Actinically-crosslinkable siloxane-containing copolymers
View Patent ↗The invention provide a class of actinically-crosslinkable silicone-containing prepolymers obtained by functionalizing an intermediary copolymer to have two or more thiol or ethylenically-unsaturated groups covalently attached thereto, wherein the intermediary copolymer is an atom-transfer radical polymerization (ATRP) product of a reactive mixture comprising a polysiloxane ATRP macroinitiator and at least one hydrophilic vinylic monomer. The present invention is also related to silicone hydrogel contact lenses made from a prepolymer of the invention and methods for making the contact lenses in a cost-effective way and with high consistency and high fidelity to the original lens design.
1. An actinically crosslinkable prepolymer of formula (1) or (2)
in which
r 1 is an integer of 2 or 3, r 2 and r 2 ′ are either 0 or 1 provided that (r 2 +r 2 ′)=1;
G 1 and G 2 independent of each other are a linear or branched C 1 -C 10 alkylene divalent radical, a divalent radical of
in which q is an integer of from 1 to 5 and alk and alk′ independent of each other is a C 1 -C 6 alkylene divalent radical, or a divalent radical of —R′ 1 —X 5 -E-X 6 —R′ 2 — in which R′ 1 and R′ 2 independent of each other is a linear or branched C 1 -C 10 alkylene divalent radical or a divalent radical of
as defined above, X 5 and X 6 independent of each other are a linkage selected from the group consisting of
in which R′ is H or C 1 -C 8 alkyl, E is an alkyl diradical, a cycloalkyl diradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or an aryl diradical with up to 40 carbon atoms which may have ether, thio, or amine linkages in the main chain, provided that if r 2 is 0, then r 1 is integer 2 or 3 and G 2 is a linear or branched C 1 -C 10 alkyl radical or a monovalent radical of
in which q and alk′ are defined as above and alk″ is C 1 -C 6 alkyl;
X 1 and X 2 independent of each other are a linkage selected from the group consisting of a direct bond,
in which R′ is H or C 1 -C 8 alkyl;
PDMS is a polysiloxane divalent radical of formula (3)
in which ν is 0 or 1, ω is an integer of from 0 to 5, U 1 and U 2 independent of each other represent a divalent radical of —R′ 1 —X 5 -E-X 6 —R′ 2 — as defined above or a divalent radical of
as defined above, D 1 , D 2 and D 3 independently of each other are a divalent radical selected from the group consisting of —(CH 2 CH 2 O) t —CH 2 CH 2 — in which t is an integer of 3 to 40, —CF 2 —(OCF 2 ) a —(OCF 2 CF 2 ) b —OCF 2 — in which a and b independent of each other is an integer of 0 to 10 provided that a+b is a number in the range of 10 to 30, and a divalent group of formula (4)
in which R 3 , R 4 , R 5 ′, R 6 , R 7 , R 8 , R 9 and R 10 , independently of one another, are C 1 -C 8 -alkyl, C 1 -C 4 alkyl- or C 1 -C 4 -alkoxy-substituted phenyl, fluoro(C 1 -C 18 -alkyl), cyano(C 1 -C 12 -alkyl), -alk-(OCH 2 CH 2 ) n —OR 11 in which alk is C 1 -C 6 -alkylene divalent radical, R 11 is C 1 -C 6 alkyl and n is an integer from 1 to 10, m and p independently of each other are an integer of from 2 to 698 and (m+p) is from 5 to 700, provided that at least one of D 1 , D 2 and D 3 is represented by formula (4);
L 1 and L 2 independent of each other are an organic radical having a valence of (r 1 +1), where the organic radical is a linear or branched C 1 -C 14 aliphatic radical, a C 5 -C 45 cycloaliphatic or aliphatic-cycloaliphatic di-, tri-, or tetra-valent radical, or a C 6 -C 24 aromatic or araliphatic di-, tri-, or tetra-valent radical, provided that each of L 1 and L 2 has valence of (r 1 +1); and
A 1 and A 2 independently of each other are a monovalent radical of formula (5)
in which r 4 is an integer of 0 or 1; X 7 is —O— or
in which R′ is H or C 1 -C 8 alkyl; X 8 is a linkage selected from the group consisting of
in which R′ is H or C 1 -C 8 alkyl; G 5 is a linear or branched C 1 -C 10 alkylene divalent radical, a divalent radical of
as defined above, or a divalent radical of —R′ 1 —X 5 -E-X 6 —R′ 2 — as defined above; G 6 is a C 2 -C 6 alkylene divalent radical; LC is a divalent radical of a linear polymer chain of one or more hydrophilic vinylic monomers; and AX is a thiol group or a radical of formula —X 8 -G 7 -X 9 -Q, in which: X 8 is an linkage as defined above; G 7 is a direct bond or a linear or branched alkylene divalent radical; X 9 is a direct bond or a linkage selected from the group consisting of
Q is an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or a norbornenyl group.
2. The prepolymer of claim 1 , wherein LC is a divalent radical of a linear polymer chain of one or more hydrophilic vinylic monomers selected from the group consisting of N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, 2-acrylamidoglycolic acid, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, N-vinyl-2-pyrrolidone, allyl alcohol, vinylpyridine, acrylic acid, a C 1 -C 4 -alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, methacrylic acid, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, allyl alcohol, N-vinyl caprolactam, and mixtures thereof.
3. The prepolymer of claim 2 , wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of N,N-dimethylacrylamide or N,N-dimethylacrylamide and one or more hydrophilic vinylic monomer other than N,N-dimethylacrylamide.
4. The prepolymer of claim 2 , wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of N-Vinylpyrrolidone or N-Vinylpyrrolidone and one or more hydrophilic vinylic monomer other than N-Vinylpyrrolidone.
5. The prepolymer of claim 2 , wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), glycerol methacrylate (GMA), allyl alcohol, a C 1 -C 4 -alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, or a combination thereof.
6. The prepolymer of claim 2 , wherein the prepolymer is represented by formula (1) in which r 2 is zero, and G 2 is a linear or branched C 1 -C 10 alkyl radical or a monovalent radical of
in which q and alk′ are defined as above and alk″ is C 1 -C 6 alkyl.
7. The prepolymer of claim 2 , wherein the prepolymer is represented by formula (1) in which r 2 is an integer of 1.
8. An actinically crosslinkable prepolymer of formula (2)
in which
r 1 is an integer of 1 to 3, r 3 is an integer of 3 or 4;
G 3 and G 4 independent of each other are a linear or branched C 1 -C 10 alkylene divalent radical, a divalent radical of
in which q is an integer of from 1 to 5 and alk and alk′ independent of each other is a C 1 -C 6 alkylene divalent radical, or a divalent radical of —R′ 1 —X 5 -E-X 6 —R′ 2 — in which R′ 1 and R′ 2 independent of each other is a linear or branched C 1 -C 10 alkylene divalent radical or a divalent radical of
as defined above, X 5 and X 6 independent of each other are a linkage selected from the group consisting of
in which R′ is H or C 1 -C 8 alkyl, E is an alkyl diradical, a cycloalkyl diradical, an alkylcycloalkyl diradical, an alkylaryl diradical, or an aryl diradical with up to 40 carbon atoms which may have ether, thio, or amine linkages in the main chain,
X 3 and X 4 independent of each other are a linkage selected from the group consisting of a direct bond,
in which R′ is H or C 1 -C 8 alkyl;
PDMS is a polysiloxane divalent radical of formula (3)
in which ν is 0 or 1, ω is an integer of from 0 to 5, U 1 and U 2 independent of each other represent a divalent radical of —R′ 1 —X 5 -E-X 6 —R′ 2 — as defined above or a divalent radical of
as defined above, D 1 , D 2 and D 3 independently of each other are a divalent radical selected from the group consisting of —(CH 2 CH 2 O) t —CH 2 CH 2 — in which t is an integer of 3 to 40, —CF 2 —(OCF 2 ) a —(OCF 2 CF 2 ) b —OCF 2 — in which a and b independent of each other is an integer of 0 to 10 provided that a+b is a number in the range of 10 to 30, and a divalent group of formula (4)
in which R 3 , R 4 , R 5 ′, R 6 , R 7 , R 8 , R 9 and R 10 , independently of one another, are C 1 -C 8 -alkyl, C 1 -C 4 alkyl- or C 1 -C 4 -alkoxy-substituted phenyl, fluoro(C 1 -C 18 -alkyl), cyano(C 1 -C 12 -alkyl), -alk-(OCH 2 CH 2 ) n —OR 11 in which alk is C 1 -C 6 -alkylene divalent radical, R 11 is C 1 -C 6 alkyl and n is an integer from 1 to 10, m and p independently of each other are an integer of from 2 to 698 and (m+p) is from 5 to 700, provided that at least one of D 1 , D 2 and D 3 is represented by formula (4);
L 3 is an organic radical having a valence of (r 1 +1), where the organic radical is a linear or branched C 1 -C 14 aliphatic radical, a C 5 -C 45 cycloaliphatic or aliphatic-cycloaliphatic di-, tri-, or tetra-valent radical, or a C 6 -C 24 aromatic or araliphatic di-, tri-, or tetra-valent radical, provided that L 3 has valence of (r 1 +1);
B 1 is a multivalent organic radical having a valence of r 3 ; and
A 3 is a monovalent radical of formula (5)
in which r 4 is an integer of 0 or 1; X 7 is —O— or
in which R′ is H or C 1 -C 8 alkyl; X 8 is a linkage selected from the group consisting of
in which R′ is H or C 1 -C 8 alkyl; G 5 is a linear or branched C 1 -C 10 alkylene divalent radical, a divalent radical of
as defined above, or a divalent radical of —R′ 1 —X 5 -E-X 6 —R′ 2 — as defined above; G 6 is a C 2 -C 6 alkylene divalent radical; LC is a divalent radical of a linear polymer chain of one or more hydrophilic vinylic monomers; and AX is a thiol group or a radical of formula —X 8 -G 7 -X 9 -Q, in which: X 8 is an linkage as defined above; G 7 is a direct bond or a linear or branched alkylene divalent radical; X 9 is a direct bond or a linkage selected from the group consisting of
Q is an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, or a norbornenyl group.
9. The prepolymer of claim 8 , wherein LC is a divalent radical of a linear polymer chain of one or more hydrophilic vinylic monomers selected from the group consisting of N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, 2-acrylamidoglycolic acid, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, 2-hydroxyethylmethacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, N-vinyl-2-pyrrolidone, allyl alcohol, vinylpyridine, acrylic acid, a C 1 -C 4 -alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, methacrylic acid, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, allyl alcohol, N-vinyl caprolactam, and mixtures thereof.
10. The prepolymer of claim 9 , wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of N,N-dimethylacrylamide or N,N-dimethylacrylamide and one or more hydrophilic vinylic monomer other than N,N-dimethylacrylamide.
11. The prepolymer of claim 9 , wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of N-Vinylpyrrolidone or N-Vinylpyrrolidone and one or more hydrophilic vinylic monomer other than N-Vinylpyrrolidone.
12. The prepolymer of claim 9 , wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), glycerol methacrylate (GMA), allyl alcohol, a C 1 -C 4 -alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, or a combination thereof.
13. The prepolymer of claim 9 , wherein in formula (2) r 3 is an integer of 3.