Process for crosslinking thermoplastic polymers with silanes employing peroxide blends and the resulting crosslinked thermoplastic polymers
View Patent ↗A composition comprising at least one silane possessing an unsaturated organic function; at least two free radical initiators, and a process for producing silane-crosslinked thermoplastic polymers comprising providing a cross-linkable compound; at least one thermoplastic polymer; and, reacting the crosslinkable compound under reactive mechanical-working conditions and exposing the crosslinkable compound to moisture to provide crosslinked thermoplastic polymers.
1. A process for producing a silane-crosslinked thermoplastic polyolefin comprising:
a. providing a mixture of:
(i) at least one silane possessing an unsaturated organic function;
(ii) at least two free radical initiators, the first initiator having a first 0.1 hour half-life temperature and the second initiator having a second 0.1 hour half-life temperature being between 30° and 90° C. higher than said first half-life temperature;
(iii) at least one thermoplastic polyolefin wherein the thermoplastic polyolefin is at least one polyolefin selected from the group consisting of high-pressure low-density polyethylene, medium/low-pressure high-density polyethylene, low-pressure low-density polyethylene, medium-density polyethylene, an ethylene-α-olefin copolymer, polypropylene, an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, an ethylene-propylene copolymer, an ethylene-propylene-diene terpolymer, an ethylene-butene copolymer, polymethyl-pentene-1, polybutene, chlorinated polyethylene, an ethylene-vinyl acetate-chlorine terpolymer, and mixtures thereof; and,
b. reacting the mixture of step (a) under reactive mechanical-working conditions and exposure to moisture to provide crosslinked polyolefin.
2. The process of claim 1 wherein the silane possesses the general formula RR′SiY 2 wherein R represents a monovalently olefinically unsaturated hydrocarbon, each Y represents a hydrolysable organic radical and R′ represents an R radical or a Y radical.
3. The process of claim 2 wherein the silane is vinyl triethoxysilane and/or vinyl trimethoxysilane.
4. The process of claim 1 wherein the 0.1 hour half-life temperatures of the first free radical initiator is from about 80° to about 160° C.
5. The process of claim 1 wherein the 0.1 hour half-life temperature of the second free radical initiator is from about 125° to about 190° C.
6. The process of claim 1 wherein the first free radical initiator is selected from the group consisting of di(2,4-dichlorobenzoyl) peroxide, tert-butyl peroxypivalate, dilauroyl peroxide, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(tert-butylperoxy)cyclohexane, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.
7. The process of claim 1 wherein the second free radical initiator is selected from the group consisting of tert-butyl peroxyacetate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3 and di-tert-butyl peroxide.
8. The process of claim 1 wherein mixture (a) further includes at least one additional component selected from the group consisting of catalysts, stabilizers, fillers, antioxidants, processing aids, oils, plasticizers, pigments and lubricants.
9. The process of claim 8 where catalyst is a metal carboxylate, an organic metal compound, an organic base, or an acid.
10. A process for producing a silane-crosslinked thermoplastic polyolefin comprising:
a. providing a mixture of:
(i) at least one silane possessing an unsaturated organic function, wherein the silane is vinyl triethoxysilane and/or vinyl trimethoxysilane;
(ii) at least two free radical initiators, the first initiator having a first 0.1 hour half-life temperature and the second initiator having a second 0.1 hour half-life temperature being between 30° and 90° C. higher than said first half-life temperature;
(iii) at least one thermoplastic polyolefin; and,
b. reacting the mixture of step (a) under reactive mechanical-working conditions and exposure to moisture to provide crosslinked polyolefin.
11. The process of claim 10 wherein the 0.1 hour half-life temperatures of the first free radical initiator is from about 80° to about 160° C.
12. The process of claim 10 wherein the 0.1 hour half-life temperature of the second free radical initiator is from about 125° to about 190° C.
13. The process of claim 10 wherein the first free radical initiator is selected from the group consisting of di(2,4-dichlorobenzoyl) peroxide, tert-butyl peroxypivalate, dilauroyl peroxide, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(tert-butylperoxy)cyclohexane, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.
14. The process of claim 10 wherein the second free radical initiator is selected from the group consisting of tert-butyl peroxyacetate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3 and di-tert-butyl peroxide.
15. The process of claim 10 wherein mixture (a) further includes at least one additional component selected from the group consisting of catalysts, stabilizers, fillers, antioxidants, processing aids, oils, plasticizers, pigments and lubricants.
16. The process of claim 15 where catalyst is a metal carboxylate, an organic metal compound, an organic base, or an acid.