Process for crosslinking thermoplastic polymers with silanes employing peroxide blends, the resulting crosslinked thermoplastic polymer composition and articles made therefrom
View Patent ↗A moisture crosslinkable thermoplastic composition is produced by a process of grafting an unsaturated silane of the formula: G 1 R 1 SiZ where G 1 is vinyl, R 1 is methyl and Z is a divalent hydrolyzable group under reactive mechanical working conditions and in the presence of at least two peroxides and subsequently is converted into a crosslinked thermoplastic composition by exposure to moisture in the presence of a crosslinking catalyst.
1. A composition comprising:
(i) one or more unsaturated silane compounds according to the Formula (2):
G 1 R 1 SiZ (2)
wherein G 1 is vinyl; R 1 is methyl; Z is a divalent hydrolyzable group containing of from 2 to 30 carbon atoms that forms a cyclic structure with the silicon atom of Formula (2) and has the general Formula (3)
—O(R 2 CR 2 ) c O— (3)
wherein each occurrence of R 2 is independently hydrogen or R 1 ; and c is an integer of from 2 to 3;
and
(ii) a system of at least two peroxides comprising a first peroxide having a first 0.1 hour half-life temperature and a second peroxide having a second 0.1 hour half-life temperature, the first and second 0.1 hour half-life temperatures in said composition having a temperature differential of from about 5° C. to about 110° C.
2. The composition of claim 1 , wherein the Z group is selected from the group consisting of 2,3-butanedioxy, 2-methyl-1,2propanedioxy, 2,2-dimethyl-1,3-propanedioxy, 2-methyl-2,4-pentanedioxy, 2,3dimethyl-2,3-butanedioxy and 2,4-dimethyl-2,4-pentanedioxy.
3. The composition of claim 1 , wherein the first peroxide is selected from the group consisting of bis-(2,4-dichlorobenzoyl)peroxide, tert-butylperoxypivalate, dilauroyl peroxide, dibenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, 1,1-bis-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, bis-(tert-butylperoxy)cyclohexane, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butylperoxyacetate, tert- butylperoxybenzoate, di-tert-amyl peroxide, dicumylperoxide, bis-(tert-butyl peroxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and combinations thereof; and the second peroxide is selected from the group consisting of tert-butylperoxyacetate, tert-butylperoxybenzoate, di-tert-amyl peroxide, dicumylperoxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis-(t-butylperoxy)hexane, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-bis-(t-butylperoxy)-3-hexyne, di-tert-butylperoxide and combinations thereof; wherein at least one first peroxide is different from at least one second peroxide.
4. A composition comprising:
(i) one or more unsaturated silane compounds according to the Formula (2):
G 1 R 1 SiZ (2)
wherein G 1 is vinyl R 1 methyl Z is a divalent hydrolyzable group containing of from 2 to 30 carbon atoms that forms a cyclic structure with the silicon atom of Formula (2) and has the general Formula (3)
—O(R 2 CR 2 ) c O— (3)
wherein each occurrence of R 2 is independently hydrogen or R 1 ; and c is an integer of from 2 to 3;
(ii) a system of at least two peroxides comprising a first peroxide having a first 0.1 hour half-life temperature and a second peroxide having a second 0.1 hour half-life temperature, the first and second 0.1 hour half-life temperatures having a temperature differential in said composition of from about 5° C. to about 110° C. and
(iii) one or more thermoplastic polymers; and
(iv) one or more crosslinking catalysts;
the composition optionally containing one or more additional components.
5. The composition of claim 4 , wherein the Z group is selected from the group consisting of 2,3-butanedioxy, 2-methyl-1,2-propanedioxy, 2,2-dimethyl-1,3-propanedioxy, 2-methyl-2,4-pentanedioxy, 2,3-dimethyl-2,3-butanedioxy and 2,4-dimethyl-2,4-pentanedioxy.
6. The composition of claim 4 , wherein the one or more thermoplastic polymers are selected from the group consisting of high-pressure low-density polyethylene, medium- or low-pressure high-density polyethylene, low-pressure low-density polyethylene, medium-density polyethylene, ethylene-α-olefin copolymers, polypropylene, ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, ethylene-butene copolymers, polymethylpentene, polybutenes, chlorinated polyethylenes, chlorinated ethylene-vinyl acetate terpolymers, and combinations thereof.
7. A silane-grafted thermoplastic polymer comprising a thermoplastic polymer grafted to one or more unsaturated silane compounds according to a process comprising subjecting a composition comprising (i) one or more unsaturated silane compounds, (ii) a system of at least two peroxides, and (iii) one or more thermoplastic polymers, to conditions suitable for grafting of the unsaturated silane compound to the thermoplastic polymer to form a silane-grafted thermoplastic polymer, wherein:
the one or more unsaturated silane compounds are according to the Formula (2):
G 1 R 1 SiZ (2)
wherein G 1 is vinyl; R 1 is methyl; Z is a divalent hydrolyzable group containing of from 2 to 30 carbon atoms that forms a cyclic structure with the silicon atom of Formula (2) and has the general Formula (3)
—O(R 2 CR 2 ) c O— (3)
wherein each occurrence of R 2 is independently hydrogen or R 1 ; and c is an integer of from 2 to 3; and
the system of at least two peroxides comprises a first peroxide having a first 0.1 hour half-life temperature and a second peroxide having a second 0.1 hour half-life temperature, the first and second 0.1 hour half-life temperatures in said composition having a temperature differential of at least about 5° C.
8. The composition of claim 7 , wherein the Z group is selected from the group consisting of 2,3-butanedioxy, 2-methyl-1,2-propanedioxy, 2,2-dimethyl-1,3-propanedioxy, 2-methyl-2,4-pentanedioxy, 2,3-dimethyl-2,3-butanedioxy and 2,4-dimethyl-2,4-pentanedioxy.
9. A process for producing a silane-grafted thermoplastic polymer, the process comprising subjecting a composition comprising (i) one or more unsaturated silane compounds, (ii) a system of at least two peroxides, and (iii) one or more thermoplastic polymers, to conditions suitable for grafting of the unsaturated silane compound to the thermoplastic polymer to form a silane-grafted thermoplastic polymer, said conditions including subjecting the composition to a reaction temperature of from about 140° C. to about 260° C. for a period of time of from about 0.5 minutes to about 10 minutes, wherein:
the one or more unsaturated silane compounds are according to the Formula (2)
G 1 R 1 SiZ (2)
wherein G 1 is vinyl; R 1 is methyl; Z is a divalent hydrolyzable group containing of from 2 to 30 carbon atoms that forms a cyclic structure with the silicon atom of Formula (2) and has the general Formula (3)
—O(R 2 CR 2 ) c O— (3)
wherein each occurrence of R 2 is independently hydrogen or R 1 ; and c is an integer of from 2 to 3; and
the system of at least two peroxides comprising a first peroxide having a first 0.1 hour half-life temperature and a second peroxide having a second 0.1 hour half-life temperature, the first and second 0.1 hour half-life temperatures in said composition having a temperature differential of from about 5° C. to about 110° C.
10. The process of claim 9 , further comprising subjecting the silane-grafted thermoplastic polymer to conditions suitable for crosslinking of the silane-grafted thermoplastic polymer to produce a crosslinked thermoplastic polymer, said conditions including contacting the silane grafted thermoplastic polymer with moisture and a crosslinking catalyst.
11. The process of claim 9 , wherein the one or more polyolefins are selected from the group consisting of high-pressure low-density polyethylene, medium- or low-pressure high-density polyethylene, low-pressure low-density polyethylene, medium-density polyethylene, ethylene-α-olefin copolymers, polypropylene, ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, ethylene-butene copolymers, polymethylpentene, polybutenes, chlorinated polyethylenes, chlorinated ethylene-vinyl acetate terpolymers, and combinations thereof.
12. The process of claim 9 , wherein the Z group is selected from the group consisting of 2,3-butanedioxy, 2-methyl-1,2-propanedioxy,2,2-dimethyl-1,3-propanedioxy, 2-methyl-2,4-pentanedioxy, 2,3-dimethyl-2,3-butanedioxy and 2,4-dimethyl-2,4-pentanedioxy.
13. The process of claim 9 , wherein the first peroxide is selected from the group consisting of bis-(2,4-dichlorobenzoyl)peroxide, tert-butylperoxypivalate, dilauroyl peroxide, dibenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, 1,1-bis-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, bis-(tert- butylperoxy)cyclohexane, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butylperoxyacetate, tert-butylperoxybenzoate, di-tert-amyl peroxide, dicumylperoxide, bis-(tert-butyl peroxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and combinations thereof; and the second peroxide is selected from the group consisting of tert-butylperoxyacetate, tert-butylperoxybenzoate, di-tert-amyl peroxide, dicumylperoxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis-(t-butylperoxy)hexane, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-bis-(t-butylperoxy)-3-hexyne, di-tert-butylperoxide and combinations thereof; wherein at least one first peroxide is different from at least one second peroxide.
14. An article produced by a process comprising:
a) providing a composition comprising:
(i) one or more unsaturated silane compounds according to the Formula (2):
G 1 R 1 SiZ (2)
wherein G 1 is vinyl R 1 is methyl Z is a divalent hydrolyzable group containing of from 2 to 30 carbon atoms that forms a cyclic structure with the silicon atom of Formula (2) and has the general Formula (3)
—O(R 2 CR 2 ) c O— (3)
wherein each occurrence of R 2 is independently hydrogen or R 1 ; and c is an integer of from 2 to 3;
(ii) a system of at least two peroxides comprising a first peroxide having a first 0.1 hour half-life temperature and a second peroxide having a second 0.1 hour half-life temperature, the first and second 0.1 hour half-life temperatures in said composition having a temperature differential of from about 5° C. to about 110° C.; and
(iii) one or more thermoplastic polymers;
b) subjecting the composition of step (a) to conditions suitable for grafting of the unsaturated silane compound to the thermoplastic polymer to form a silane-grafted thermoplastic polymer;
c) subjecting the silane-grafted thermoplastic polymer of step (b) to conditions suitable for crosslinking of the silane-grafted thermoplastic polymer to form a crosslinked thermoplastic polymer; and,
d) producing the article therefrom before, and/or during and/or after conducting step (c), wherein the conditions for silane grafting according to step (b) and for crosslinking according to step (c) are the same or different, and wherein steps (b) and (c) are conducted simultaneously or consecutively.