(Meth)acryloxy-containing trisiloxane, siloxane-containing polymers and biomedical devices therefrom
View Patent ↗There is provided a trisiloxane having a 3-(meth)acryloxy-substituted (hydroxylcyclohexyl)ethyl group, useful in making water absorbing silicone-hydrogel films for biomedical devices, such as contact lens, and a process for producing these monomers. This invention also provides for copolymers made from the trisiloxane having a 3-(meth)acryloxy-substituted (hydroxylcyclohexyl)ethyl group described herein.
1. A trisiloxane of the general Formula (I):
wherein R is hydrogen or methyl; Y 1 is hydrogen or hydroxyl; and, Y 2 is hydrogen or hydroxyl, with the proviso that at least one Y 1 or Y 2 is a hydroxyl group.
2. The trisiloxane of claim 1 selected from the group consisting of acrylic acid 2-hydroxy-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, methacrylic acid 2-hydroxy-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, acrylic acid 2-hydroxy-3-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, methacrylic acid 2-hydroxy-3-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, and mixtures thereof.
3. The trisiloxane of claim 2 wherein the trisiloxane is selected from the group consisting of acrylic acid trans-2-hydroxy-trans-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, methacrylic acid trans-2-hydroxy-trans-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, acrylic acid trans-2-hydroxy-trans-3-[2-bis-(trimethylsiloxy)-methylsilanyl-ethyl]-cyclohexyl ester, methacrylic acid trans-2-hydroxy-trans-3-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, and mixtures thereof.
4. The trisiloxane of claim 1 , wherein the trisiloxane has the stereochemical structure of Formula (II):
wherein R is hydrogen or methyl.
5. The trisiloxane of claim 3 comprising from 40 to 99 weight percent acrylic acid trans-2-hydroxy-trans-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester and from 1 to 60 weight percent of acrylic acid trans-2-hydroxy-cis-4-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester based on the total weight of the two isomers, or from 40 to 99 weight percent methacrylic acid trans-2-hydroxy-trans-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester and from 1 to 60 weight percent methacrylic acid trans-2-hydroxy-cis-4-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester based on the total weight of the two isomers.
6. A process for preparing trisiloxane of claim 1 which comprises:
a) reacting ethenyl-oxa-bicyclo[4.1.0]heptane with 1,1,1,2,3,3,3-heptamethyl-trisiloxane in the presence of a hydrosilylation catalyst to provide a hydrosilylated product; and,
b) reacting the hydrosilylated product of step (a) with (meth)acrylic acid, optionally in the presence of an oxirane ring-opening catalyst to produce trisiloxane of claim 1 .
7. The process of claim 6 wherein greater than 85 weight percent of the ethenyl-oxa-bicyclo[4.1.0]heptane is 3-ethenyl-7-oxa-bicyclo[4.1.0]heptane which has the oxygen atom of the oxirane ring bonded to the 1 and 6-carbon atoms of the cyclohexyl ring in the C-1 equatorial and C-6 axial positions and has the ethenyl group bonded to the 3-carbon atom of the cyclohexyl ring in the equatorial position, or greater than 85 weight percent of the ethenyl-oxa-bidcyclo[4.1.0]heptane is 2-ethenyl -7-oxa-bicyclo[4.1.0]heptane which has the oxygen atom of the oxirane ring bonded to the 1 and 6-carbon atoms of the cyclohexyl ring in the C-1 axial and C-6 equatorial positions and has the ethenyl group bonded to the 2-carbon atom of the cyclohexyl ring in the equatorial position.
8. A copolymer obtained by the copolymerization of copolymerizable mixture comprising trisiloxane of claim 1 , monomer containing an activated carbon-carbon double bond and crosslinker.
9. The copolymer of claim 8 wherein the monomer containing an activated carbon-carbon double bond is selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, methyl acrylate, 2-hydroxyethyl methacrylate, N-vinylpyrrolidone, methacrylic acid and dimethylacrylamide, and mixtures thereof.
10. The copolymer of claim 8 wherein the crosslinker is selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, ethylene glycol dicrotonate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol dimethacrylate, dipropylene glycol diacrylate, trimethylene glycol diacrylate, triethylene glycol diemthacrylate, triethylene glycol dicrotonate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, tributylene glycol dimethacrylate, tetrabutylene glycol dimethacrylate, hexamethylene glycol dimethacrylate, octamethylene glycol dimethacrylate, decamethylene glycol dimethacrylate, allyl methacrylate, divinylbenzene, diallyl phthalate, trimethylolpropane trimethacrylate, diallyl tartrate, diallyl maleate, triallylmelamine, N,N′-methylenebisacrylamide, divinyl citraconate, diallyl fumarate, divinyl sulfone, triallyl phosphite, diallyl benzenephosphonate, hexahydro-1,3,5-triacryltriazine, divinyl ether, triallyl citrate, polysiloxanylbis(alkylglycerol acrylate), polysiloxanylbis(alkylglycerol methacrylate), and mixtures thereof.
11. The copolymer of claim 8 wherein the ratio of trisiloxane to monomer containing an activated carbon-carbon double bond is from 1:2 to 2:1.
12. The copolymer of claim 8 wherein the copolymerizable mixture comprises from 40 to 60 weight percent trisiloxane, from 20 to 30 weight percent dimethylacrylamide, from 15 to 25 weight percent 2-hydroxyethyl (meth)acrylate, from 1 to 10 weight percent N-vinylpyrrolidone and from 0.1 to 3 weight percent ethylene glycol dimethyl acrylate based on the total weight of the mixture.
13. A contact lens comprising copolymer of claim 8 .
14. A contact lens comprising copolymer of claim 11 .
15. A contact lens comprising copolymer of claim 12 .
16. The contact lens of claim 13 wherein the trisiloxane is selected from the group consisting of acrylic acid 2-hydroxy-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, methacrylic acid 2-hydroxy-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, acrylic acid 2-hydroxy-3-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]cyclohexyl ester, methacrylic acid 2-hydroxy-3-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, and mixtures thereof.
17. The contact lens of claim 13 wherein the trisiloxane is selected from the group consisting of acrylic acid trans-2-hydroxy-trans-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, methacrylic acid trans-2-hydroxy-trans-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, acrylic acid trans-2-hydroxy-trans-3-[2-bis-(trimethylsiloxy)-methylsilanyl-ethyl]-cyclohexyl ester, methacrylic acid trans-2-hydroxy-trans-3-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester, and mixtures thereof.
18. The contact lens of claim 13 wherein the siloxane comprises from 40 to 99 weight percent acrylic acid trans-2-hydroxy-trans-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester and from 1 to 60 weight percent of acrylic acid trans-2-hydroxy-cis-4-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester based on the total weight of the two isomers, or from 40 to 99 weight percent methacrylic acid trans-2-hydroxy-trans-5-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester and from 1 to 60 weight percent methacrylic acid trans-2-hydroxy-cis-4-[2-bis-(trimethylsiloxy)methylsilanyl-ethyl]-cyclohexyl ester based on the total weight of the two isomers.
19. A coating composition comprising trisiloxane of claim 1 .
20. A coating composition comprising copolymer of claim 8 .