Hydrosilylation for functionalization of polyolefin particles

Abstract

Embodiments are directed to a process comprising: mixing particles of olefin-SiH polymer with structure (I) (I) where h ≥ 0, i ≥ 0, and j > 0, with a monovinyl graft component having a formula of H2C=CH2-X in a solvent in the presence of a hydrosilylation catalyst to graft the monovinyl graft component to the olefin-SiH polymer particles to thereby form functionalized particles with structure (II) where h ≥ 0, i ≥ 0, m ≥ 0, and l > 0, wherein the solvent comprises one or more of an organosilicon, or an alicyclic hydrocarbon optionally substituted with one or more pendant O heteroatoms; X and Y are selected from a C4-C20 hydrocarbyl group, or a C4-C20 heterohydrocarbyl group with one or more heteroatoms selected from the group consisting of O, N, and Si; and R and R'' are independently selected from H, C1-C12 alkyl, and R' is a C1-C12 alkenyl.

Description

HYDROSILYLATION FOR FUNCTIONALIZATION OF POLYOLEFIN PARTICLESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 677,585 filed July 31, 2024, the contents of which are incorporated in their entirety herein.BACKGROUND

[0002] Polyolefins have many advantages, in terms of cost, mechanical robustness, chemical resistance, and compositional range. However, polyolefins have limitations in terms of what functionalities they may contain. Functionalization of ethylene-based polymer (polyethylene), for example, is generally incompatible with solution phase polyethylene synthesis. Radical high pressure processes can generate polyethylene with polar functionality, but the process is capital intensive and compositional range is limited.

[0003] It is possible to functionalize a polymer via melt blending and then grinding to small particle size; however, this particle functionalization typically leads to agglomeration. Moreover, this process is typically low yielding, meaning that much more functionalized polymer must be synthesized to begin with, resulting in a waste of the hydrosilylation catalyst and polyolefin particles. Accordingly, there is a continual need for improved processes of functionalizing polyolefin particles with improved yield.SUMMARY

[0004] Embodiments of the present disclosure meet this need for improved processes for polyolefin particle functionalization.

[0005] According to one embodiment of the present disclosure, the process comprises: mixing particles of olefin-SiH polymer with structure (I)h > 0, i > 0, and j > 0, with a monovinyl graft component having a formula of H2C=CH2-X in a solvent in the presence of a hydrosilylation catalyst to graft the monovinyl graft component to theolefin-SiH polymer particles to thereby form functionalized particles with structurewhere h > 0, i > 0, m > 0, and I > 0, wherein the solvent comprises one or more of an organosilicon, or an alicyclic hydrocarbon optionally substituted with one or more pendant O heteroatoms; X and Y are selected from a C4-C20 hydrocarbyl group, or a C4-C20 heterohydrocarbyl group with one or more heteroatoms selected from the group consisting of O, N, and Si; and R and R” are independently selected from H, C1-C12 alkyl, and R’ is a C1-C12 alkenyl.

[0006] Without being limited by theory, this process can be performed without significantly altering the particle size distribution. Advantageously, the non-functionalized material can be ground first, and just the material with the desired particle size can be functionalized.DEFINITIONS

[0007] The numerical ranges disclosed herein include all values from, and including, the lower and upper value. For ranges containing explicit values (c.g, 1 or 2, or 3 to 5, or 6, or 7), any subrange between any two explicit values is included (c.g, the range 1-7 above includes subranges of 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0008] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weight, and all test methods are current as of the filing date of this disclosure.

[0009] The term "composition" refers to a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0010] The terms "comprising," "including," "having" and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of' excludes from the scope of any succeeding recitation any other component, step, or procedure, excepting those that are not essential to operability. The term "consisting of' excludes any component, step, or procedure not specifically delineated or listed. The term "or," unless stated otherwise, refers to the listedmembers individually as well as in any combination. Use of the singular includes use of the plural and vice versa.

[0011] An "ethylene-based polymer" or "polyethylene" is a polymer that contains a majority amount of polymerized ethylene based on the weight of the polymer and, optionally, may comprise at least one comonomer. Ethylene-based polymers typically comprise at least 50 mole percent (mol%) units derived from ethylene (based on the total amount of polymerizable monomers).

[0012] A "hydrocarbon" (or, "hydrocarbyl" a “hydrocarbyl group”) is a compound containing only hydrogen atoms and carbon atoms.

[0013] The terms “heterohydrocarbon” (“heterohydrocarbyl,” or heterohydrocarbyl group") and similar terms, as used herein, refer to a respective hydrocarbon, in which at least one carbon atom is substituted with a heteroatom group (for example, Si, O, N or P).

[0014] The terms “substituted hydrocarbon,” (or “substituted hydrocarbyl,” or "“substituted hydrocarbyl group") refers to a hydrocarbon in which one or more hydrogen atoms is / are independently substituted with a heteroatom group. The terms “substituted heterohydrocarbon,” (“substituted heterohydrocarbyl,” or "substituted heterohydrocarbyl group") and similar terms, as used herein, refer to a respective heterohydrocarbon in which one or more hydrogen atoms is / are independently substituted with a heteroatom group.

[0015] An "olefin-based polymer" or "polyolefin" is a polymer that contains a majority mole percent polymerized olefin monomer (based on total amount of polymerizable monomers), and optionally, may contain at least one comonomer. Nonlimiting examples of olefin-based polymer include ethylene-based polymer and propylene-based polymer. Representative polyolefins include polyethylene, polypropylene, poly butene, poly isoprene and their various interpolymers.

[0016] A "polymer" is a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term "homopolymer" (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term "interpolymer," as defined hereinafter. Trace amounts of impurities, for example, catalyst residues, may be incorporated into and / or within the polymer, ft also embraces all forms of copolymer, e.g., random, block, etc. The terms "ethylene / a-olefm polymer" and "propylene / a-olefm polymer" are indicative of copolymer as described above prepared from polymerizing ethylene or propylene respectively and one or more additional, polymerizable a-olefm monomer. It is noted that although a polymer is often referred to as being "made of' one or more specified monomers, "based on" aspecified monomer or monomer type, "containing" a specified monomer content, or the like, in this context the term "monomer" is understood to be referring to the polymerized remnant of the specified monomer and not to the unpolymerized species. In general, polymers herein are referred to as being based on "units" that are the polymerized form of a corresponding monomer.

[0017] A "propylene-based polymer" is a polymer that contains a majority amount of polymerized propylene based on the weight of the polymer and, optionally, may comprise at least one comonomer. Propylene-based polymers typically comprise at least 50 mole percent (mol%) units derived from propylene (based on the total amount of polymerizable monomers).DETAILED DESCRIPTION

[0018] In one or more embodiments, the process comprises: mixing particles of olefin-SiH polymer with structure (I)where h > 0, i > 0, and j > 0, with a mono vinyl graft component having a formula of H2C=CH2-X in a solvent in the presence of a hydrosilylation catalyst to graft the monovinyl graft component to the olefin-SiH polymer particles to thereby form functionalized particles with structurewhere h > 0, i > 0, m > 0, and I > 0, wherein the solvent comprises one or more of an organosilicon, or an alicyclic hydrocarbon optionally substituted with one or more pendant O heteroatoms; X and Y are selected from a C4-C20 hydrocarbyl group, or a C4-C20 heterohydrocarbyl group with one or more heteroatoms selected from the group consisting of O, N, and Si; and R and R” are independently selected from H, C1-C12 alkyl, and R’ is a C1-C12 alkenyl. The variable r denotes that the polymer may be a random copolymer.

[0019] Referring further embodiment, R' of Structure II is selected from the group consisting of -CH2- and -(CH2)4-, and R" is CH3. In one embodiment, X and Y have the same moiety. In another embodiment, X, Y or both comprise a C4-C10 alkyl. In yet another embodiment, X, Y orboth comprise a moiety selected from the group consisting of epoxide, ether, ester, alcohol, amine, anhydride, ketone, phenol, and combinations thereof.

[0020] Referring to Structure I, the monovinyl graft component may be selected from the group consisting of allyl glycidyl ester, 1 -octene, or 1 -decene.

[0021] Olefin-SiH Polymer Particles

[0022] The olefin-SiH polymer particles may comprise an ethylene-SiH polymer (an ethylenebased polymer) or a propylene-SiH polymer (a propylene-based polymer). In an embodiment, the olefin-SiH polymer is an ethylene-SiH polymer and is composed of (1) ethylene monomer, (2) from 0.1 wt.% to 20 wt.% of a SiH comonomer, and (3) optional C3-C12 a-olefin termonomer or C4-C8 a-olefin termonomer.

[0023] In an embodiment, the olefin-SiH polymer is a propylene-SiH polymer and is composed of (1) propylene monomer, (2) from 0.1 wt.% to 20 wt.% of a SiH comonomer, and (3) optional C2 a-olefin (ethylene) or C4-C8 a-olefin termonomer.

[0024] An "SiH comonomer," (interchangeably referred to as "SiH") as used herein, is a silane monomer of 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, and 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;H is hydrogen, and x > 0;E is a hydrocarbyl group or hydrogen,F is a hydrocarbyl group or hydrogen, E and F may be the same or different, when E is a hydrocarbyl group F is a hydrocarbyl group, E and F may be the same hydrocarbyl group. Nonlimiting samples of suitable SiH comonomer of Formula 1 include compounds si) (allyldimethylsilane), s2) (propenyldimethylsilane), s3) (butenyldimethylsilane), s4) (hexenyldimethylsilane), s5) (octenyldimethylsilane), s6), (decenyldimethylsilane), s7) norbornylethyldimethylsilane, s8) octahydrodimethanonaphthalenylethyldimethysilane, s9) vinyltetramethyldisiloxane, slO) allyltetramethyldisiloxane, sl l) butenyltetramethyldisiloxane, si 2, hexenyltetramethyldisiloxane, si 3) octenyltetramethyldisiloxane, si 4) decenyltetramethyldisiloxane, si 5) norbornylethyltetramethyldisiloxane, si 6) octahydrodimethanonaphthalenylethyltetramethyldisil oxane below:

[0025] In an embodiment, the SiH comonomer is selected from allyldimethylsilane, hexenyldimethylsilane, octenyldimethylsilane, and hexenyltetramethyldisiloxane.

[0026] In an embodiment, the ethylene-SiH polymer is an ethylene / a-olefin / SiH terpolymer. The a-olefm in the ethylene / a-olefin / SiH comonomer terpolymer can be a C3-C12 a-olefm or a C4-Cs a-olefm. Nonlimiting examples of suitable a-olefm include propylene, butene, hexene, octene, and ethylidene norbornene for respective ethylene / propylene SiH terpolymer, ethylene / butene / SiH terpolymer, ethylene / hexene / SiH terpolymer, ethylene / octene / SiH terpolymer and ethylene / ethylidene norbornene / SiH terpolymer.

[0027] In an embodiment, the ethylene / a-olefin / SiH terpolymer is an ethylene / octene / SiH terpolymer. Nonlimiting examples of suitable ethylene / octene / SiH terpolymer include ethylene / octene / hexenyldimethylsilane (HDMS) terpolymer, ethylene / octene / octenyldimethylsilane (ODMS) terpolymer, ethylene / octene / allyldimethylsilane and combinations thereof.

[0028] In an embodiment, the ethylene-SiH polymer is ethylene / octene / hexenyldimethylsilane. In an embodiment, the ethylene-SiH polymer is ethylene / octene / allyldimethylsilane (ADMS) terpolymer.

[0029] In an embodiment, the olefin-SiH polymer is a propylene / ethylene SiH polymer. In a further embodiment, the propylene / ethylene / SiH polymer (a propylene-based polymer) is propylene / ethylene / HDMS terpolymer.

[0030] In further embodiments, the olefin-SiH polymer particles are ground prior to mixing. The ground material may then be suspended in the solvent. At which point, the mono vinyl graft component and hydrosilylation catalyst are added. In some embodiments, the monovinyl graft component is added first. The reaction may occur at elevated temperature, for example, a temperature of at least 70 °C, of at least 80 °C, at least 90 °C, or at least at least 100 °C.

[0031] At the conclusion of the reaction, the particles may be filtered from the reaction, washed with a solvent to remove reaction impurities, and dried.

[0032] While the solvent may comprise one or more of an organosilicon, or an alicyclic hydrocarbon optionally substituted with one or more pendant O heteroatoms, other solvents are contemplated with the proviso that the solvent is not an amine, an alcohol, or an aromatic. In one or more embodiments, the solvent is selected from hexamethyldisiloxane, tetrakis(trimethylsiloxy)silane, tridecane, and 1,4-dioxane.

[0033] Various catalysts are considered suitable for the hydrosilylation catalyst. The hydrosilylation catalyst is a platinum catalyst. The platinum catalyst may be Speier’s catalyst, or chloroplatinic acid. Additionally, the process may occurs in the absence of a peroxide catalyst.

[0034] The particle size distribution does not change significantly due to functionalization. In one or more embodiments, the change in D90 from ground olefin-SiH polymer particles to functionalized particles is less than + / -25%, or in some embodiments, less than + / -20%, or less than + / -10%.TEST METHODS

[0035] Density. ASTM D4703 was used to make a polymer plaque for density analysis. ASTM D792, Method B was used to measure the density of each polymer (g / cc or g / cm3).

[0036] Melt Index. The melt index (or “I2”) of an ethylene-based polymer is measured in accordance with ASTM D-1238, condition 190°C / 2.16 kg (melt index 110 at 190°C / 10.0 kg). The I10 / I2 was calculated from the ratio of I10 to the I2. The melt flow rate MFR of a propylene-based polymer is measured in accordance with ASTM D-1238, condition 230°C / 2.16 kg.

[0037] Nuclear Magnetic Resonance (NMR) Characterization of Copolymers.

[0038] For ' l l NMR experiments, each sample was dissolved, in 8 mm NMR tubes, in tetrachloroethane-d2. The concentration was approximately 10 mg polymer in 0.6 mF deuteratedsolvent. Each tube was then heated in a heating block set at 110°C. The sample tube was repeatedly vortexed and heated to achieve a homogeneous flowing fluid. TheXH NMR spectrum was taken on a BRUKER AVANCE 500 MHz spectrometer, equipped with a 10 mm C / H DUAL cryoprobe. A standard single pulse ' l l NMR experiment was performed. The following acquisition parameters were used: 60 seconds relaxation delay, 90 degree pulse of 17.2 ps, 32 scans. The spectrum was centered at 1.3 ppm, with a spectral width of 20 ppm. All measurements were taken, without sample spinning, at 110°C. The ' l l NMR spectrum was referenced to “5.99 ppm” for the resonance peak of the solvent (residual protonated tetrachloroethane).

[0039] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples.EXAMPLES

[0040] Materials: All solvents used for polymerization or catalyst makeup were run through solvent purification columns to remove any impurities that may affect polymerization. The Isopar E was supplied by ExxonMobil Chemical Company, and was passed through two columns, the first containing activated A2 alumina, the second containing activated Q5 reactant. The ethylene was passed through two columns, the first containing A204 alumina and 4A mol sieves, the second containing Q5 reactant. Octenyldimethylsilane (ODMS) was provided by Gelest Inc. and was stirred over activated alumina and then filtered. The N2, used for transfers, is passed through a single column containing A204 alumna, 4A mol sieves and Q5.

[0041] Catalysts and co-catalysts

[0042] Batch Reactor Polymerization Procedure: The batch reactor polymerizations are conducted in a 2-L Parr™ batch reactor. The reactor is heated by an electrical heating mantle and is cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by a Camile™ TG process computer. The bottom of the reactor is fitted with a dump valve, which empties the reactor contents into a stainless-steel dump pot prefilled with a catalyst kill solution (5 mT of an Irgafos-168 / Irganox- 1076 / toluene mixture). The dump pot is vented to a 30-gallon blow-down tank, with both the pot and the tank purged with nitrogen.

[0043] The reactor is loaded first from the shot tank that contains Isopar E solvent (600 g) and ODMS (4.4 g). The shot tank is filled to the load set points by use of a lab scale to which the shot tank is mounted. After liquid feed addition, the reactor is heated to 170 °C. Ethylene is added to the reactor when at reaction temperature to maintain reactor pressure (226 psi). Ethylene addition amounts are monitored by a micro-motion flow meter.

[0044] PE Cat (0.8 pmol), Catalyst Component B (0.96 pmol), and Catalyst Component C (20 pmol) are mixed with the appropriate amount of purified toluene to achieve a solution of the desired molarity. The catalyst and co-catalysts components are handled in an inert glove box, drawn into a syringe and pressure transferred into the catalyst shot tank. This is followed by three rinses of toluene, 5 mE each. Immediately after catalyst addition the run timer begins. Ethylene is then added by the Camile to maintain reaction the pressure set point in the reactor. These polymerizations are run for 10 minutes, then the agitator is stopped, and the bottom dump valve is opened to empty reactor contents into the dump pot. The dump pot contents are poured into trays placed in a lab hood where the solvent is evaporated off overnight. The trays containing theremaining polymer are then transferred to a vacuum oven, where they are heated at 140 °C under vacuum to remove any remaining solvent. Approximately 20 g of polymer were obtained per run. The collected polymer was found to have Mw = 31 kDa, Mn = 12 kDa, 2.4 wt% ODMS.

[0045] Functionalization procedure: In a glass 20-mL scintillation vial equipped with a magnetic stirring bar, previously-ground polyethylene particles (1.00 g) were suspended in solvent (5 mL) at room temperature, and the monovinyl graft component was added (5 molar equivalents with respect to the polyethylene SiH), followed by addition of Speier’s catalyst (0.5 mg). The vial was capped and heated to 100 °C in a pre-heated anodized aluminum heating block and stirred for 20 minutes. At the conclusion of the reaction, the vial was allowed to cool to room temperature. The vial was uncapped, and the functionalized particles were collected by filtration on a disposable polypropylene frit. These particles were then washed with methanol (50 mL) and acetone (50 mL). Then, the material was transferred to a new glass 20-mL scintillation vial and dried under vacuum (to a pressure of 200 mtorr) at 50 °C over 18 h. Conversion was assessed by proton NMR (detailed above).

[0046] Table 1N.D.: Not determined.

[0047] Inventive examples IE1-IE7 produced greater than 95% conversion of functionalized particles. As shown, the particle size changed minimally for the inventive examples with the maximum particle size deviation being 24 pm. CE1 resulted in the material dissolving under the reaction conditions and becoming one solid mass. CE2 resulted in a complex mixture of products (presumably via reaction with the alcohol solvent). Additionally, the D90 change was less than -+7-25% for all of the inventive examples.

[0048] It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combination of elements of different embodiments as come within the scope of the following claims.

Claims

CLAIMS1. A process comprising: mixing particles of olefin-SiH polymer with structure (I)where h > 0, i > 0, and j > 0, with a monovinyl graft component having a formula of H2C=CH2-X in a solvent in the presence of a hydrosilylation catalyst to graft the monovinyl graft component to the olefin-SiH polymer particles to thereby form functionalized particles with structurewherein where h > 0, i > 0, m > 0, and I > 0; the solvent comprises one or more of an organosilicon, or an alicyclic hydrocarbon optionally substituted with one or more pendant O heteroatoms;X and Y are selected from a C4-C20 hydrocarbyl group, or a C4-C20 heterohydrocarbyl group with one or more heteroatoms selected from the group consisting of O, N, and Si; andR and R” are independently selected from H, C1-C12 alkyl, and R’ is a C1-C12 alkenyl.

2. The process of claim 1, wherein the hydrosilylation catalyst is a platinum catalyst.

3. The process of claim 1 or 2, wherein the olefin-SiH polymer particles are ground prior to mixing.

4. The process of claim 3, wherein the change in D90 from ground olefin-SiH polymer particles to functionalized particles is less than 25%.

5. The process of any one of claims 1 to 4, wherein R' is selected from the group consisting of -CH2- and -(CH2)4-, and R" is CH3.

6. The process of any one of claims 1 to 5, wherein X and Y have the same moiety.

7. The process of any one of claims 1 to 6, wherein X, Y or both comprise a C4-C10 alkyl.

8. The process of any one of claims 1 to 6, wherein Y comprises a moiety selected from the group consisting of epoxide, ether, ester, alcohol, amine, anhydride, ketone, phenol, and combinations thereof.

9. The process any one of claims 1 to 8, wherein the process occurs in the absence of a peroxide.

10. The process of any one of claims 1 to 9, wherein the mono vinyl graft component of Structure (1) is selected from the group consisting of allyl glycidyl ester, 1 -octene, or 1- decene.

11. The process of any one of claims 1 to 10, wherein the solvent is free of aromatics, amines, and alcohols.

12. The process of any one of claims 1 to 11, wherein the solvent is selected from hexamethyldisiloxane, tetrakis(trimethylsiloxy)silane, tridecane, and 1,4-dioxane.

13. The process of any one of claims 1 to 12, wherein the process occurs at a temperature of at least 80 °C.

14. Functionalized particles produced from the method of any one of claims 1 to 13.

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