Multifunctional crosslinking agents and ophthalmic devices formed therefrom
A multifunctional crosslinking agent includes one or more repeating units of a siloxanyl group or a silyl-alkyl-siloxanyl group, and at least two ethylenically unsaturated reactive end groups. One of the at least two ethylenically unsaturated reactive end groups is a (meth)acrylate-containing reactive end group or an acrylamide-containing reactive end group and the other one is an allyl-containing reactive end group or a vinyl-containing reactive end group. Ophthalmic devices are formed from a polymerization product of a monomeric mixture containing one or more of the multifunctional crosslinking agents, one or more first ophthalmic device-forming comonomers having at least one reactive group that preferentially reacts with the (meth)acrylate-containing reactive end group or the acrylamide-containing reactive end group of the multifunctional crosslinking agent, and one or more second ophthalmic device-forming comonomers having at least one reactive group that preferentially reacts with the allyl-containing reactive end group or the vinyl-containing reactive end group of the multifunctional crosslinking agent.
1 . An ophthalmic device which is a polymerization product of a monomeric mixture comprising:
(a) one or more multifunctional crosslinking agents comprising one or more repeating units of a siloxanyl group or a silyl-alkyl-siloxanyl group, and at least two ethylenically unsaturated reactive end groups, wherein one of the at least two ethylenically unsaturated reactive end groups is a (meth) acrylate-containing reactive end group or an acrylamide-containing reactive end group and the other one of the at least two ethylenically unsaturated reactive end groups is an allyl-containing reactive end group;
(b) one or more first ophthalmic device-forming comonomers having at least one reactive group that preferentially reacts with the (meth) acrylate-containing reactive end group or the acrylamide-containing reactive end group of the multifunctional crosslinking agent, wherein the one or more first ophthalmic device-forming comonomers comprise one or more silicone-containing comonomers represented by a structure of Formula I:
wherein V is an ethylenically unsaturated polymerizable group, L is a linker group or a bond; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently H, a C 1 to C 12 alkyl group, a halo alkyl group, a C 3 to C 12 cycloalkyl group, a heterocycloalkyl group, a C 2 to C 12 alkenyl group, a haloalkenyl group, or a C 6 to C 12 aromatic group; R 10 and R 11 are independently H or a C 1 to C 12 alkyl group, wherein at least one of R 10 and R 11 is hydrogen; y is 2 to 7 and n is 1 to 100; and
(c) one or more second ophthalmic device-forming comonomers having at least one reactive group that preferentially reacts with the allyl-containing reactive end group of the multifunctional crosslinking agent.
2 . The ophthalmic device according to claim 1 , wherein the one or more multifunctional crosslinking agents comprise from 3 to about 300 repeating units of the siloxanyl group.
3 . The ophthalmic device according to claim 1 , wherein the one or more multifunctional crosslinking agents comprise one or more repeating units of the siloxanyl group represented by the following structure:
wherein R 1 and R 2 are independently hydrogen, a C 1 to C 12 alkyl group, a halo alkyl group, a C 3 to C 12 cycloalkyl group, a C 3 to C 12 heterocycloalkyl group, a C 2 to C 12 alkenyl group, a haloalkenyl group, or a C 6 to C 12 aromatic group and y is from 3 to about 300.
4 . The ophthalmic device according to claim 1 , wherein the one or more multifunctional crosslinking agents comprise 1 to about 100 repeating units of the silyl-alkyl-siloxanyl group, and the alkyl group of the silyl-alkyl-siloxanyl group has from 2 to about 4 carbon atoms.
5 . The ophthalmic device according to claim 1 , wherein the one or more multifunctional crosslinking agents comprise one or more repeating units of the silyl-alkyl-siloxanyl group represented by the following structure:
wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independently hydrogen, a C 1 to C 12 alkyl group, a halo alkyl group, a C 3 to C 12 cycloalkyl group, a C 3 to C 12 heterocycloalkyl group, a C 2 to C 12 alkenyl group, a haloalkenyl group, or a C 6 to C 12 aromatic group; a is from 2 to 4 and x is from 1 to about 100.
6 . The ophthalmic device according to claim 1 , wherein the one or more first ophthalmic device-forming comonomers further comprise one or more additional silicone-containing comonomers.
7 . The ophthalmic device according to claim 6 , wherein the one or more additional silicone-containing comonomers are selected from the group consisting of a silicone-containing comonomer represented by a structure of Formula II:
wherein R 12 is H or methyl; X is O or NR 16 ; wherein R 16 is selected from H, or a C 1 to C 4 alkyl group, optionally substituted with one or more hydroxyl groups; R 13 is a divalent alkyl group, optionally functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R 14 is independently a phenyl group or a C 1 to C 4 alkyl group, optionally substituted with fluorine, a hydroxyl group or an ether group; R 15 is a C 1 to C 4 alkyl group; and a is 2 to 50, a polysiloxane prepolymer represented by a structure of Formula III:
wherein each V is an independently reactive functional end group; R 17 to R 22 are independently a straight or branched, substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 4 -C 30 cycloalkylalkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkenyl group, a substituted or unsubstituted C 6 -C 30 aryl group, and a substituted or unsubstituted C 7 -C 30 arylalkyl group, and L is independently a linking group; and x is 37, a silicone-containing comonomer represented by a structure of Formula IV:
wherein X denotes —O— or —NR 19 —, wherein R 19 is hydrogen or a C 1 -C 4 alkyl group; R 17 denotes hydrogen or methyl; each R 18 independently denotes a C 1 -C 6 alkyl group, a phenyl group or a group represented by:
wherein each R 18′ independently denotes a C 1 -C 6 alkyl, or a phenyl radical; and h is 1 to 10, and a silicone-containing comonomer represented by a structure of Formula V:
wherein X denotes —NR 19 —, wherein R 19 denotes hydrogen or a C 1 -C 4 alkyl group; R 17 denotes hydrogen or methyl; each R 18 independently denotes a C 1 -C 6 alkyl group, a phenyl group or a group represented by:
wherein each R 18′ independently denotes a C 1 -C 6 alkyl group, or a phenyl group; and h is 1 to 10.
8 . The ophthalmic device according to claim 1 , wherein the one or more second ophthalmic device-forming comonomers comprise one or more hydrophilic comonomers.
9 . The ophthalmic device according to claim 8 , wherein the one or more hydrophilic comonomers are selected from the group consisting of a hydrophilic vinyl monomer, an acrylamide and mixtures thereof.
10 . The ophthalmic device according to claim 1 , wherein the monomeric mixture comprises:
about 0.1 wt. % to about 50 wt. %, based on the total weight of the monomeric mixture, of the one or more multifunctional crosslinking agents;
about 1 wt. % to about 80 wt. %, based on the total weight of the monomeric mixture, of the one or more first ophthalmic device-forming comonomers; and
about 1 wt. % to about 80 wt. %, based on the total weight of the monomeric mixture, of the one or more second ophthalmic device-forming comonomers.
11 . The ophthalmic device according to claim 1 , which is a contact lens or a soft hydrogel.
12 . A method for making an ophthalmic device, comprising:
a) curing a monomeric mixture in a mold, the monomeric mixture comprising:
(i) one or more multifunctional crosslinking agents comprising one or more repeating units of one or more siloxanyl units or one or more silyl-alkyl-siloxanyl units, and at least two ethylenically unsaturated reactive end groups, wherein one of the at least two ethylenically unsaturated reactive end groups is a (meth) acrylate-containing reactive end group or an acrylamide-containing reactive end group and the other one of the at least two ethylenically unsaturated reactive end groups is an allyl-containing reactive end group;
(ii) one or more first ophthalmic device-forming comonomers having at least one reactive group that preferentially reacts with the (meth) acrylate-containing reactive end group or the acrylamide-containing reactive end group of the multifunctional crosslinking agent, wherein the one or more first ophthalmic device-forming comonomers comprise one or more silicone-containing comonomers represented by a structure of Formula I:
wherein V is an ethylenically unsaturated polymerizable group, L is a linker group or a bond; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently H, a C 1 to C 12 alkyl group, a halo alkyl group, a C 3 to C 12 cycloalkyl group, a heterocycloalkyl group, a C 2 to C 12 alkenyl group, a haloalkenyl group, or a C 6 to C 12 aromatic group; R 10 and R 11 are independently H or a C 1 to C 12 alkyl group, wherein at least one of R 10 and R 11 is hydrogen; y is 2 to 7 and n is 1 to 100; and
(iii) one or more second ophthalmic device-forming comonomers having at least one reactive group that preferentially reacts with the allyl-containing reactive end group of the multifunctional crosslinking agent; and
(b) dry releasing the ophthalmic device from the mold.
13 . The method according to claim 12 , wherein the one or more multifunctional crosslinking agents comprise 1 to about 100 repeating units of the silyl-alkyl-siloxanyl group, and the alkyl group of the silyl-alkyl-siloxanyl group has from 2 to about 4 carbon atoms.
14 . The method according to claim 12 , wherein the one or more first ophthalmic device-forming comonomers further comprise one or more additional silicone-containing comonomers selected from the group consisting of a silicone-containing comonomer represented by a structure of Formula II:
wherein R 12 is H or methyl; X is O or NR 16 ; wherein R 16 is selected from H, or a C 1 to C 4 alkyl group, optionally substituted with one or more hydroxyl groups; R 13 is a divalent alkyl group, optionally functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R 14 is independently a phenyl group or a C 1 to C 4 alkyl group, optionally substituted with fluorine, a hydroxyl group or an ether group; R 15 is a C 1 to C 4 alkyl group; and a is 2 to 50, a polysiloxane prepolymer represented by a structure of Formula III:
wherein each V is an independently reactive functional end group; R 17 to R 22 are independently a straight or branched, substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 4 -C 30 cycloalkylalkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkenyl group, a substituted or unsubstituted C 6 -C 30 aryl group, and a substituted or unsubstituted C 7 -C 30 arylalkyl group, and L is independently a linking group; and x is 37, a silicone-containing comonomer represented by a structure of Formula IV:
wherein X denotes —O— or —NR 19 —, wherein R 19 is hydrogen or a C 1 -C 4 alkyl group; R 17 denotes hydrogen or methyl; each R 18 independently denotes a C 1 -C 6 alkyl group, a phenyl group or a group represented by:
wherein each R 18′ independently denotes a C 1 -C 6 alkyl, or a phenyl radical; and h is 1 to 10, and a silicone-containing comonomer represented by a structure of Formula V:
wherein X denotes —NR 19 —, wherein R 19 denotes hydrogen or a C 1 -C 4 alkyl group; R 17 denotes hydrogen or methyl; each R 18 independently denotes a C 1 -C 6 alkyl group, a phenyl group or a group represented by:
wherein each R 18′ independently denotes a C 1 -C 6 alkyl group, or a phenyl group; and h is 1 to 10.
15 . The method according to claim 12 , wherein the one or more second ophthalmic device-forming comonomers comprise one or more hydrophilic comonomers selected from the group consisting of a hydrophilic vinyl monomer, an acrylamide and mixtures thereof.
16 . The method according to claim 12 , wherein the monomeric mixture comprises:
about 0.1 wt. % to about 50 wt. %, based on the total weight of the monomeric mixture, of the one or more multifunctional crosslinking agents;
about 1 wt. % to about 80 wt. %, based on the total weight of the monomeric mixture, of the one or more first ophthalmic device-forming comonomers; and
about 1 wt. % to about 80 wt. %, based on the total weight of the monomeric mixture, of the one or more second ophthalmic device-forming comonomers.
17 . The method according to claim 12 , wherein the ophthalmic device is a contact lens or a soft hydrogel.
18 . The method according to claim 12 , wherein the one or more second ophthalmic device-forming comonomers comprise N-vinyl pyrrolidone.
19 . The ophthalmic device according to claim 4 , wherein the one or more repeating units include a silyl-alkyl-siloxanyl group derived from a stepwise anionic polymerization reaction comprising hexamethylcyclotrisiloxane.
20 . The ophthalmic device according to claim 1 , wherein the one or more second ophthalmic device-forming comonomers comprise N-vinyl pyrrolidone.