Compositions and methods for crosslinking polymers in the presence of atmospheric oxygen

Patent metadata

Field	Value
Publication number	US-10563039-B2
Application number	US-201515531755-A
Country	US
Kind code	B2
Filing date	Dec 3, 2015
Priority date	Dec 9, 2014
Publication date	Feb 18, 2020
Grant date	Feb 18, 2020

Abstract

An organic peroxide formulation comprises at least one organic peroxide, at least one drying oil, and at least one free radical trap. A process comprises curing mixtures that include at least one elastomer and the organic peroxide formulation in the presence of oxygen. Elastomer compositions, methods of manufacturing elastomer articles, and elastomer articles made from the elastomer compositions are also disclosed.

First claim

We claim:

1. An organic peroxide formulation for curing a solid elastomer composition in the full or partial presence of oxygen consisting essentially of:
A) at least one organic peroxide which undergoes decomposition by heat to generate radicals, selected from the group consisting of 2,5-di(t-butylperoxy)-2,5-dimethyl hexane; t-butyl cumyl peroxide; 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3; t-butylperoxy-isopropenylcumylperoxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane; 3,6,9, triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane; m/p-di(t-butylperoxy)diisopropyl benzene; m-di(t-butylperoxy)diisopropyl benzene; p-di(t-butylperoxy)diisopropyl benzene; di-t-butyl peroxide; di-t-amyl peroxide; dicumyl peroxide; 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(t-butylperoxy)cyclohexane; n-butyl 4,4-di(t-butylperoxy)valerate; ethyl 3,3-di(t-butylperoxy)butyrate; OO-t-butyl)-O-(2-ethyl hexyl)monoperoxy carbonate; OO-t-butyl-O-ispropylmonoperoxy carbonate; polyether poly-t-butylperoxy carbonate; t-butyl-2-ethylhexylmonoperoxycarbonate; t-butylperoxybenzoate; t-butylperoxyacetate; t-butylperoxymaleic acid; di(4-methylbenzoyl)peroxide; dibenzoyl peroxide; di(2,4-dichlorobenzoyl)peroxide; dilauroyl peroxide; cumene hydroperoxide; and di(4-tert-butylcyclohexyl)peroxydicarbonate,
B) at least one drying oil, and
C) at least one free radical trap selected from the group consisting of nitroxides and quinones,
wherein the amounts of the at least one organic peroxide, the at least one drying oil and the at least one free radical trap are selected such that the formulation cures the solid elastomer composition in the full or partial presence of oxygen, wherein at least one drying oil is selected from the group consisting of: Lung oil, hemp oil, linseed oil, poppy oil, walnut oil, sunflower oil, cottonseed oil, corn oil, soybean oil, sardine oil, herring oil, safflower oil, flax seed oil, perilla oil, and a combination thereof.

2. The formulation of claim 1 , wherein the at least one free radical trap is selected from the group consisting of 4-hydroxy TEMPO and mono-tert-butyl hydroquinone (MTBHQ).

3. The formulation of claim 1 , wherein the at least one drying oil is tung oil and the at least one free radical trap is MTBHQ.

4. An elastomer composition which cures in the full or partial presence of oxygen comprising:
A) at least one solid elastomer selected from the group consisting of ethylene-propylene-diene terpolymer (EPDM), fluoroelastomers (FKM, FFKM, FVMQ), vinyl silicone rubber (VMQ), nitrile rubber (NBR), acrylonitrile-butadiene-styrene (ABS), styrene-butadiene rubber (SBR), styrene-butadiene-styrene block copolymers (SBS), polybutadiene rubber (BR), styrene-isoprene-styrene block copolymers (SIS), partially hydrogenated acrylonitrile butadiene (HNBR), natural rubber (NR), synthetic polyisoprene rubber (IR), neoprene rubber (CR), polychloroprene, bromobutyl rubber (BHR), chlorobutyl rubber, and combinations thereof,
B) at least one organic peroxide which undergoes decomposition by heat to generate radicals selected from the group consisting of 2,5-di(t-butylperoxy)-2,5-dimethyl hexane; t-butyl cumyl peroxide; 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; t-butylperoxy-isopropenylcumylperoxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane; 3,6,9, triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane; m/p-di(t-butylperoxy)diisopropyl benzene; m-di(t-butylperoxy)diisopropyl benzene; p-di(t-butylperoxy)diisopropyl benzene; di-t-butyl peroxide; di-t-amyl peroxide; dicumyl peroxide; 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(t-butylperoxy)cyclohexane; n-butyl 4,4-di(t-butylperoxy)valerate; ethyl 3,3-di(t-butylperoxy)butyrate; OO-t-butyl-O-(2-ethyl hexyl)monoperoxy carbonate; OO-t-butyl-O-ispropylmonoperoxy carbonate; polyether poly-t-butylperoxy carbonate; t-butyl-2-ethylhexylmonoperoxycarbonate; t-butylperoxybenzoate; t-butylperoxyacetate; t-butylperoxymaleic acid; di(4-methylbenzoyl)peroxide; dibenzoyl peroxide; di(2,4-dichlorobenzyl)peroxide; dilauroyl peroxide; cumene hydroperoxide; and di(4-tert-butylcyclohexyl)peroxydicarbonate,
C) at least one drying oil selected from the group consisting of: tung oil, hemp oil, linseed oil, poppy oil, walnut oil, sunflower oil, cottonseed oil, corn oil, soybean oil, sardine oil, herring oil, safflower oil, flax seed oil, perilla oil, and a combination thereof, and
D) at least one free radical trap selected from the group consisting of nitroxides and quinones,
wherein the elastomer composition is solid is not a liquid coating, and cures in the full or partial presence of oxygen.

5. The elastomer composition of claim 4 further comprising at least one polymer, wherein the polymer is selected from the group consisting of: ethylene-propylene copolymer (EPM), poly(ethylene α-olefins), poly(ethylene-octene), poly(ethylene-hexene), poly(ethylene-butylene), poly(ethylene-heptene), poly(ethylene-butene), poly(ethylene) (PE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), poly(ethylene-vinyl acetate) (EVA), poly(ethylene acrylate) elastomer, polysulfide rubber, chlorinated poly(ethylene) (CM or CPE), polyurethane (AU, EU), vinylidene fluoride copolymers (CFM), silicone rubber (PMQ), poly(ethylene methylacrylate) (ACM), chlorosulfonated poly(ethylene) (CSM), fluorosilicone rubber (FVMQ), fluoelastomer (FKM), and a combination thereof.

6. The elastomer composition of claim 4 , wherein the at least one free radical trap is selected from the group consisting of 4-hydroxy-TEMPO and MTBHQ.

7. A process for curing the solid elastomer composition of claim 4 , the process comprising:
curing the solid elastomer composition in the presence of oxygen
wherein the elastomer composition comprises at least one solid elastomer, at least one organic peroxide, at least one drying oil, and at least one free radical trap.

8. A cured solid elastomer composition prepared by the process of claim 7 which is not a liquid coating.

9. An organic peroxide formulation for curing a solid elastomer composition in the full or partial presence of oxygen comprising:
A) at least one organic peroxide which undergoes decomposition by heat to generate radicals selected from the group consisting of 2,5-di(t-butylperoxy)-2,5-dimethyl hexane; t-butyl cumyl peroxide; 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3; t-butylperoxy-isopropenylcumylperoxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane; 3,6,9, triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane; m/p-di(t-butylperoxy)diisopropyl benzene; m-di(t-butylperoxy)diisopropyl benzene; p-di(t-butylperoxy)diisopropyl benzene; di-t-butyl peroxide; di-t-amyl peroxide; dicumyl peroxide; 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane; 1,1-di(t-butylperoxy)cyclohexane; n-butyl 4,4-di(t-butylperoxy)valerate; ethyl 3,3-di(t-butylperoxy)butyrate; OO-t-butyl-O-(2-ethyl hexyl)monoperoxy carbonate; OO-t-butyl-O-isopropylmonoperoxy carbonate; polyether poly-t-butylperoxy carbonate; t-butyl-2-ethylhexylmonoperoxycarbonate; t-butylperoxybenzoate; t-butylperoxyacetate; t-butylperoxymaleic acid; di(4-methylbenzoyl)peroxide; dibenzoyl peroxide; di(2,4-dichlorobenzoyl)peroxide; dilauroyl peroxide; cumene hydroperoxide; and di(4-tert-butylcyclohexyl)peroxydicarbonate,
B) at least one drying oil selected from the group consisting of: tung; oil, hemp oil, linseed oil, poppy oil, walnut oil, sunflower oil, cottonseed oil, corn oil, soybean oil, sardine oil, herring oil, safflower oil, flax seed oil, perilla oil, and a combination thereof, and
C) at least one crosslinking coagent,
D) at least one free radical trap selected from the group consisting of nitroxides and quinones,
wherein the amounts of the at least one organic peroxide, the at least one drying oil and the at least one free

Assignees

• Arkema Inc

Inventors

• Pavlek William P
• Dluzneski Peter R
• Palys Leonard H
• Despotopoulou Marina

Classifications

• B29C71/04

  by wave energy or particle radiation {, e.g. for curing or vulcanising preformed articles (during moulding, e.g. in a mould B29C35/08)} · CPC title

• C08K5/0025 Primary

  Crosslinking or vulcanising agents; including accelerators · CPC title

• C08J2323/16

  Ethene-propene or ethene-propene-diene copolymers · CPC title

• B29C48/022

  characterised by the choice of material · CPC title

• C08J2331/04

  Homopolymers or copolymers of vinyl acetate · CPC title