x 100 (for PE)). In DSC measurements, it is common to observe multiple T m peak and is recorded here as the T m The highest temperature peak.

[0031] FTIR-ATR.Infrared spectra were collected on a Perkin ElmerFrontier Fourier transform infrared spectrometer (FT-IR) with an attenuated total reflectance (ATR) attachment (single bounce diamond / ZnSe). The sample was cut with scissors to expose the clean inner surface, then placed in the attachment and kept at a peak absorbance of about 0.4, and 4-16 scans were collected depending on the quality of the spectrum. Spectra were collected at least in triplicate to ensure representative sampling of the entire sample. SiH conversion rate. The SiH conversion is the mole % of SiH bonds in the ethylene-SiH polymer that are converted to Si-C bonds ("SiC") due to the hydrosilylation reaction. The SiH conversion is calculated by -1 The peak at 942 cm -1 The baseline at 887 cm was set to 0. -1 The conversion rate is determined by the Si-H peak at 887 cm -1 Absorbance at 887 cm before hydrosilylation reaction) / ( -1 absorbance at ).

[0032] Gel content analysis A Soxhlet extraction apparatus was used following a procedure similar to that described in ASTM D2765. A known mass of sample (m0) was placed in a pre-weighed glass fiber sleeve (m t ) and extracted by boiling xylene (bp 136°C) under N2 for 15 hours. The thimble was then dried under vacuum at 50°C along with any sample residue. The final mass (m1) of the thimble and residual sample was measured and the gel content was calculated using the following equation.

[0033]

[0034] Gel Permeation Chromatography. For P1 polymer, P2 polymer and P3 polymer (in the Examples section), the chromatographic system consists of a PolymerCharGPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven chamber is set to 160 degrees Celsius, and the column chamber is set to 150 degrees Celsius. The columns are four AGILENT "Mixed A" 30cm 20 micron linear mixed bed columns. The chromatographic solvent is 1,2,4-trichlorobenzene containing 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0035] The GPC column set was calibrated using 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 molecular weights and arranged in six "cocktail" mixtures with at least ten times the interval between individual molecular weights. The standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 grams of polystyrene standards were prepared in 50 milliliters of solvent, and for molecular weights less than 1,000,000, 0.05 grams of polystyrene standards were prepared in 50 milliliters of solvent. The polystyrene standards were dissolved at 80 degrees Celsius with gentle stirring for 30 minutes. The polystyrene standard peak molecular weight was converted to polyethylene molecular weight using Equation 1 (as described by Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0036] M 聚乙烯 =Ax(M 聚苯乙烯 ) B (EQ1),

[0037] Where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0038] A fifth-order polynomial was used to fit the calibration points of the corresponding polyethylene equivalents. A small adjustment (approximately 0.375 to 0.445) was made to A to correct column resolution and band broadening effects so that a linear homopolymer polyethylene standard was obtained at 120,000 Mw. Total plate counts for the GPC column set were performed with decane ("prepared as 0.04 g in 50 ml TCB" and dissolved for 20 minutes under slow stirring). Plate counts (Equation 2) and symmetry (Equation 3) were measured at 200 microliter injections according to the following equations:

[0039]

[0040] wherein RV is the retention volume in milliliters, Peak Width is in milliliters, Peak Maximum is the maximum height of the peak, and 1 / 2 Height is 1 / 2 the height of the Peak Maximum; and

[0041]

[0042] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak maximum is the maximum position of the peak, tenth height is 1 / 10 of the height of the peak maximum, and where post-peak refers to the tail of the peak with a retention volume later than the peak maximum, and where pre-peak refers to the front of the peak with a retention volume earlier than the peak maximum. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0043] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set to 2 mg / ml, and the solvent (containing 200 ppm BHT) was added to a septum-covered vial previously sparged with nitrogen by the PolymerChar high temperature autosampler. The samples were dissolved at 160 degrees Celsius for two hours under "low speed" shaking.

[0044] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer, according to Equations 4-6, the PolymerChar GPCOne TM The software was used to calculate the Mn of the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation of. Equation 4-6 is as follows:

[0045]

[0046] and

[0047]

[0048] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (flow rate (nominal)) for each sample by comparing the RV of the corresponding decane peak in the sample (RV (FM sample)) with the RV of the decane peak in the narrow standard calibration (RV (FM calibrated)). It was then assumed that any changes in the time of the decane marker peak were related to linear changes in the flow rate (flow rate (effective)) for the entire run. In order to promote the highest accuracy of the RV measurement of the flow marker peak, the peak of the flow marker concentration chromatogram was fit to a quadratic equation using a least squares fitting procedure. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 7: Flow rate (effective) = flow rate (nominal) * (RV (FM calibration) / RV (FM sample)) (EQ7). By PolymerChar GPCOne TM The software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.7% of the nominal flow rate.

[0049] For P4 polymer (in the embodiment section), the chromatographic system is composed of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The automatic sampler oven chamber is set to 160 degrees Celsius, and the column chamber is set to 150 degrees Celsius. These posts are an Agilent PLgel MIXED 7.5 × 50mm, 20 μm linear mixed bed guard column followed by four Agilent PLgel MIXED-A 7.5 × 300mm, 20 μm linear mixed bed columns. The chromatographic solvent is 1,2,4-trichlorobenzene (TCB), which contains 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0050] Calibration of the GPC column set was performed using Agilent EasiCal polystyrene standards (EasiCal PS-1 and EasiCal PS-2). Each EasiCal system consists of two different spatulas supporting a mixture of 5 polymer standards (approximately 5 mg) to obtain 20 molecular weight points ranging from approximately 580 g / mole to 6,570,000 g / mole. A single spatula was added to a vial covered with a septum, sealed and loaded into the PolymerChar autosampler. 8 mL of solvent was added to each vial using the PolymerChar instrument control software, and the standards were dissolved at 160 ° C for 15 minutes under high-speed shaking before being injected into the chromatography system. The polystyrene standard peak molecular weight was converted to polyethylene molecular weight using equation 1 (as described in Williams and Ward, Journal of Polymer Science, Polymer Letters (J. Polym. Sci., Polym. Let.), 6, 621 (1968)):

[0051] M 聚乙烯 =Ax(M 聚苯乙烯 ) B (EQ1),

[0052] Where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0053] A third-order polynomial was used to fit the corresponding polyethylene equivalent calibration points. A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band broadening effects so that a linear low density polyethylene standard was obtained at 120,000 Mw. Total plate counts for the GPC column set were performed with decane (3% v / v TCB introduced by a micro pump). Plate counts (Equation 2) and symmetry (Equation 3) were measured at 200 microliter injections according to the following equations:

[0054]

[0055] wherein RV is the retention volume in milliliters, Peak Width is in milliliters, Peak Maximum is the maximum height of the peak, and 1 / 2 Height is 1 / 2 the height of the Peak Maximum; and

[0056]

[0057] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak maximum is the maximum position of the peak, tenth height is 1 / 10 of the height of the peak maximum, and where post-peak refers to the tail of the peak with a retention volume later than the peak maximum, and where pre-peak refers to the front of the peak with a retention volume earlier than the peak maximum. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0058] The samples were prepared semi-automatically using PolymerChar "Instrument Control" software, where the target weight of the sample was set to 2 mg / ml and the solvent (containing 200 ppm BHT) was added to a septum-covered vial by a PolymerChar high temperature autosampler. The samples were dissolved at 160°C for two hours under high speed shaking.

[0059] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer, according to Equations 4-6, the PolymerChar GPCOne TM The software was used to calculate the Mn of the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation of. Equation 4-6 is as follows:

[0060]

[0061] and

[0062]

[0063] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (flow rate (nominal)) for each sample by comparing the RV of the corresponding decane peak in the sample (RV (FM sample)) with the RV of the decane peak in the narrow standard calibration (RV (FM calibrated)). It was then assumed that any changes in the time of the decane marker peak were related to linear changes in the flow rate (flow rate (effective)) for the entire run. In order to promote the highest accuracy of the RV measurement of the flow marker peak, the peak of the flow marker concentration chromatogram was fit to a quadratic equation using a least squares fitting procedure. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 7: Flow rate (effective) = flow rate (nominal) * (RV (FM calibration) / RV (FM sample)) (EQ7). By PolymerChar GPCOne TM The software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.7% of the nominal flow rate.

[0064] For P5 polymer (in the embodiment section), the chromatographic system is composed of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment is set to 160°C and the column compartment is set to 150°C. These columns are an Agilent PLgel MIXED 7.5×50mm, 20μm linear mixed bed guard column followed by four Agilent PLgel MIXED-A 7.5×300mm, 20μm linear mixed bed columns. The chromatographic solvent is 1,2,4-trichlorobenzene (TCB), which contains 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0065] Agilent EasiCal polystyrene standards (EasiCal PS-1 and EasiCal PS-2) were used to calibrate the GPC column set. Each EasiCal system consists of two different scrapers supporting a mixture of 5 polymer standards (approximately 5 mg) to obtain 20 molecular weight points in the range of approximately 580 g / mole to 6,570,000 g / mole. A single scraper was added to a vial covered with a septum, sealed and loaded into the PolymerChar autosampler. 8 mL of solvent was added to each vial using the PolymerChar instrument control software, and the standards were dissolved at 160 ° C for 15 minutes under high-speed shaking before being injected into the chromatography system. Equation 8 was used to convert the polystyrene standard peak molecular weight to polypropylene molecular weight (modified from Williams and Ward, Journal of Polymer Science, Polymer Express (J. Polym. Sci., Polym. Let.), 6, 621 (1968)):

[0066] M 聚乙烯 =Ax(Mpolystyrene) B (Equation 8), where M is the molecular weight, A has a value of 0.647, and B equals 1.0.

[0067] A third-order polynomial was used to fit the corresponding polypropylene equivalent calibration points. Total plate counts for the GPC column set were performed with decane (3% v / v TCB introduced via a micro pump). Plate counts (Equation 9) and symmetry (Equation 3) were measured at 200 microliter injections according to the following equations:

[0068] where RV is the retention volume in milliliters, peak width is in milliliters, peak maximum is the maximum height of the peak, and 1 / 2 height is 1 / 2 the height of the peak maximum.

[0069]

[0070] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak maximum is the maximum position of the peak, tenth height is 1 / 10 of the height of the peak maximum, and where post-peak refers to the tail of the peak with a retention volume later than the peak maximum, and where pre-peak refers to the front of the peak with a retention volume earlier than the peak maximum. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0071] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set at 2 mg / ml and the solvent (containing 200 ppm BHT) was added to the septum-capped vials by the PolymerChar high temperature autosampler. The samples were dissolved at 160°C for two hours under "high speed" shaking.

[0072] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer, according to Equations 10-12, the PolymerChar GPCOne TM The software calculates Mn(GPC), Mw(GPC) and Mz(GPC) from the baseline-subtracted IR chromatogram at each equally spaced data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. Equations 10-12 are as follows:

[0073]

[0074] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (flow rate (nominal)) for each sample by comparing the RV of the corresponding decane peak in the sample (RV (FM sample)) with the RV of the decane peak in the narrow standard calibration (RV (FM calibrated)). It was then assumed that any changes in the time of the decane marker peak were related to linear changes in the flow rate (flow rate (effective)) for the entire run. In order to promote the highest accuracy of the RV measurement of the flow marker peak, the peak of the flow marker concentration chromatogram was fit to a quadratic equation using a least squares fitting procedure. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 7: Flow rate (effective) = flow rate (nominal) * (RV (FM calibration) / RV (FM sample)) (EQ7). By PolymerChar GPCOne TM The software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.7% of the nominal flow rate.

[0075] Melt index. The melt index (or "I2") of ethylene-based polymers is measured according to ASTM D-1238 at 190°C / 2.16 kg (melt index I10 at 190°C / 10.0 kg).10 Calculate I by the ratio of I2 10 / I2. The melt flow rate MFR of the propylene-based polymer is measured according to ASTM D-1238 at 230°C / 2.16kg.

[0076] Nuclear Magnetic Resonance (NMR) Characterization of Terpolymers. for 13 For C NMR experiments, samples were dissolved in tetrachloroethane-d2 (with or without 0.025M Cr(acac)3) in 10 mm NMR tubes. The concentration was approximately 300 mg / 2.8 mL. Each tube was then heated in a heating block set at 110 °C. The sample tubes were repeatedly vortexed and heated to obtain a uniformly flowing fluid. The data were collected on a BRUKER AVANCE 600 MHz spectrometer equipped with a 10 mm C / H DUAL cryogenic probe. 13 C NMR spectra. The following acquisition parameters were used: 60 s relaxation delay, 12.0 μs 90 degree pulse, 256 scans. The spectra were centered at 100 ppm and had a spectral width of 250 ppm. All measurements were performed at 110 °C without sample rotation. For the resonance peaks of the solvent, 13 The C NMR spectrum was located at "74.5 ppm". For samples containing Cr, data were collected at "7 sec relaxation delay" and 1024 scans.

[0077] for 1 For H NMR experiments, each sample was dissolved in tetrachloroethane-d2 (with or without 0.001M Cr(acac)3) in an 8mm NMR tube. The concentration was approximately 100mg / 1.8mL. Each tube was then heated in a heating block set at 110°C. The sample tubes were repeatedly vortexed and heated to obtain a uniformly flowing fluid. The data were collected on a BRUKER AVANCE 600MHz spectrometer equipped with a 10mm C / H DUAL cryogenic probe. 1 H NMR spectroscopy. Standard single pulse 1 H NMR experiments. The following acquisition parameters were used: 70 s relaxation delay, 17.2 μs 90 degree pulse, 32 scans. The spectrum was centered at 1.3 ppm and the spectrum width was 20 ppm. All measurements were performed at 110 °C without sample rotation. For the resonance peak of the solvent (residual protonated tetrachloroethane), 1 The H NMR spectrum was located at "5.99 ppm". For samples containing Cr, data were collected at "16 sec relaxation delay" and 128 scans.

[0078] SiH conversion rate. See FTIR-ATR Test Methods. The SiH conversion percentage (%) is described under FTIR-ATR Test Methods. DETAILED DESCRIPTION

[0079] The present disclosure provides a method. In one embodiment, the method includes 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 of the structure (1) is a heteroalkyl group containing a moiety selected from epoxides, ethers, esters, alcohols, alkyl chains, amines, anhydrides, ketones, phenols, and combinations thereof. The method includes grafting the monovinyl graft component onto the olefin-SiH polymer to form a functionalized olefin-Si polymer.

[0080] The method comprises 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 one 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) optionally C3-C 12 The terpolymer consists of α-olefin terpolymer monomers or C4-C8 α-olefin terpolymer monomers.

[0081] In one 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% SiH comonomer, and (3) optional C2 α-olefin (ethylene) or C4-C8 α-olefin termonomer.

[0082] As used herein, a "SiH comonomer" (interchangeably referred to as "SiH') is a silane monomer of Formula 1:

[0083] (Formula 1)

[0084] A-(SiBC-O) x -Si-EFH

[0085] wherein A is an alkenyl group,

[0086] B is a hydrocarbon group or hydrogen,

[0087] C is a hydrocarbyl group or hydrogen, and

[0088] wherein B and C may be the same or different, and further B is a hydrocarbyl group, C is a hydrocarbyl group, and further B and C are the same;

[0089] H is hydrogen, and x ≥ 0;

[0090] E is a hydrocarbon group or hydrogen,

[0091] F is a hydrocarbyl group or hydrogen, 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 examples of suitable SiH comonomers of Formula 1 include compounds s1) (allyl dimethyl silane), s2) (propylene dimethyl silane), s3) (butenyl dimethyl silane), s4) (hexenyl dimethyl silane), s5) (octenyl dimethyl silane), s6) (decenyl dimethyl silane), s7) norbornenyl ethyl dimethyl silane, s8) octahydrodimethylene naphthyl ethyl dimethyl silane, s9) vinyl tetramethyl disiloxane, s10) allyl tetramethyl disiloxane, s11) butenyl tetramethyl disiloxane, s12) hexenyl tetramethyl disiloxane, s13) octenyl tetramethyl disiloxane, s14) decenyl tetramethyl disiloxane, s15) norbornenyl ethyl tetramethyl disilane, s16) octahydrodimethylene naphthyl ethyl tetramethyl disiloxane, as follows:

[0092]

[0093] In one embodiment, the SiH comonomer is selected from allyldimethylsilane, hexenyldimethylsilane, octenyldimethylsilane and hexenyltetramethyldisiloxane.

[0094] In one embodiment, the ethylene-SiH polymer is an ethylene / α-olefin / SiH terpolymer. The α-olefin in the ethylene / α-olefin / SiH comonomer terpolymer can be C3-C 12 α-olefin or 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.

[0095] In one embodiment, the ethylene / α-olefin / SiH terpolymer is an ethylene / octene / SiH terpolymer. Non-limiting examples of suitable ethylene / octene / SiH terpolymers include ethylene / octene / hexenyldimethylsilane (HDMS) terpolymers, ethylene / octene / octenyldimethylsilane (ODMS) terpolymers, ethylene / octene / allyldimethylsilane, and combinations thereof.

[0096] In one embodiment, the ethylene-SiH polymer is ethylene / octene / hexenyldimethylsilane.

[0097] In one embodiment, the ethylene-SiH polymer is an ethylene / octene / allyldimethylsilane (ADMS) terpolymer.

[0098] In one embodiment, the olefin-SiH polymer is a propylene / ethylene SiH polymer. In another embodiment, the propylene / ethylene / SiH polymer (propylene-based polymer) is a propylene / ethylene / HDMS terpolymer.

[0099] The monovinyl grafted component is melt blended with an ethylene-SiH polymer in the presence of a platinum group metal catalyst. The monovinyl grafted component has a single vinyl group and has the structure (1)

[0100] Structure (1)

[0101] H2C=CH2-X

[0102] wherein X of structure (1) is a C4-C ... 20 In one embodiment, "X" of structure (1) is a C4-C5C6- ... 20 Heteroalkyl groups.

[0103] In one embodiment, the monovinyl grafted component of structure (1) is a C4-C ... 20 Heteroalkyl group or C6-C 18 In another embodiment, structure (1) is selected from the group consisting of allyl glycidyl ether, 5-hexen-2-one, eugenol, 10-undecenoic acid methyl ester, vinyl triethoxysilane, N,N-diethylallylamine, 2,6-di-tert-butyl-4-vinylphenol and bicyclo[2.2.1]hept-5-ene-2-carboxylic acid tert-butyl ester.

[0104] The method comprises 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, a "platinum group metal catalyst" is an organometallic compound containing a metal selected from the group consisting of iridium (Ir), palladium (Pd), platinum (Pt), rhodium (Rh) and ruthenium (Ru), which accelerates the hydrosilylation reaction between the SiH portion of the ethylene-SiH polymer and the vinyl group of the monovinyl graft component of structure (1).

[0105] In one embodiment, the platinum group metal catalyst comprises a metal selected from the group consisting of Ir, Pt, and Rh. In another embodiment, the platinum group metal catalyst comprises platinum (Pt).

[0106] In one embodiment, the platinum group metal catalyst is (H3O)2(PtCl6)(H2O) in isopropanol solution. 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.

[0107] The ethylene-SiH polymer (or propylene-SiH polymer), the monofunctional monovinyl graft component and the platinum group metal catalyst are melt blended or mixed at a temperature and time sufficient to completely homogenize the mixture. The melt blending is carried out 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 by intermittent mixing or continuous mixing. In the presence of the platinum group metal catalyst, the melt blending initiates a hydrosilylation reaction between the Si-H portion of the ethylene-SiH polymer (or propylene-SiH polymer) and the vinyl group of the monovinyl graft component, thereby grafting the monovinyl graft component to 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 grafted component, wherein the monovinyl grafted component is grafted or otherwise covalently bonded to the ethylene-SiH polymer at the silicon atom of the SiH moiety through a Si-CCY bond, wherein "Y" is a C4-C4 oligomer having one or more heteroatoms selected from O, N and Si. 20 Heteroalkyl group or C6-C 18 In one embodiment, "Y" is C4-C 20 The heteroalkyl group and includes moieties selected from the group consisting of epoxides, ethers, esters, alcohols, amines, anhydrides, ketones, phenols, and combinations thereof.

[0108] As used herein, "functionalized propylene-Si polymer" is the reaction product between a propylene-SiH polymer and a monovinyl grafted component, wherein the monovinyl grafted component is grafted or otherwise covalently bonded to the propylene-SiH polymer at the silicon atom of the SiH moiety through a Si-CCY bond, wherein "Y" is a C4-C4 oligomer having one or more heteroatoms selected from O, N and Si. 20 Heteroalkyl group or C6-C 18 In one embodiment, "Y" is C4-C 20 The heteroalkyl group and includes moieties selected from the group consisting of epoxides, ethers, esters, alcohols, amines, anhydrides, ketones, phenols, and combinations thereof.

[0109] In one embodiment, the method comprises forming a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having the following structure (2):

[0110] Structure (2)

[0111]

[0112] in

[0113] R is selected from hexyl, methyl, hydrogen atom and their combination,

[0114] R' is selected from CH2 and -(CH2)4-,

[0115] R″ is CH3, and

[0116] Y is a heteroalkyl group having a moiety selected from epoxides, ethers, esters, alcohols, alkyl chains, amines, anhydrides, ketones, phenols and combinations thereof. In another embodiment, Y is a compound selected from the following s17) to s24):

[0117]

[0118] In one embodiment, melt blending is performed by batch mixing in a batch mixer. The ethylene-SiH polymer (or propylene-Si polymer), the monovinyl grafting component and the platinum group metal catalyst are added to the batch mixer and melt blended or otherwise mixed 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. Non-limiting examples of suitable batch mixers include BANBURY TM Mixer, BOLLING TM Mixer or HAAKE TM Mixer. Intermittent mixing forms a functionalized ethylene-Si polymer (or propylene-Si polymer) having structure (2).

[0119] In one embodiment, melt blending 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. Ethylene-SiH polymer (or propylene-Si polymer), monovinyl grafted component and platinum group metal catalyst are introduced into the extruder and melt blended or otherwise mixed 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 to form a uniform mixture. Non-limiting examples of suitable extruders include FARREL TM Continuous mixer, COPERION TM Twin screw extruder or BUSSTM Kneading continuous extruder. The homogeneous composition leaves the outlet die of the extruder as an extrudate, which is a functionalized ethylene-Si polymer (or propylene-Si polymer) having structure (2).

[0120] In one embodiment, the method comprises reacting (i) 50 wt % to 98 wt % of an ethylene-SiH polymer (which is ethylene / C3-C4H ... 12 α-olefin / SiH terpolymer) and (ii) 50 wt % to 2 wt % of a monovinyl grafted component of structure (1) (the weight percentage is based on the total weight of the ethylene-SiH polymer and the monovinyl grafted component) are melt blended to form a functionalized ethylene-Si polymer having structure (2).

[0121] In one embodiment, the method includes forming a functionalized ethylene-Si polymer (having structure 2) having a gel content of 0% to less than 2.5%. Gel content is measured according to ASTM D2765-16.

[0122] In one embodiment, the process comprises reacting (i) 50 wt % to 98 wt % of an ethylene-SiH polymer (which is ethylene / C3-C4H ... 12 The invention relates to a method for melt blending an α-olefin / SiH terpolymer) with (ii) 50 wt % to 2 wt % of a monovinyl grafted component of structure (1) (the weight percentages are based on the total weight of the ethylene-SiH polymer and the monovinyl grafted component) for a duration of 1 minute to 20 minutes, and converting greater than 90%, or greater than 93%, or greater than 95%, or greater than 95% to 99% of the SiH to SiC to form a functionalized ethylene-Si polymer having structure (2).

[0123] In one embodiment, the process is carried out (i) in the absence of a solvent, (ii) in the absence of a peroxide, and (iii) in the combination of (i) and (ii). As used herein, "solvent" is a liquid including water, hydrocarbons, alcohols, ketones, esters, acids, bases, and combinations thereof, under the following conditions: (1) present in an amount sufficient to dissolve the ethylene-SiH polymer (or propylene-Si polymer), (2) at a temperature above the melting temperature of the ethylene-SiH polymer (or propylene-Si polymer). It should be understood that the carrier liquid for the Speier catalyst (isopropanol) is not a solvent as defined herein because the ethylene-SiH polymer (or propylene-Si polymer) is not soluble in isopropanol. Even if soluble, the amount of isopropanol is so small that the ethylene-SiH polymer (or propylene-Si polymer) will not dissolve and the isopropanol will evaporate at the melting temperature of the ethylene-SiH polymer (or propylene-Si polymer) because the boiling point of isopropanol is 82.5°C.

[0124] In one embodiment, the process comprises reacting (i) 50 wt % to 98 wt % of an ethylene-SiH polymer, i.e., ethylene / C3-C4H6O2, 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. 12 The α-olefin / SiH terpolymer is melt blended with (ii) 50 wt % to 2 wt % of a monovinyl graft component of structure (1) (the weight percentage is based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) for a duration of 1 minute to 20 minutes. The monovinyl graft component is selected from allyl glycidyl ester, 5-hexen-2-one, eugenol, 10-undecenoic acid methyl ester, vinyl triethoxysilane and 2,6-di-tert-butyl-4-vinylphenol, triethylamine and combinations thereof. The method includes forming a functionalized ethylene-Si polymer having structure (2).

[0125] In one embodiment, the method comprises melt blending (i) 50 wt % to 98 wt % of an ethylene-SiH polymer, i.e., an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, with (ii) 50 wt % to 2 wt % of a monovinyl graft component of structure (1), i.e., allyl glycidyl ester (the weight percentages are based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) at a temperature of 80° C. to 120° C. in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst for a duration of 1 minute to 20 minutes. The method comprises forming a functionalized ethylene-Si polymer having structure (3):

[0126] Structure (3)

[0127]

[0128] In one embodiment, the method comprises melt blending (i) 50 wt % to 98 wt % of an ethylene-SiH polymer, i.e., an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, with (ii) 50 wt % to 2 wt % of a monovinyl graft component of structure (1), i.e., 5-hexen-2-one (the weight percentages are based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) at a temperature of 80° C. to 120° C. in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst for a duration of 1 minute to 20 minutes. The method comprises forming a functionalized ethylene-SiH polymer having structure (4):

[0129] Structure (4)

[0130]

[0131] In one embodiment, the method comprises melt blending (i) 50 wt % to 98 wt % of an ethylene-SiH polymer, i.e., an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, with (ii) 50 wt % to 2 wt % of a monovinyl grafted component of structure (1), i.e., eugenol (the weight percentages are based on the total weight of the ethylene-SiH polymer and the monovinyl grafted component) at a temperature of 80° C. to 120° C. in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst for a duration of 1 minute to 20 minutes. The method comprises forming a functionalized ethylene-SiH polymer having structure (5):

[0132] Structure (5)

[0133]

[0134] In one embodiment, the method comprises melt blending (i) 50 wt % to 98 wt % of an ethylene-SiH polymer, i.e., an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, with (ii) 50 wt % to 2 wt % of a monovinyl graft component of structure (1), i.e., methyl 10-undecenoate (the weight percentages are based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) at a temperature of 80° C. to 120° C. in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst for a duration of 1 minute to 20 minutes. The method comprises forming a functionalized ethylene-SiH polymer having structure (6):

[0135] Structure (6)

[0136]

[0137] In one embodiment, the method comprises melt blending (i) 50 wt % to 98 wt % of an ethylene-SiH polymer, i.e., an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, with (ii) 50 wt % to 2 wt % of a monovinyl graft component of structure (1), i.e., vinyltriethoxysilane (the weight percentages are based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) at a temperature of 80° C. to 120° C. in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst for a duration of 1 minute to 20 minutes. The method comprises forming a functionalized ethylene-Si polymer having structure (7):

[0138] Structure (7)

[0139]

[0140] In one embodiment, the method comprises melt blending (i) 50 wt % to 98 wt % of an ethylene-SiH polymer, i.e., an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, with (ii) 50 wt % to 2 wt % of a monovinyl graft component of structure (1), i.e., 2,6-di-tert-butyl-4-vinylphenol (the weight percentages are based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) at a temperature of 80° C. to 120° C. in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst for a duration of 1 minute to 20 minutes. The method comprises forming a functionalized ethylene-SiH polymer having structure (8):

[0141] Structure (8)

[0142]

[0143] In one embodiment, the method comprises melt blending (i) 50 wt % to 98 wt % of an ethylene-SiH polymer, i.e., an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, with (ii) 50 wt % to 2 wt % of a monovinyl graft component of structure (1), i.e., diethylallylamine (the weight percentages are based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) at a temperature of 80° C. to 120° C. in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst for a duration of 1 minute to 20 minutes. The method comprises forming a functionalized ethylene-Si polymer having structure (9):

[0144] Structure (9)

[0145]

[0146] In one embodiment, the method comprises melt blending (i) 50 wt % to 98 wt % of an ethylene-SiH polymer, i.e., an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, with (ii) 50 wt % to 2 wt % of a monovinyl graft component of structure (1), i.e., diethylallylamine (the weight percentages are based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) at a temperature of 80° C. to 120° C. in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst for a duration of 1 minute to 20 minutes. The method comprises forming a functionalized ethylene-Si polymer having structure (9):

[0147] Structure 10

[0148]

[0149] In one embodiment, the method comprises melt blending (i) 50 wt % to 98 wt % of an ethylene-SiH polymer, i.e., an ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, with (ii) 50 wt % to 2 wt % of a monovinyl graft component of structure (1), i.e., tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (the weight percentages are based on the total weight of the ethylene-SiH polymer and the monovinyl graft component) at a temperature of 80° C. to 120° C. in the presence of 1 ppm to 60 ppm or 2 ppm to 50 ppm of a platinum group metal catalyst for a duration of 1 minute to 20 minutes. The method comprises forming a functionalized ethylene-Si polymer having structure (10).

[0150] Applicants have discovered that the monovinyl grafted component unexpectedly does not crosslink during hydrosilylation. The resulting functionalized ethylene-Si polymer of structure (2) has little or no gel content, or a gel content of 0% to less than 2.5% gel content. Applicants have discovered a method for producing functionalized polyolefins (functionalized polyethylene) without the use of solvents (solvent-free process), without the use of peroxides (peroxide-free process), and without the use / need for inhibitors or antioxidants (antioxidant-free process). The present method advantageously reduces production costs. For example, in contrast to oligomeric / polymeric grafting in solvent-based free radical grafting of polyethylene, the present method obtains monomer grafting. The ability of the present method to obtain monomer grafting in polyethylene is unexpected.

[0151] The present disclosure provides a composition. In one embodiment, the composition includes a functionalized ethylene-Si polymer (or a functionalized propylene-Si polymer) having structure (2)

[0152] Structure (2)

[0153]

[0154] in

[0155] R is selected from hexyl, methyl, hydrogen atom and their combination,

[0156] R' is selected from CH2 and -(CH2)4-,

[0157] R″ is CH3,

[0158] Y is a compound selected from the following structures s17)-s24):

[0159]

[0160] In one embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (3)

[0161] Structure (3)

[0162]

[0163] In one embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (4)

[0164] Structure (4)

[0165]

[0166] In one embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (5)

[0167] Structure (5)

[0168]

[0169] In one embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (6)

[0170] Structure (6)

[0171]

[0172] In one embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (7)

[0173] Structure (7)

[0174]

[0175] In one embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (8)

[0176] Structure (8)

[0177]

[0178] In one embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (9)

[0179] Structure (9)

[0180]

[0181] In one embodiment, the composition is a functionalized ethylene-Si polymer (or functionalized propylene-Si polymer) having structure (10)

[0182] Structure (10)

[0183]

[0184] By way of example and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples.

[0185] Example

[0186] A. Synthesis and Properties of Polymers P1, P2, P3, P4, and P5

[0187] The ethylene / propylene / silane copolymerization for the production of P5 (propylene-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. The bottom of the reactor was equipped with a dump valve, which emptied the reactor contents into a dump pot connected to the atmosphere. All chemicals and catalyst solutions used for polymerization were passed through a purification column before use. ISOPAR-E, propylene, ethylene and silane monomers were also passed through the column. Ultra-high purity grades of nitrogen (Airgas) and hydrogen (Airgas) were used. The catalyst mixture was prepared by mixing a scavenger (MMAO), an activator (bis(hydrogenated tallow alkyl) methylamine tetra(pentafluorophenyl) borate (1<->)) and a catalyst with an appropriate amount of toluene in an inert glove box to obtain a solution of the desired molar concentration. The solution was then diluted with ISOPAR-E or toluene to achieve the amount required for polymerization and drawn into a syringe to transfer to a catalyst injection tank.

[0188] In a typical polymerization, ISOPAR-E and propylene are loaded into the reactor via separate flow meters. The silane monomer is then added via an injection tank input through an adjacent glove box. After the addition of solvent / comonomer, hydrogen is added (if necessary) while the reactor is heated to a polymerization set point of 120°C. Ethylene is then added to the reactor via a flow meter at the desired reaction temperature to maintain a predetermined reaction pressure set point. The catalyst solution is transferred to an injection tank via a syringe and then added to the reactor via a high pressure nitrogen stream after the reactor pressure set point is reached. The run timer is started upon injection of the catalyst, after which an exotherm and a decrease in reactor pressure are observed to indicate a successful run.

[0189] Ethylene was then added using a pressure controller to maintain the reaction pressure set point in the reactor. The polymerization was run for a set time or until ethylene was absorbed, after which the agitator was stopped and the bottom dump valve was opened to empty the reactor contents into a dump tank. The tank contents were poured into a tray placed in a fume hood and the solvent was allowed to evaporate 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 residual solvent. After cooling to ambient temperature, the polymer was weighed to obtain the yield / efficiency, transferred to a container for storage and submitted for analytical testing.

[0190] Interpolymers P1, P2 and P3 (ethylene-SiH polymers) were each prepared in a one-gallon polymerization reactor that was full of liquid and operated under steady-state conditions. The solvent was ISOPAR-E supplied by ExxonMobil Chemical Company. 5-Hexenyldimethylsilane (HDMS) supplied by Gelest was used as a terpolymer monomer and purified by AZ-300 alumina supplied by UOP Honeywell before use. HDMS was fed to the reactor as a 22 wt% ISOPAR-E solution. The reactor temperature was measured at or near the reactor outlet. The interpolymers were separated and pelletized. The polymerization conditions are listed in Tables 1C-1E, and the catalyst is 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.

[0191] Interpolymer P4 (ethylene-SiH polymer) was prepared in a 100 mL polymerization reactor that was full of liquid and operated under steady-state conditions. The solvent was ISOPAR-E supplied by ExxonMobil Chemical Company. Allyldimethylsilane (ADMS) was used as a terpolymer monomer and purified via AZ-300 alumina supplied by UOP Honeywell before use. ADMS synthesis is described below. ADMS was fed to the reactor as a 250 g / L ISOPAR-E solution. The reactor temperature was measured at or near the reactor outlet. The polymer solution was collected in a tray placed in a fume hood, and the solvent was allowed to evaporate 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 residual solvent. After cooling to ambient temperature, the polymer was weighed to obtain the yield / efficiency, transferred to a container for storage and submitted for analytical testing. The polymerization conditions are listed in Table 1C-Table 1E, and the catalyst is shown in Table 1B. The polymer properties of each olefin-SiH polymer are shown in Table 2A and Table 2B.

[0192] B. ADMS Synthesis

[0193] 35 kg of anhydrous toluene (>99%) obtained from Sigma-Aldrich and dried to <5 ppmw through an alumina column) was added to a nitrogen purged and dried 30-gallon glass-lined steel reactor. Then 20.2 L of 1 M allylmagnesium bromide in ether (Sigma-Aldrich) was added to the reactor and stirred at 25°C and 120 rpm. 2 L of dimethylsilyl chloride (DOWSIL TM Z-1219) to obtain 1.8 kg of allyl dimethyl silane (ADMS) in toluene and ether. The mixture was then transferred to a 20-gallon glass-lined steel reactor and the volatiles were distilled from the top at a jacket temperature of 110°C-140°C and 800 torr. The ADMS mixture was further distilled using a 12L batch still (4 feet x 2 inches) packed column to obtain about 1.2 kg of ADMS.

[0194] Table 1A: Polymerization conditions to produce P5 polymer

[0195]

[0196] Table 1B: Catalysts and co-catalysts

[0197]

[0198]

[0199] Table 1C: Polymerization conditions to produce P1-P4 polymers

[0200]

[0201] *Fed as 250g / L Isopar E solution

[0202] + -P4 uses ADMS instead of HDMS

[0203] Table 1D: Catalyst feed flow rates and efficiency of producing P1-P4 polymers

[0204]

[0205] *"ppm" amounts are based on the weight of the corresponding catalyst feed solution.

[0206] Table 1E: Cocatalyst Feed Flow Rates for Production of P1-P4 Polymers

[0207]

[0208] *"ppm" amounts are based on the weight of the co-catalyst feed solution. **"ppm" amounts of Al are based on the weight of the co-catalyst feed solution. ***Molar concentrations are based on the molar concentration of Al atoms

[0209] Table 2A: Polymer Properties

[0210]

[0211] *Mole % silane is based on the total moles of monomers in the polymer and is determined by 13C NMR (P1, P2, P3 and P5) and 1H NMR (P4). **Silane weight % is calculated by mole % and is based on the weight of the interpolymer.

[0212] Table 2B: Polymer Properties (Conventional GPC)

[0213] Resin Mn(kg / mol) Mw(kg / mol) Mw / Mn P1 45 100 2.2 P2 8.2 19 2.3 P3 24 50 2.1 P4 42 99 2.4 P5 72 189 2.6

[0214] C. Fang Law

[0215] 1. Materials

[0216] The materials used in the comparative samples (CS) and the inventive examples (IE) are provided in Table 3 below.

[0217] Table 3

[0218]

[0219]

[0220] The olefin-SiH polymers are listed in Table 4. Monovinyl grafted components 1-8 were obtained from Sigma-Aldrich or Oakwood Chemical and used without further modification. The synthesis of monovinyl grafted component 7 is provided in the literature (Org. Lett. 2005, 3721). Monovinyl grafted component 8 was obtained from TCI America.

[0221] Table 4

[0222]

[0223]

[0224] Embodiments 1-5 of the present invention

[0225] For Inventive Examples (IE) 1-5, 30 g-35 g (shown in Table 5) of olefin-SiH polymer was added to a preheated Haake mixer (Haake mixer equipped with a 50 cc mixing bowl) at a blending rate of 100 rpm at a specified temperature (shown in Table 5). Mixing was continued until the polymer became uniform. The monovinyl grafted component was added and mixing was continued for 1-5 minutes. Then, a catalyst (shown in Table 5 below) was added and the hydrosilylation reaction was allowed to proceed for 10 minutes. At the end of the hydrosilylation reaction, the functionalized polymer was collected. 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 polymer are provided in Table 5 below.

[0226] Embodiments 11-12 of the present invention

[0227] For IE11 and IE12, 35 g-50 g (shown in Table 5) of the silane polymer was added to a heating bottle with an overhead stirrer at a blending rate of 100 rpm in a nitrogen-filled glove box at the specified temperature (shown in Table 5). Mixing was continued until the polymer became homogeneous. The monovinyl graft component (5 molar equivalents relative to the silane) was added and mixing was continued for 1-5 minutes. Then, the catalyst (shown in Table 5 below) was added and the hydrosilylation reaction was allowed to proceed for 10 minutes.

[0228] Embodiments 13-16 of the present invention

[0229] For IE13-IE16, ethylene-SiH polymers were processed in a 11mm diameter Thermo Fisher Scientific Process 11 twin screw extruder (TSE) maintained in a chemical fume hood. This is a compact, parallel co-rotating TSE with a clamshell barrel. The extruder length is 44L / D, including a barrel of 40L / D and an extension of 4L / D. The barrel has 6 multifunctional barrel ports for reagent injection or vacuum, and 8 independent heating zones along the barrel. Before use, the polymer was ground to a particle size less than 2mm to facilitate its feeding. The polymer was fed into the extruder at a rate of 180g / h using a MovaColor MCBALANCE single screw metering feeder. A solution of Speier catalyst in allyl glycidyl ether was injected into the extruder at barrel position #4 using a 1000D ISCO pump. To achieve the desired loading of allyl glycidyl ether and catalyst, a solution was formed at a concentration of 0.18 mg to 0.50 mg Speier catalyst / mL allyl glycidyl ether. A residence time of 2.5 minutes was used. Typically, the extruder was run for about 5 minutes to reach equilibrium, and then about 10 g to 20 g of sample was collected for analysis.

[0230] Purification was performed by precipitation of 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.

[0231]

[0232] Comparison samples 1-2

[0233] For comparative samples (CS) 1-2, 35 g (shown in Table 5) of silane polymer were added to a preheated Haake mixer (Haake mixer equipped with a 50 cc mixing bowl) at a blending rate of 100 rpm at 100°C. Mixing was continued until the silane polymer became uniform. The monovinyl grafted component was added and mixing was continued for 1-5 minutes. Then, the catalyst (shown in Table 5) was added and the hydrosilylation reaction was allowed to proceed for 10 minutes. At the end of the hydrosilylation reaction, the functionalized polymer was collected. 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 polymer are provided in Table 4 below.

[0234] CS1 shows that the Custer catalyst provides material with unacceptable levels of gel content (13%) when applied to polymers with high molecular weight (P1 polymer Mw 100 kDa), whereas IE6 (P3 polymer Mw 50 kDa) exhibits acceptable gel content (1%).

[0235] IE16 shows that a lower limit of catalyst loading of 3 ppm Pt can produce functionalized ethylene-Si polymers with 0% or greater than 0% to 3% gel content (IE16 -2% gel content) and greater than 75% desired product (IE16 79% desired product).

[0236] Applicants have discovered that the ability to produce functionalized ethylene-Si polymers by melt blending ethylene-SiH polymers with monovinyl grafted components of structure (1) at temperatures of 80°C to 120°C and obtaining SiH conversions greater than 95% and gel contents of 0% to 3% is unexpected (as shown in IE1-16). The use of non-radical chemistry enables the grafting of functional groups that would otherwise react undesirably in the presence of free radical initiators. In particular, antioxidant (hindered phenol) functional groups and amine functional groups have undesirable reactivity in the presence of free radical initiators. The present method and its use of non-radical grafting facilitates the placement of antioxidant (hindered phenol) functional groups and amine functional groups, such as in structures 8 and 9.

[0237] It is particularly intended that the present disclosure is not limited to the embodiments and descriptions contained herein, but includes modifications of those embodiments including parts of the embodiments and combinations of elements of different embodiments as appear within the scope of the following claims.

Claims

1. A method comprising: Melt blending in the presence of platinum group metal catalysts (i) Olefin-SiH polymers (ii) Monovinyl grafted component having structure (1) Structure (1) H2C=CH2-X wherein X of structure (1) is a C4-C ... 20 Heteroalkyl groups; and The monovinyl grafting component is grafted onto the olefin-SiHH polymer to form a functionalized olefin-Si polymer.

2. The method according to claim 1, wherein the olefin-SiHH polymer is selected from the group consisting of ethylene-SiHH polymers and propylene-SiHH polymers.

3. The method according to any one of claims 1 to 2, wherein the C4-C 20 Heterohydrocarbyl groups include moieties selected from epoxides, ethers, esters, alcohols, amines, anhydrides, ketones, phenols, and combinations thereof.

4. The method of any one of claims 1-3, wherein the functionalized olefin-SiHH polymer has a gel content of 0% to less than 2.5% as measured according to ASTM D2765-16.

5. The method according to any one of claims 1 to 4, comprising melt blending at a temperature of 80°C to 120°C for a duration of 1 minute to 20 minutes; and More than 90% of SiH is converted to SiC.

6. The process according to any one of claims 1 to 5, wherein the process (i) is carried out in the absence of a solvent, (ii) in the absence of a peroxide, and (iii) in a combination of (i) and (ii).

7. The method according to any one of claims 1 to 6, wherein the monovinyl grafted component of structure (1) is selected from allyl glycidyl ester, 5-hexen-2-one, eugenol, 10-undecenoic acid methyl ester, vinyltriethoxysilane, 2,6-di-tert-butyl-4-vinylphenol, N,N-diethylallylamine and 2,6-tert-butyl bicyclo[2.2.1]hept-5-ene-2-carboxylate.

8. The method according to any one of claims 1 to 7, wherein the functionalized olefin-Si polymer comprises a -Si-CCY bond, wherein Si is the silicon atom, C is a carbon atom, and Y is a C4-C ... 20 Heteroalkyl groups.

9. The method of claim 8, comprising forming a functionalized olefin having structure (2): Si polymer Structure (2) in R is selected from hexyl, methyl, hydrogen atom and their combination, R' is selected from -CH2- and -(CH2)4-, R″ is CH3, and Y is a heteroalkyl group having a moiety selected from the group consisting of epoxides, ethers, esters, alcohols, alkyl chains, amines, anhydrides, ketones, phenols, and combinations thereof.

10. A composition comprising: Functionalized olefin-Si polymer having structure (2) Structure (2) in R is selected from hexyl, methyl, hydrogen atom and their combination, R' is selected from -CH2- and -(CH2)4-, R″ is CH3, and Y is a heteroalkyl 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. A composition according to any one of claims 9 to 12, wherein Y is a compound selected from the following s17)-s24)

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