Crosslink agents and dual radical cure polymer
View Patent ↗Crosslink agents used to copolymerize at least one hydrophilic monomer with at least one lens monomer typically used to prepare polymeric materials for ophthalmic lenses. The crosslink agents have a relatively high selectivity for the hydrophilic monomer and limited reactivity with the crosslink agent used to polymerize the lens monomer. Accordingly, the invention is also directed to a hydrophilic crosslinked polymer that comprises at least two monomeric units and at least two different crosslink units. The use of the dual crosslink system provides an improved means to control the final chemical, physical and structural characteristics of the resulting polymer.
1. A polymer comprising the reaction product of two or more crosslink agents, a hydrophilic monomer and a lens monomer, wherein at least one of the crosslink agents is of general formula I
wherein R 1 , R 2 , R 3 , R 4 , R 7 and R 8 are independently selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 2 alkanol or hydroxyl;
A is O, O(CH 2 CH 2 O) v or [SiR 5 R 6 O] w SiR 5 R 6 , wherein R 5 and R 6 are independently selected from methyl, ethyl or phenyl, and v is from 1-20 and w is from 0 to 60;
D is a straight or branched alkyl with two to eight carbons or a cyclic hydrocarbon with five to eight ring carbons, wherein one or two of the alkyl or cyclic carbon atoms is optionally substituted for an oxygen atom, sulfur atom or nitrogen radical; and
m and n are integers independently selected from 1 to 10; p is 0 or 1; and q is an integer from 0 to 6.
2. A polymer comprising the reaction product of two or more crosslink agents, a hydrophilic monomer and a lens monomer, wherein at least one of the crosslink agents is of general formula III
wherein R 1 , R 2 , R 3 , R 4 , R 7 and R 8 are independently selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 2 alkanol or hydroxyl;
A is O, O(CH 2 CH 2 O) v or [SiR 5 R 6 O] w SiR 5 R 6 , wherein R 5 and R 6 are independently selected from C 1 -C 4 alkyl or phenyl, and v is from 1-20 and w is from 0 to 60;
D is a straight or branched alkyl with two to eight carbons or a cyclic hydrocarbon with five to eight ring carbons, wherein one or two of the alkyl or cyclic carbon atoms is optionally substituted for an oxygen atom, sulfur atom or nitrogen radical; and
m and n are integers independently selected from 1 to 10; p is 0 or 1; and q is an integer from 0 to 6.
3. The polymer of claim 1 wherein the hydrophilic monomer is selected from the group consisting of N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl-ε-caprolactam, N-vinylimidazolidone, N-vinylsuccinimide and mixtures thereof.
4. The polymer of claim 2 wherein the hydrophilic monomer is selected from the group consisting of N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl-ε-caprolactam, N-vinylimidazolidone, N-vinylsuccinimide and mixtures thereof.
5. The polymer of claim 3 wherein the lens monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, tris-(trimethylsiloxy)-3-methacryloxypropylsilane, dimethylacrylamide, ethylene glycol dimethacrylate, methacrylic acid, 2-phenylethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, glycerol monomethacrylate, monomethoxy polyethyleneglycol methacrylates and any mixture thereof.
6. The polymer of claim 4 wherein the lens monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, tris-(trimethylsiloxy)-3-methacryloxypropylsilane, dimethylacrylamide, ethylene glycol dimethacrylate, methacrylic acid, 2-phenylethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, glycerol monomethacrylate, monomethoxy polyethyleneglycol methacrylates and any mixture thereof.
7. The polymer composition of claim 2 wherein the hydrophilic monomer and the lens monomer have a reactivity ratio, R H /R L , greater than 10 or less than 0.1, the reactivity ratio, R H /R L , defined by the following radical polymerization reactions, wherein M h represents the hydrophilic monomer, M h * represents the hydrophilic monomer radical, M l represents the lens monomer, M l * represents the lens monomer radical, M i represents the crosslink agent, and M i * represents the crosslink agent radical,
M h *+M h →M h M h *k hh ;
M h *+M i →M h M i *k hi ;
M i *+M i →M i M i *k ii ;
M i *+M h →M i M h *k ih ; and R H is R h /R i ,
and
M l *+M l →M l M l *k ll ;
M l *+M i →M l M i *k li ;
M i *+M i →M i M i *k ii ;
M i *+M l →M i M l *k il ; and R L is R l /R i ,
wherein the hydrophilic monomer has a reactivity ratio R h =k hh /k hi , the lens monomer has a reactivity ratio R l =k ll /k li and the crosslink agent has a reactivity ratio R i =k ii /k ih .
8. The polymer composition of claim 1 wherein the hydrophilic monomer and the lens monomer have a reactivity ratio, R H /R L , greater than 10 or less than 0.1, the reactivity ratio, R H /R L , defined by the following radical polymerization reactions, wherein M h represents the hydrophilic monomer, M h * represents the hydrophilic monomer radical, M l represents the lens monomer, M l * represents the lens monomer radical, M i represents the crosslink agent, and M i * represents the crosslink agent radical,
M h *+M h →M h M h *k hh ;
M h *+M i →M h M i *k hi ;
M i *+M i →M i M i *k ii ;
M i *+M h →M i M h *k ih ; and R H is R h /R i ,
and
M l *+M l →M l M l *k ll ;
M l *+M i →M l M i *k li ;
M i *+M i →M i M i *k ii ;
M i *+M l →M i M l *k il ; and R L is R l /R i ,
wherein the hydrophilic monomer has a reactivity ratio R h =k hh /k hi , the lens monomer has a reactivity ratio R l =k ll /k li and the crosslink agent has a reactivity ratio R l =k il /k ih .
9. Th polymer of claim 1 wherein the lens monomer is a silicone-containing monomer or macromonomer to provide a siloxane polymer for manufacture of a ophthalmic lens material.
10. The polymer of claim 9 wherein the silicon-containing monomer or macromonomer is of Structure A
wherein R l is H or CH 3 , q is 1 or 2 and for each q, R l , R m and R n are independently selected from ethyl, methyl, benzyl, phenyl or a monovalent siloxane chain comprising from 1 to 30 repeating Si—O units, p is an integer from 1 to 10, r is (3−q), X is O, NH or N(C 1-4 alkyl), a is 0 or 1, and L is a divalent linking group.
11. The polymer of claim 9 wherein the silicon-containing monomer or macromonomer is selected from the group consisting of (3-methacryloyloxypropyl)-bis(trimethylsiloxy)methylsilane, (3 methacryloyloxypropyl)-pentamethyldisiloxane, and (3-methacryloyloxy-2-hydroxypropyloxy)bis(trimethylsiloxy)methylsilane.
12. The polymer of claim 9 wherein the silicon-containing monomer or macromonomer is of Structure B
where b=0 to 100, and R k is selected from any C 1-10 aliphatic or aromatic group which can include hetero atoms, and a C 3-8 alkyl group; and R l is and ethylemically unsaturated moiety.
13. The polymer of claim 2 wherein the lens monomers is a silicone-containing monomer or macromonomer to provide a siloxane polymer for the manufacture of an ophthalmic lens material.
14. The polymer of claim 13 wherein the silicon-containing monomer or macromonomer is of Structure A
wherein R l is H or CH 3 , q is 1 or 2 and for each q, R l , R m and R n are independently selected from ethyl, methyl, benzyl, phenyl or a monovalent siloxane chain comprising from 1 to 30 repeating Si—O units, p is an integer from 1 to 10, r is (3−q), X is O, NH or N(C 1-3 alkyl), a is 0 or 1, and L is a divalent linking group.
15. The polymer of claim 13 wherein the silicon-containing monomer or macromonomer is selected from the group consisting of (3-methacryloyloxypropyl)-bis(trimethylsiloxy)methylsilane, (3 methacryloyloxypropyl)-pentamethyldisiloxane, and (3-methacryloyloxy-2-hydroxypropyloxy)bis(trimethylsiloxy)methylsilane.
16. The polymer of claim 13 wherein the silicon-containing monomer or macromonomer is of Structure B
where b=0 to 100, and R k is selected from any C 1-10 aliphatic or aromatic group which can include hetero atoms, and a C 3-8 alkyl group; and R j is and ethylemically unsaturated moiety.