Hydrophilic macromers and hydrogels comprising the same

Patent metadata

Field	Value
Publication number	US-10101499-B2
Application number	US-201414492722-A
Country	US
Kind code	B2
Filing date	Sep 22, 2014
Priority date	Mar 22, 2012
Publication date	Oct 16, 2018
Grant date	Oct 16, 2018

Abstract

A composition, suitable for use in producing hydrogel polymer films from which biomedical devices such as contact lenses can be made, comprising at least one hydrophilic silicone macromer. In one aspect, a hydrophilic silicone macromer is of the Formula 1:

X—Si(R 1 )(R 2 )O—(Si(R 3 )(R 4 )O) a —Si(R 5 )(R 6 )—Y  (1)

wherein R 1 , R 2 , R 3 R 4 , R 5 and R 6 are independently selected from a monovalent linear, branched, or cyclic radical with 1 to 50 carbon atoms, that can optionally contain a heteroatom or I; I is R L —R P ; Y is a free radical polymerization-effective hydrophilic group with the general structure: R L —R P —Z; R L is a linking residue from a non-isomerizable hydrosilylation effective terminal olefin comprising the general structure —CH 2 —C(R b R 7 )—(CR 8 R 9 ) n , the subscript n is selected from integers from 1 to 10; R 7 , R 8 , and R 9 can be selected from hydrogen and a mono-valent hydrocarbon radical with 1 to 10 carbon atoms that optionally contain a heteroatom; R b is selected from a monovalent hydrocarbon radical with 1 to 6 carbon atoms; R P is a spacer group comprising a diavelant hydrophilic organic radical with 0 to 100 carbon atoms and optionally contains heteroatoms, and X is a free radical polymerizable group. The said composition can be polymers and films suitable for use in making contact lenses.

First claim

What is claimed is:

1. A composition comprising at least one hydrophilic silicone macromer of the Formula 1:
R—Si(R 1 )(R 2 )O—(Si(R 3 )(R 4 )O) a —Si(R 5 )(R 6 )—Y  (1)

wherein R 1 , R 2 , R 3 R 4 , R 5 , and R 6 are independently selected from a monovalent linear, branched, or cyclic radical with 1 to 50 carbon atoms and optionally contain I;
wherein I is R L —R P ; R L is a linking residue from non-isomerizable hydrosilylation effective terminal olefin comprising the general structure —CH 2 —C(R b R 7 )—(CR 8 R 9 ) n , n is selected from integers from 1 to 10; R 7 , R 8 and R 9 are independently selected from hydrogen, a mono-valent hydrocarbon radical with 1 to 10 carbon atoms, that does not contain a heteroatom; R b is selected from a monovalent hydrocarbon radical with 1 to 6 carbon atoms; R P is a hydrogen, a hydroxyl radical, or a hydrophilic organic radical with 1 to 100 carbon atoms that optionally contain a heteroatom; a is 0 to about 500;
wherein R is a linear or branched alkyl having 1 to 10 carbon atoms;
wherein Y is a free radical polymerization-effective group containing I—Z, where Z is a functional moiety, independently selected from a bivalent linear, branched, or cyclic radical with 1 to about 20 carbons that optionally contain a heteroatom; and
wherein at least one of R 1 , R 2 , R 3 R 4 , R 5 , or R 6 contains an I group where R p is a hydrophilic organic radical.

2. The composition of claim 1 , where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from methyl, ethyl, propyl, isopropyl, phenyl, polyether, and —CH 2 CH 2 CF 3 groups; R is selected from methyl, ethyl, propyl, isopropyl, butyl, and isobutyl groups; the subscript a is selected from 0 to 50; R b is methyl; R 7 , R 8 and R 9 are hydrogen atoms; the subscript n is selected from 1 to 6; R p includes a polyether group with the general formula:
—O(CH 2 CH 2 O) b (CH 2 CH(CH 3 )O) c (CH 2 CH 2 CH 2 CH 2 O) d —

where the subscript b is 1 to 100, subscript c is 0 to 100, and subscript d is 0 to 100 such that b+c+d>0; the free radical polymerizable group Y is selected from an acrylate or an acrylamide with the general formula:
—Z—C(R 10 )═C(R 11 )(R 12 )

where R 10 , R 11 , and R 12 are independently selected from hydrogen and a monovalent alkyl group with 1 to 10 carbon atoms, that optionally contain a heteroatom, —COOH, and —CH 2 COOH.

3. The composition of claim 1 , wherein a is 1 to 50.

4. The composition of claim 1 , wherein n is 1 to 6.

5. The composition of claim 1 wherein Z is independently selected from one or more of the following functional moieties:

6. The composition of claim 1 , wherein Y is chosen from an acrylate, an acrylamide, a methacrylate, a methacrylamide, a vinyl, an alkyl, a methalkyl, an internal olefinic bond containing molecule, or a combination of two or more thereof.

7. The composition of claim 1 , comprising the silicone monomer of the formula:

wherein R 10 , R 11 , and R 12 are independently selected from hydrogen and a monovalent alkyl group with 1 to 10 carbon atoms, that optionally contain a heteroatom, —COOH, and —CH 2 COOH; R 13 and R 17 are independently selected from methyl, ethyl, isopropyl, phenyl, phenylmethyl, naphthyl, naphthylmethyl, and —CH 2 CH 2 CF 3 radicals; R 14 , R 16 , and R 18 are independently selected from hydrogen, ethyl, isopropyl, phenyl, phenylmethyl, naphthyl, naphthylmethyl, and —CH 2 CH 2 CF 3 radicals; R 15 is methyl; G is independently selected from hydrogen, alkyl, aryl, and aralkyl residues; subscripts p and r are independently 0-50 such that p+r>0; and 1<(m+n)<500, subject to the limitation that n>0.

8. The composition according to claim 1 , wherein the composition is a hydrogel.

9. The hydrogel of claim 8 , further comprising a free-radical polymerizable organic monomer, an initiator, and optionally a crosslinker.

10. The hydrogel of claim 9 , wherein the free-radical polymerizable organic monomer is chosen from a vinylic monomer, an acrylide monomer, an acrylic monomer, or a combination of two or more thereof.

11. The hydrogel of claim 9 , 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, vinyl containing silicone, or a combination of two or more thereof.

12. The hydrogel of claim 9 , wherein the acrylic 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-dimethylacrylamide, N-isopropylacrylamide, acrylamide, methacrylamide, acrylic acid, methacrylic acid, acrylated hydrophilic or hydrophobic organo-silicone, or a combination of two or more thereof.

13. The hydrogel of claim 9 , wherein the hydrophilic silicone macromer is present in an amount of from about 5 weight percent to about 50 weight percent of the hydrogel composition.

14. The hydrogel of claim 9 , wherein the ratio of the hydrophilic silicone macromer to the free-radical polymerizable organic monomer is from about 1:100 to about 100:1 wt. %.

15. The hydrogel of claim 9 , wherein the ratio of the hydrophilic silicone macromer to the free-radical polymerizable organic monomer is from about 1:50 to about 50:1 wt. %.

16. The hydrogel of claim 9 , wherein the ratio of the hydrophilic silicone macromer to the free-radical polymerizable organic monomer is from about 1:10 to about 10:1 wt. %.

17. The hydrogel of claim 9 , wherein the ratio of the hydrophilic silicone macromer to the free-radical polymerizable organic monomer is about 1:1 wt. %.

18. The composition of claim 8 , optionally 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.

19. The hydrogel composition of claim 8 , wherein the composition 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), peroxides, benzoin methyl ether, diethoxyacetophenone, a benzoylphosphine oxide, 2-hydroxy-2-methyl propiophenone (HMPP), 1-hydroxycyclohexyl phenyl ketone, or a combination of two or more thereof.

20. A contact lens comprising a hydrogel film formed from the composition of claim 8 .

21. The contact lens according to claim 20 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.

22. The composition according to claim 1 , wherein the composition is a polymer.

23. The composition of claim 22 comprising free-radically polymerized emulsions and latex compositions.

24. The free radical polymerized composition according

Assignees

• Saxena Anubhav
• Phukan Monjit
• Bhat Shreedhar
• Lewis Kenrick M
• Umapathy Senthilkumar
• Momentive Performance Mat Inc

Inventors

• Saxena Anubhav
• Phukan Monjit
• Bhat Shreedhar
• Lewis Kenrick M
• Umapathy Senthilkumar

Classifications

• C08L2201/10

  Transparent films; Clear coatings; Transparent materials · CPC title

• G02B1/043 Primary

  Contact lenses · CPC title

• C08L83/08

  containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen · CPC title

• C08L83/04

  Polysiloxanes · CPC title

• C08G77/20 Primary

  containing silicon bound to unsaturated aliphatic groups · CPC title