CN-121986122-A - Silanol functional polyolefins

Abstract

Embodiments of the present disclosure relate to a method of preparing a silanol-functional polyolefin comprising combining starting materials comprising a) a silyl hydride-functional polyolefin, optionally B) a solvent, C) a peroxyacid, optionally D) a neutralizing agent under thermal conditions for effecting synthesis of a silanol moiety, thereby forming a reaction mixture that produces the silanol-functional polyolefin having the silanol moiety under the thermal conditions.

Inventors

• Z. S. Keane
• R. Marr
• J. ROBERTS
• J.WANG
• D.S. Lethal
• LAI SHUQI

Assignees

• 陶氏环球技术有限责任公司

Dates

Publication Date

20260505

Application Date

20240927

Priority Date

20230927

Claims (15)

1. 1. A method of preparing a silanol-functional polyolefin, the method comprising: combining starting materials comprising the following under thermal conditions for effecting synthesis of the silanol moiety: a) Silyl hydride functionalized polyolefin, Optionally B) a solvent, C) A peroxy acid, Optionally D) a neutralizing agent; Thereby forming a reaction mixture that under the thermal conditions produces the silanol-functional polyolefin having the silanol moieties.
2. 2. The method of claim 1, wherein the silyl hydride functionalized polyolefin comprises a silyl hydride moiety of formula I: -SiR 2 H(I), Wherein each R is independently selected from the group consisting of an alkyl group of 1 to 4 carbon atoms and an aryl group of 6 to 10 carbon atoms.
3. 3. The method of claim 2, wherein each R is a methyl group.
4. 4. A process according to any one of claims 2 to 3, wherein silyl hydride functionalized polyolefin comprises from 0.10 weight percent (wt%) to 10wt% of the silyl hydride moiety of formula I based on the total weight of the silyl hydride functionalized polyolefin.
5. 5. The method of any one of claims 1 to 4, wherein the silyl hydride functionalized polyolefin is selected from the group consisting of silyl hydride functionalized polyethylene and silyl hydride functionalized polypropylene.
6. 6. The method of any one of claims 1 to 5, wherein the silyl hydride functionalized polyolefin is a branched silyl hydride functionalized polyolefin.
7. 7. The method of any one of claims 1-6, wherein the thermal conditions for achieving synthesis of the silanol moieties comprise melt blending the reaction mixture at a temperature of 100 ℃ to 180 ℃ for a duration of 30 seconds to 60 minutes.
8. 8. The method of claim 7, wherein the method is performed in the presence of a solvent.
9. 9. The method of any one of claims 1 to 6, wherein the thermal conditions for achieving synthesis of the silanol moieties comprise dissolving the silyl hydride functionalized polyolefin in the solvent of B) the reaction mixture.
10. 10. The method of claim 9, wherein the thermal conditions for achieving synthesis of the silanol moieties comprise heating the reaction mixture at a temperature of 60 ℃ to 120 ℃ for a duration of one minute to 60 minutes.
11. 11. The method of any one of claims 1 to 10, further comprising separating the silanol-functional polyolefin from the reaction mixture.
12. 12. The process of any one of claims 1 to 11, wherein C) the peroxyacid is used in an amount of 1 molar equivalent to 3 molar equivalents of peroxyacid based on a) the silicon-bonded hydrogen content of the silyl hydride functionalized polyolefin.
13. 13. The method of any one of claims 1 to 12, wherein the peroxyacid is selected from the group consisting of peracetic acid, m-chloroperoxybenzoic acid, peroxybenzoic acid, and combinations thereof.
14. 14. The method of any one of claims 1 to 13, wherein D) the neutralizing agent is present in the reaction mixture.
15. 15. A silanol-functional polyolefin formed by any of claims 1 to 14.

Description

Silanol functional polyolefins Technical Field Embodiments of the present disclosure relate to polyolefins, more particularly silanol-functional polyolefins. Background The synthesis of polar polyolefins is a long standing problem for at least some of the following reasons. Polar comonomers can be copolymerized with ethylene monomers, however this is a capital intensive high pressure process and the resulting polymers have a wide range of branching and other characteristics/composition limitations. Free radical grafting can be performed on high density polyethylene or linear low density polyethylene polymers, but the range of graftable monomers is limited and generally only mixtures of grafting points and non-uniform lengths (e.g., single, low, multiple grafts) are available. In addition, solution phase polyolefin synthesis in commercial reactors cannot tolerate polar monomers because polar monomers are not compatible with the catalyst. In another approach, silane (-SiH) functionality may be incorporated "in-reactor" and compatible with conventional catalysts, but is non-polar and requires additional reaction to produce polar functionality. The simplest reaction to generate polar functionality from-SiH is by oxidation or hydrolysis to produce SiOH (silanol). However, silanol is difficult to synthesize in a controlled manner without further condensation into Si-O-Si. Transition metal compounds (e.g., pd, ru, ir, cr and Rh) can also be used, but these compounds are expensive and require isolation from the final reaction product, which is also problematic. In addition, several silane hydrolysis processes have been reported using stoichiometric oxidants such as bis-ethylene oxide and potassium permanganate. Unfortunately, dioxiranes are unstable and unsuitable for the temperatures required for polyolefin functionalization, and potassium permanganate is costly, highly colored and difficult to remove from the final product. It is therefore desirable to develop alternative, ideal in-reactor processes for synthesizing polar polyolefins that do not include these drawbacks. Disclosure of Invention The present disclosure provides various embodiments, including addressing the above-described drawbacks by providing a method of preparing a silanol-functional polyolefin, comprising combining under thermal conditions for effecting synthesis of a silanol moiety, starting materials comprising a) a silyl hydride-functional polyolefin, optionally B) a solvent, C) a peroxyacid, and optionally D) a neutralizing agent, thereby forming a reaction mixture that produces a silanol-functional polyolefin having a silanol moiety under thermal conditions. As disclosed herein, the silyl hydride functionalized polyolefin may comprise a silyl hydride moiety of formula I: , (e.g., comprising a silyl hydride moiety of formula I), wherein each R is independently selected from the group consisting of an alkyl group of 1 to 4 carbon atoms and an aryl group of 6 to 10 carbon atoms. As disclosed herein, each R can be a methyl group (e.g., each R is a methyl group). Further, as disclosed herein, the silyl hydride functionalized polyolefin can comprise from 0.10 weight percent (wt%) to 10 wt% of the silyl hydride moiety of formula I based on the total weight of the silyl hydride functionalized polyolefin (e.g., the silyl hydride functionalized polyolefin comprises from 0.10 wt% to 10 wt% of the silyl hydride moiety of formula I based on the total weight of the silyl hydride functionalized polyolefin). In particular embodiments, the silyl hydride functionalized polyolefin may be selected from the group consisting of silyl hydride functionalized polyethylene and silyl hydride functionalized polypropylene (e.g., the silyl hydride functionalized polyolefin is selected from the group consisting of silyl hydride functionalized polyethylene and silyl hydride functionalized polypropylene). In one embodiment, the silyl hydride functionalized polyolefin may be a branched silyl hydride functionalized polyolefin (e.g., the silyl hydride functionalized polyolefin is a branched silyl hydride functionalized polyolefin). As disclosed herein, the thermal conditions for achieving synthesis of the silanol moiety can include melt blending the reaction mixture at a temperature of 100 ℃ to 180 ℃ for a duration of 30 seconds to 60 minutes (e.g., the thermal conditions for achieving synthesis of the silanol moiety include melt blending the reaction mixture at a temperature of 100 ℃ to 180 ℃ for a duration of 30 seconds to 60 minutes). As disclosed herein, the method can occur in the absence of a solvent (e.g., in the absence of a solvent). As disclosed herein, the thermal conditions for achieving synthesis of the silanol moiety include dissolving the silyl hydride functionalized polyolefin in the solvent of the B) reaction mixture. As disclosed herein, the thermal conditions for achieving synthesis of the silanol moiety include heating the reaction mixture at a temperature