Process for the production of crosslinked polymer employing low VOC-producing silane crosslinker and resulting crosslinked polymer
View Patent ↗A process for crosslinking polymers employs a silane crosslinker which, upon hydrolysis, produces a reduced quantity of volatile organic compound.
1. A crosslinkable polymer comprising a thermoplastic polymer possessing a hydrolyzable silane which is a cyclic diol-substituted silane grafted thereto.
2. The crosslinkable polymer of claim 1 wherein the polymer is at least one member selected from the group consisting of homopolymers and copolymers of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene and decene.
3. The crosslinkable polymer of claim 1 wherein the polymer is at least one copolymer selected from the group consisting of (i) ethylene copolymerized with one or more other ethylenically unsaturated monomer, ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid ester and/or ethenically unsaturated dicarboxylic acid anhydride, (ii) olefin-based rubber and (iii) ionomer resin.
4. The crosslinkable polymer of claim 1 wherein the silane is introduced into the structure of the polymer by being grafted thereto employing a free radical generator.
5. The crosslinkable polymer of claim 1 wherein the silane has the general formula:
[Y[-G(—SiX u Z b v Z c w ) s ] r ] n (Formula 1)
wherein each occurrence of G is independently chosen from a set of groups comprising a polyvalent group derived by substitution of one or more hydrogen atoms of an alkyl, alkenyl, aryl or aralkyl group, or a molecular component which can be obtained by removal of one or more hydrogen atoms of a heterocarbon, with G containing from about 1 to about 30 carbon atoms; each occurrence of X is independently selected from the group consisting of —Cl, —Br, R 1 O—, R 1 C(═O)O—, R 1 R 2 C═NO—, R 1 R 2 NO— or R 1 R 2 N—, —R 1 , —(OSiR 1 R 2 ) t (OSi R 1 R 2 R 3 ), and—O(R 10 CR 11 ) f OH, wherein each occurrence of R 1 , R 2 , R 3 , R 10 and R 11 is independently R; each occurrence of Z b is independently (—O—) 0.5 , and [—O(R 10 CR 11 ) f O—] 0.5 , wherein each occurrence of R 10 and R 11 is independently R; each occurrence of Z c is independently given by —O(R 10 CR 11 ) f O— wherein each occurrence of R 10 and R 11 is independently R; each occurrence of R is chosen independently from the set of groups comprising hydrogen; straight, cyclic or branched alkyl groups and can contain unsaturated, alkenyl groups, aryl groups and aralkyl groups; or molecular components obtained by removal of one or more hydrogen atoms of a heterocarbon; each occurrence of R containing 1 to about 20 carbon atoms; each occurrence of the subscript f is an integer from 1 to about 15, each occurrence of n is an integer from 1 to about 100, with the proviso that when n is greater than 1, v is a greater than 0 and all the valences for Z b have a silicon atom bonded to them, each occurrence of the subscript u is an integer from 0 to about 3, each occurrence of the subscript v is an integer from 0 to about 3, each occurrence of the subscript w is an integer from 0 to about 1, with the proviso that u+v+2w=3, each occurrence of the subscript r is an integer from 1 to about 6, each occurrence of the subscript t is an integer from 0 to about 50, and each occurrence of the subscript s is an integer from 1 to about 6; and each occurrence of Y is an organofunctional group of valence r; and at least one cyclic and bridging dialkoxy organofunctional silane comprising the cyclic and bridging dialkoxy organofunctional silane composition containing at least one occurrence of Z b or Z c .
6. The crosslinkable polymer of claim 5 wherein Y is selected from the group consisting of a univalent organofunctional group, a divalent organofunctional group, a trivalent organofunctional group, a tetravalent organofunctional group and a polyvalent organofunctional group.
7. The crosslinkable polymer of claim 6 wherein the univalent organofunctional group is selected from the group consisting of CH 2 ═CH—, CHR═CH—, CR 2 ═CH—, mercapto, acryloxy, methacryloxy, acetoxy, —O—CH 2 —C 2 H 3 O, —CH 2 —CH 2 —C 6 H 9 O, —C 6 H 9 O, —CR 6 (—O—)CR 4 R 5 , —OH, —NR 4 C(═O)OR 5 , —OC(═O)NR 4 R 5 , —NR 4 C(═O)SR 5 , —SC(═O)NR 4 R 5 , —NR 4 C(═S)OR 5 , —OC(═S)NR 4 R 5 , —NR 4 C(═S)SR 5 , —SC(═S)NR 4 R 5 , maleimide, maleate, substituted maleate, fumarate, substituted fumarate, —CN, citraconimide, —OCN, —N═C═O, —SCN, —N═C═S, —OR 4 , —F, —Cl, —Br; —I, —SR 4 , —S—SR 4 , —S—S—SR 4 , —S—S—S—SR 4 , —S—S—S—S—SR 4 , —S—S—S—S—S—SR 4 , —S x R 4 , —SC(═S)OR 4 , SC(═S)SR 4 , —SC(═O)SR 4 , —NR 4 C(═O)NR 5 R 6 , —NR 4 C(═S)NR 5 R 6 , R 4 C(═O)NR 5 —, —C(═O)NR 4 R 5 —, R 4 C(═S)NR 4 —, melamine, cyanurato, —NH 2 , —NHR 4 , —NR 4 R 5 , —NR 4 -L 1 -NR 5 R 6 , —NR 4 -L (—NR 5 R 6 ) 2 , —NR 4 -L 1 -NR 5 -L 2 -NR 6 R 7 , —NR 4 -L 1 (—NR 5 R 6 ) 3 , —NR 4 -L 1 -NR 5 -L 2 -NR 6 -L 1 -NR 7 R 8 and —NR 4 -L 1 -N(-L 2 NR 5 R 6 ) 2 ; the divalent organofunctional group is selected from the group consisting of -(—)C(—O—)CR 4 R 5 , —CR 5 (—O—)CR 4 —, —O(R 10 CR 11 ) f O—, -(—) NC(═O)OR 5 , —OC(═O)NR 4 —, -(—)NC(═O)SR 5 , —SC(═O)NR 4 —, -(—)NC(═S)OR 5 , —OC(═S)NR 4 —, -(—)NC(═S)SR 5 , —SC(═S)NR 4 —, —O—, maleate, substituted maleate, fumarate, substituted fumarate, —S—, —S—S—, —S—S—S—, —S—S—S—S—, —S—S—S—S—S—, —S—S—S—S—S—S—, —S x —, —SC(═S)O—, —SC(═S)S—, —SC(═O)S—, -(—)NC(═O)NR 4 R 5 , —NR 4 C(═O)NR 5 —, -(—)NC(═S)NR 4 R 5 , —NR 4 C(═S)NR 5 —R 4 C(═O)N(—)-, —C(═O)NR 4 —, R 4 C(═S)N(—)-, divalent melamine, divalent cyanurato, —NH—, —NR 4 —, -(—)N-L 1 -NR 4 R 5 , —NR 4 -L 1 -NR 5 —,(-)NR 4 ) 2 -L 1 -NR 5 R 6 , -(—)N-L 1 -NR 5 -L 2 -NR 6 R 7 , —NR 4 -L 1 -N(—)-L 2 -NR 5 R 6 , —NR 4 -L 1 -NR 5 -L 2 -NR 6 —, -(—)N-L 1 -(NR 5 R 6 ) 3 , (—NR 4 ) 2 -L 1 -(NR 5 R 6 ) 2 , -(—)N-L 1 -NR 4 -L 2 -NR 5 -L 3 -NR 6 R 7 , —NR 4 -L 1 -N(—)-L 2 -NR-L 3 -NR 6 R 7 , —NR 4 -L 1 -NR 5 -L 2 -N(—)-L 3 -NR 6 R 7 , —NR 4 -L 1 -NR 5 -L 2 -NR 6 -L 3 -NR 7 —, -(—)N-L 1 -N(-L 2 NR 5 R 6 ) 2 and (—NR 4 L 1 -) 2 N-L 2 NR 5 R 6 ; the trivalent organofunctional group is selected from the group consisting of —(—)C(—O—)CR 4 —, —(—)NC(═O)O—, -(—)NC(═O)S—, —( )NC(═S)O—, —(—)NC(═S)S—, —(—)NC(═O)NR 4 —, —(—)NC(═S)NR 4 —, —C(═O)N(—)—, —C(═S)N(—)—, trivalent melamino; trivalent cyanurato, —N(—)—, —(—)N-L 1 -NR 4 —, (—NR 4 ) 3 -L 1 , (—NR 4 ) 2 -L 1 -NR 5 —, —(—)N-L 1 -N(—)-L 2 -NR 3 R 4 , —NR 4 -L 1 -N(—)-L 2 -NR 5 —, —(—)N-L 1 -NR 4 -L 2 -NR 5 —, —(—)N-L 1 -N(—)-L 2 -NR 5 -L 3 -NR 3 R 4 , —NR 4 -L 1 -N(—)-L 2 -N(—)-L 3 -NR 3 R 4 , —(—)N-L 1 -NR 5 -L 2 -N(—)-L 3 -NR 3 R 4 , —NR 4 -L 1 -N(—)-L 2 -NR 3 -L 3 -NR 4 —, —(—)N-L 1 -N(-L 2 NR 3 R 4 )(-L 2 NR 5 —) and (—NR 4 L 1 -) 3 N; the tetravalent organofunctional group is selected from the group consisting of —(—)C(—O—)C(—)—, —(—)NC(═O)N(—)—, —(—)NC(═S)N(—)—, tetravalent melamino, —(—)N-L 1 -N(—)—, (—NR 4 ) 4 -L 1 , (—NR 4 ) 2 -L 1 -N(—)—, —(—)N -L 1 -N(—)-L 2 -NR 3 —, —(—)N-L 1 -NR 4 -L 2 (—)—, —(—)N-L 1 -N(—)-L 2 -N(—)-L 3 -NR 4 R 3 , —NR 4 -L 1 -N(—)-L 2 -N(—) -L 3 -NR 3 —, —(—)N-L 1 -NR 4 -L 2 -NR 3 -L 3 -N(—)—and —(—)N-L 1 -N(-L 2 NR 3 —) 2 ; and, the polyvalent organofunctional group is selected from the group consisting of polyvalent hydrocarbon groups, (—NR 3 )(—N—) 2 C 3 N 3 ,(—N—) 3 C 3 N 3 , —(—)N-L 1 -N(—)-L 2 -N(—)—, —(—)N-L 1 -N(—)-L 2 -N(—)-L 3 -NR 3 —, —(—)N-L 1 -NR 3 -L 2 -N(—)-L 3 -N(—)—, [—(—)N-L 1 -] 2 N-L 2 NR 3 —, —(—)N-L 1 -N(—)-L 2 -N(—)-L 3 -N(—)—and [—(—)N-L 1 -] 3 ,
wherein each occurrence of L 1 , L 2 , and L 3 is selected independently from the set of structures given above for G, each occurrence of R is independently given by one of the structures listed above for R and R 1 through R 11 and x is independently an integer from 1 to 10.
8. The crosslinkable polymer of claim 7 wherein the dialkoxy or difunctional alkoxy is represented by the formula:
—O(R 10 CR 11 ) f O— (Formula 3).
9. The crosslinkable polymer of claim 5 wherein G is selected from the group consisting of a monovalent hydrocarbon group, CH 3 (CH 2 ) p — wherein p is 1 to 20, diethylene cyclohexane, 1, 2,4-triethylene cyclohexane, diethylene benzene,phenylene, —(CH 2 ) m — wherein m is 1 to 12 and CH 2 (CH 2 ) q CH(CH 3 )— wherein q is zero to 17.
10. The crosslinkable polymer of claim 5 wherein R and R 1 through R 11 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, octenyl, cyclohexyl, butyl, phenyl, benzyl, tolyl, allyl, methoxyethyl, ethoxyethyl, dimethylaminoethyl and cyanoethyl.
11. The crosslinkable polymer of claim 5 wherein R 10 and R 11 are each independently selected from a group consisting of hydrogen, methyl and ethyl.
12. The process of claim 5 wherein R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl and propyl.
13. The crosslinkable polymer of claim 5 wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from the group consisting of phenyl, methyl, butyl, hydrogen and ethyl.
14. The crosslinkable polymer of claim 5 wherein X is selected from the group consisting of methoxy, ethoxy, isobutoxy, propoxy, isopropoxy, acetoxy, methoxyethoxy, oximato and monovalent alkoxy groups derived from diols.
15. The crosslinkable polymer of claim 5 wherein Z b and Z c are selected from the group consisting of divalent alkoxy groups derived from the diols consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol and 2-methyl-2,4-pentanediol.
16. The crosslinkable polymer of claim 5 wherein a ratio of w/v is between 1 and 9;
X is R 1 O— or R 1 C(═O)O—;
Z b and Z c are derived from the group of diols consisting of 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol and 2-methyl-2,4-pentanediol;
R 1 is independently selected from the group consisting of an alkyl of C 1 to C 4 and H; and,
G is a divalent straight chain alkyl of 2 to 18 carbon atoms.
17. The crosslinkable polymer of claim 5 wherein the ratio of w/v is between about 2 and about 8;
X is ethoxy or one or more of the divalent alkoxy groups derived from the diols selected from the group consisting of 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol and 2-methyl-2,4-pentanediol; and,
G is a C 2 -C 12 straight-chain alkyl derivative.
18. The crosslinkable polymer of claim 5 wherein v is 0, X is RO— or RC(═O)—, R is an alkyl of C 1 to C 4 or H, and G is a divalent straight chain alkyl of 2 to 18 carbon atoms.
19. The crosslinkable polymer of claim 1 wherein the silane is introduced into the structure of the polymer by being grafted thereto employing a free radical generator.
20. A crosslinked polymer comprising the crosslinkable polymer of claim 1 .