One-pot process for preparing long-chain branched polyolefins

Patent metadata

Field	Value
Publication number	US-10787533-B2
Application number	US-201616064368-A
Country	US
Kind code	B2
Filing date	Dec 20, 2016
Priority date	Dec 21, 2015
Publication date	Sep 29, 2020
Grant date	Sep 29, 2020

Abstract

This invention relates to a novel one-pot process for polyolefin modification to form long-chain branched polymers containing polar functional groups, and the long-chain branched polymer resulting from the process. The process comprises reacting the following components (a) through (d) in a one pot process to form a long-chain branched polyolefin. Component (a) is a polyolefin; component (b) includes one or more silane compounds having the formula R″SiRnR′(3-n), component (c) is an ethylenically unsaturated polycarboxylic acid; and component (d) is a free radical initiator. In the formula R″SiRnR′(3-n) for component (b), R″ is an ethylenically or acetylenically unsaturated radical; R is a hydrolyzable group selected from the group consisting of an alkoxy, acyloxy, alkylamino, and arylamino; R′ is a hydrocarbyl group having 1 to 6 carbon atoms; and n is 1, 2, or 3.

First claim

What is claimed is:

1. A process for forming a long-chain branched polyolefin, comprising reacting:
(a) a polyolefin;
(b) one or more silane compounds having the formula R″SiR n R′ (3-n) , wherein:
R″ is an ethylenically or acetylenically unsaturated radical,
R is a hydrolyzable group selected from the group consisting of an alkoxy, acyloxy, alkylamino, and arylamino,
R′ is a hydrocarbyl group having 1 to 6 carbon atoms, and
n is 1-3;

(c) an ethylenically unsaturated polycarboxylic acid; and
(d) a free radical initiator,
in a one-pot process to form a long-chain branched polyolefin,
wherein the reacting step includes subjecting components (a)-(d) to a melt processing at a temperature to at least partially melt the polyolefin, and
wherein reacting components (a)-(d) in a one-pot process dehydrates the carboxylic acid groups of the ethylenically unsaturated polycarboxylic acids to produce water, which is used to hydrolyze one or more of said silane compounds.

2. The process of claim 1 , further comprising mixing one or more component (a), (b), (c), and (d) with silicon dioxide, prior to the reacting step.

3. The process of claim 1 , wherein the polyolefin is a polymer or copolymer of one or more olefins having from 2 to 12 carbons.

4. The process of claim 3 , wherein the one or more olefins are selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3 -methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1 -pentene, 4, 6-dimethyl-1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene, and combinations thereof.

5. The process of claim 3 , wherein the polyolefin is polyethylene, polypropylene, a copolymer thereof, or polymer blends containing polyethylene and/or polypropylene.

6. The process of claim 5 , wherein the polyolefin is a polymer blend containing ethylene propylene rubber (EPR).

7. The process of claim 1 , wherein the free radical initiator is a peroxide.

8. The process of claim 7 , wherein the peroxide is selected from the group consisting of a diacyl peroxide, a peroxyester, a peroxyketal, a dialkyl peroxide, an organic peroxycarbonate or organic peroxydicarbonate, and combinations thereof.

9. The process of claim 8 , wherein the peroxide is selected from the group consisting of benzoyl peroxide, dimyristoyl peroxide, tert-butylperoxy benzoate, tert-butylperoxy acetate, O,O-tert-butyl-O-(2-ethylhexyl)monoperoxy carbonate, n-butyl-4,4 -di-(tert-butyl peroxy)valerate, 1,1-bis(tertbutylperoxy)cyclohexane, 1,1-bis (tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-bis(tert-butylperoxy)butane, dicumylperoxide, tert-butylcumylperoxide, di-(2-tert-butylperoxy-isopropyl-(2))benzene, di-tert-butylperoxide (DTBP), 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5 -dimethyl-2,5-di(tert-butylperoxy)hexyne, 3,3,5,7,7-pentamethyl 1,2,4-trioxepane, dimyristyl peroxydicarbonate, dicetyl peroxydicarbonate, tert-butylperoxy 2-ethylhexyl carbonate, di(2-ethylhexyl) peroxydicarbonate, tert-butylperoxy isopropyl carbonate and combinations thereof.

10. The process of claim 1 , wherein the ethylenically unsaturated polycarboxylic acid is selected from the group consisting of itaconic acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid.

11. The process of claim 10 , wherein the ethylenically unsaturated polycarboxylic acid is itaconic acid.

12. The process of claim 1 , wherein:
R″ is an ethylenically unsaturated radical having the formula

wherein R 1 and R 2 each are independently H or C 1 -C 6 alkyl, or, alternatively, R 1 and R 2 together form a cyclic hydrocarbyl; X is absent, —C(═O)—O—, or —C(═O)—NH—; and m is 0-6.

13. The process of claim 12 , wherein R″ is selected from the group consisting of vinyl, allyl, isopropenyl, butenyl, cyclohexanyl, acryloxymethyl, acryloxypropyl, (meth)acryloxy methyl, (meth)acryloxy propyl, and styryl.

14. The process of claim 1 , wherein R is methoxy, ethoxy, formyloxy, acetoxy, or propionyloxy; and R′, if present, is methyl, ethyl, propyl, decyl, or phenyl.

15. The process of claim 14 , wherein R is a methoxy or ethoxy.

16. The process of claim 1 , wherein n is 3.

17. The process of claim 1 , wherein the silane compound is vinyltrimethoxysilane, vinyl triethoxysilane, 3-(trimethoxysilyl)propyl methacrylate, 3 -(triethoxysilyl)propyl methacrylate, trimethoxysilyl propyl acrylate, trimethoxysilyl methyl acrylate, 3-[dimethoxy(methyl)silyl]propyl acrylate, 3-[methoxy(dimethyl)silyl]propyl acrylate, methoxy(dimethyl)silyl]methyl acrylate, vinyl triacetoxysilane, p-styryltrimethoxysilane or combinations thereof.

18. The process of claim 17 , wherein the silane compound is 3-(trimethoxysilyl)propyl methacrylate, vinyltrimethoxysilane, or combination thereof.

19. The process of claim 1 , wherein:
the polyolefin (a) is polypropylene homopolymer,
the silane compound (b) is an mixture of

the ethylenically unsaturated polycarboxylic acid (c) is

and
the free radical initiator (d) is

20. The process of claim 1 , wherein the reacting step further involves:
covalently bonding one or more ethylenically unsaturated polycarboxylic acids at one or more binding sites along the polyolefin chain,
condensating the hydrolyzed one or more silane compounds, and
covalently bonding one or more condensated silane compounds at one or more binding sites along the polyolefin chain.

Assignees

• Braskem America Inc

Inventors

• Datashvili Tea
• Gallaschun Cassandra L
• Shin Sangyoung
• Zhang Songsheng

Classifications

• C08F255/04 Primary

  on to ethylene-propylene copolymers {(C08F255/023 takes precedence)} · CPC title

• C08F255/02 Primary

  on to polymers of olefins having two or three carbon atoms · CPC title

• C08J3/247

  Heating methods · CPC title

• C08F8/48

  Isomerisation; Cyclisation · CPC title

• C08L19/00

  Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00 · CPC title