Hydrophilic silicone monomers, process for preparation thereof and thin films containing the same
View Patent ↗The present invention relates to a fast curing compositions comprising a (meth)acrylamide functionalized hydrophilic silicone monomers having a polyether moiety containing a branched linking group. In one embodiment, such compositions are useful for preparing water-absorbing silicone-hydrogel films for contact lens applications. In one embodiment, the (meth)acrylamide monomers disclosed here have a branched linking group on the polyether moiety which makes it possible to produce hydrophilic polyether modified silicone copolymers without the need to separate various by-products including, but not limited to, unreacted, isomerized polyether and associated high molecular weight by-products.
1. A hydrogel composition comprising at least one silicone acrylamide monomer, the silicone acrylamide monomer having a formula as set forth in Formulas (I) or (II) below:
wherein a is 1 to 50; b is 0 to 100; each R is independently selected from the group comprising of a monovalent aliphatic, cycloaliphatic, or aromatic hydrocarbon group of 1 to about 10 carbons, a halogenated hydrocarbon group of 1 to about 10 carbons, and a radical comprising 1 to about 50 silicon atoms, or a trialkylsilyloxy group and Z is a polyether moiety having a non-isomerizable hydrosilylation effective terminal olefinic residue having Formula (III):
—H 2 C—CHR b —(CH 2 ) n —O—(C 2 H 4 O) p —(C 3 H 6 O) q —(C 4 H 8 O) r —X (III)
wherein n is 1 to about 20; p and q are independently 0 to about 100; r is 0 to about 50, and (p+q+r) is greater than 0; Rb is an alkyl group having from 1 to about 4 carbon atoms, X is a vinyl group, an N-vinyl derivative, even an N-vinyl-pyrrolidone derivative, or a polyether-capping group having Formula (IVb):
wherein R 3 and R 4 independently are either hydrogen or a substituted or unsubstituted saturated monovalent hydrocarbon group of 1 to about 20 carbons or —COOH or —CH 2 —COOH.
2. The hydrogel composition of claim 1 , wherein the silicone acrylamide monomer comprises (a) a reaction of (i) silicone-containing compound having Formula (V):
R 3 Si—O—[SiH(R)] a —[OSiR 2 ] b —OSiR 3 (V)
wherein a is 1 to 50; b is 0 to 100; each R is independently selected from the group consisting of a monovalent aliphatic, cycloaliphatic, or aromatic hydrocarbon group of 1 to about 10 carbons, and halogenated hydrocarbon groups of 1 to about 10 carbons; with (ii) a polyether having at least one end terminated with hydroxyl, a halogen, or an epoxy, and the other end terminated with a branched alkene having Formula (VI):
CH 2 ═CHR b —CH 2 ) n —(OC 2 H 4 (OC 3 H 6 ) q —(OC 4 H 8 ) r —Y (VI)
wherein n is 1 to about 20, p and q are 0 to about 100; r is 0 to about 50; Rb is an alkyl group having from 1 to about 4 carbon atoms, Y is —OH, a halogen, an epoxy or an amine, the reaction of (i) and (ii) being conducted in the presence of a catalyst to produce a polyether siloxane, and (b) reacting the polyether siloxane with an acryl compound having Formula (VII):
wherein L is an optional linker group chosen from a monovalent aliphatic, a cycloaliphatic, or an aromatic hydrocarbon radical of 1 to about 16 carbons, which can optionally contain a heteroatom or a halogen; G is a halogen or —OH and its organic or inorganic salts, and R 3 and R 4 independently are either hydrogen or a hydrocarbon group of 1 to about 10 carbons or —COOH or —CH 2 —COOH to produce said silicone acrylamide monomer.
3. The hydrogel composition of claim 2 , wherein L is a moiety having Formula:
wherein s is an integer selected from 0 to about 15.
4. The hydrogel composition of claim 1 , comprising the silicone acrylamide monomer is of the formula:
wherein R* is a trialkylsilyloxy group or a methyl group, p is 1 to about 50, and b is 0 to about 100.
5. The hydrogel composition of claim 1 , comprising the silicone acrylamide monomer of the formula:
wherein R* is a trialkylsilyloxy group or a methyl group, p is 1 to about 50, and b is 0 to about 100.
6. The hydrogel composition of claim 1 , comprising the silicone acrylamide monomer of the formula:
wherein R* is a trialkylsilyloxy group or a methyl group, p is 1 to about 50 and b is 0 to about 100.
7. The hydrogel composition of claim 1 , comprising the silicone acrylamide monomer of the formula:
wherein R* is a trialkylsilyloxy group or a methyl group, p is 1 to about 50, and b is 0 to about 100.
8. The hydrogel of claim 1 , wherein the co-monomer is chosen from a silicone-containing monomer, an organic based monomer, or a combination of two or more thereof.
9. The hydrogel of claim 1 , wherein the hydrogel further comprises a co-monomer chosen from a vinylic monomer, an allylic monomer, an acrylide monomer, an acrylic monomer, or a combination of two or more thereof.
10. The hydrogel of claim 8 , wherein the vinylic monomer is chosen from N-vinyl-pyrrolidone, N-vinyl-caprolactam, N-vinyl-acetamide, N-vinyl-formamide, N-vinyl-isopropylamide, vinyl benzene, vinyl naphthalene, vinyl pyridine, vinyl alcohol, a vinyl containing silicones, or a combination of two or more thereof.
11. The hydrogel of claim 8 , wherein the vinyl, allyl, or acrylide, or acrylic monomer is chosen from 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate; methyl-di(trimethylsiloxy)-silyl propyl glycerol methacrylate; 3-(trimethylsilyl)propyl vinyl carbonate; 3-(vinyloxycarbonylthio)propyl-[tris(trimethylsiloxy)silane]; 3-[tris(tri-methylsiloxy)silyl]propyl vinyl carbamate; 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate; 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, or a combination of two or more thereof.
12. The hydrogel of claim 8 , wherein the acrylic organic monomer is chosen from 2-hydroxy-ethyl-methacrylate (HEMA), 2-hydroxy-ethyl-acrylate (HEA), hydroxyl propyl methacrylate, trimethylammonium 2-hydroxy propyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, N,N-dimethyl acrylamide, N-isopropylacrylamide, acrylamide, methacrylamide, acrylic acid, methacrylic acid, an acrylated hydrophilic or hydrophobic organo-silicone, or a combination of two or more thereof.
13. The hydrogel of claim 1 , further comprising a cross-linker chosen from ethylene glycol dimethacrylate, trimethyloylpropane trimethacrylate, diethyleneglycol dimethacrylate, bisphenol A dimethacrylate, diglycidyl bisphenol A dimethacrylate, dimethacrylate-terminated polyethylene glycol, a reactive linear or pendant polyether modified silicone, or a combination of two or more thereof.
14. The hydrogel composition of claim 1 , wherein the composition further comprises a thermal or a photo initiator chosen from 2,2′-azobis (2,4-dimethylpentanenitrile), 2,2′-azobis (2-methylpropanenitrile), 2,2′-azobis (2-methylbutanenitrile), benzoyl peroxide, benzoin methyl ether, diethoxyacetophenone, a benzoylphosphine oxide, 2-hydroxy-2-methyl propiophenone (HMPP), 1-hydroxycyclohexyl phenyl ketone, a Darocur-type initiator, an Irgacure-type initiator or a combination of two or more thereof.
15. The hydrogel composition of claim 1 , wherein, the hydrogel composition cures to a self-standing film in time of about 10 seconds or less using 365 nm light with an intensity of 105 mW/cm 2 .
16. A contact lens comprising the hydrogel film of claim 1 .
17. The contact lens according to claim 16 comprising a limited extraction protocol that further comprises a green or aqueous solvents chosen from water, an organic or inorganic salt solutions, a buffer, an emulsion, a commercial lens cleaning solution, or an ophthalmically compatible solvent in the temperature range of 15-125° C. for extraction.
18. The composition according of claim 1 , wherein the composition is a film forming additive in a textile, paper, leather, personal care, health care, home care, coating, painting, or seed treatment formulations.
19. The hydrogel composition of claim 4 , wherein p is from 2 to 15.
20. The hydrogel composition of claim 5 , wherein p is from 2 to 15.
21. The hydrogel composition of claim 6 , wherein p is from 2 to 15.
22. The hydrogel composition of claim 7 , wherein p is from 2 to 15.