Hydrophilic macromers and hydrogels comprising the same

Patent metadata

Field	Value
Publication number	US-9804296-B2
Application number	US-201414492433-A
Country	US
Kind code	B2
Filing date	Sep 22, 2014
Priority date	Mar 22, 2012
Publication date	Oct 31, 2017
Grant date	Oct 31, 2017

Abstract

A hydrophilic silicone macromer composition suitable for use in producing hydrogel polymer films from which biomedical devices such as contact lenses can be made. The hydrophilic silicone macromer comprises a polyether backbone comprising a silicone-containing pendant group. In one aspect, a hydrophilic silicone macromer is of the Formula 1:

The hydrophilic silicone macromer can be used to form a polymer and a hydrogel film suitable for forming contact lenses.

First claim

What is claimed is:

1. A composition comprising at least one hydrophilic silicone macromer of the Formula:

where R 2 is a group defined as M f D g T h Q i R 6 j with M=R 7 R 8 R 9 SiZ 1/2 , D=R 10 D 11 SiZ 2/2 , T=R 12 SiZ 3/2 , Q=SiZ 4/2 , R 6 =—(CH 2 ) 1/2 (R 13 ) k (CH 2 ) 1/2 —; R 1 is independently selected from —OH, —OC(O)R 15 , Y, or —OR 15 ; R 5 is independently selected from hydrogen, a —C(O)R 15 group, Y, or a monovalent hydrocarbon radical having from about 1 to about 40 carbon atoms that optionally contain a heteroatom and/or a hydroxyl group; at least one of R 1 and R 5 is Y; Y is a free radical polymerizable group; Z is O or CH 2 group subject to the limitation that the macromer contains an even number of O 1/2 and an even number of (CH 2 ) 1/2 groups and they both are all paired in the molecule; R 3 is a trivalent hydrocarbon radical having 1 to about 40 carbon atoms that optionally contain a heteroatom and/or a hydroxyl group; R 7 , R 8 , R 9 , R 10 , R 11 R 12 and R 15 are each independently selected from OR 14 , a monovalent hydrocarbon radical having 1 to about 20 carbon atoms that optionally contain a heteroatom and/or a hydroxyl group; R 4 is a divalent, linear, or branched unsaturated or saturated hydrocarbon radical containing at least one and less than about 30 carbon atoms that optionally contain a heteroatom and/or a hydroxyl group; R 13 is oxygen or divalent linear or branched unsaturated or saturated hydrocarbon radicals containing at least one and less than about 30 carbon atoms that optionally contain a heteroatoms and/or a hydroxyl group; R 14 is a monovalent, linear or branched unsaturated or saturated hydrocarbon radical having 1 to about 20 carbon atoms that optionally contain a heteroatom and/or hydroxyl group; a+e>2; b, c, and d are zero or positive subject to the limitation 3<a+b+c+d+e<about 1000; d+e>1; f, g, h, i and j are 0 or positive subject to the limitation f+g+h+i+j<about 300; f+g+h+i is greater than 0; and k is 0 or 1.

2. The composition of claim 1 , wherein the hydrophilic silicone macromer has a structure according to the formula R 1 (CH 2 CH 2 O) a (CH(CH 3 )CH 2 O) b (CH[CH 2 ) 1/2 R 2 ]CH 2 O) d R 5 .

3. The composition of claim 2 , where R 2 is a group defined as M f D g T h Q i R 6 j with M=R 7 R 8 R 9 Si(O) 1/2 ; D=R 10 Si(O) 2/2 (CH 2 ) 1/2 ; f=2; g=1; h=0; i=0; j=1; and R 6 =—(CH 2 ) 1/2 R 13 (CH 2 ) 1/2 .

4. The composition of claim 2 , where R 2 is a group defined as M f D g T h Q i R 6 j with M=R 7 R 8 R 9 Si(O) 1/2 ; T=Si(O) 3/2 (CH 2 ) 1/2 ; f=3; g=0; h=1; i=0; j=1; and R 6 =—(CH 2 ) 1/2 R 13 (CH 2 ) 1/2 —.

5. The composition of claim 2 , where R 2 is a group defined as R 7 R 8 R 9 SiO(Si(R 10 )(R 11 )(O) l Si(R 7 )(R 8 )(CH 2 ) 1/2 ; and where 0≦1≦200.

6. The composition of claim 1 , wherein the hydrophilic macromer has a structure according to the formula:

wherein R 2 is a group defined as R 7 R 8 R 9 SiO(Si(R 10 )(R 11 )O) l Si(R 7 )(R 8 )(CH 2 ) 1/2 ; and where 0≦1≦200.

7. The composition of claim 1 , wherein the hydrophilic macromer is of the formula:

wherein R 1 is independently selected from —OH, —OC(O)R 15 , —OR 15 , or Y; R 5 is independently selected from hydrogen, a —C(O)R 15 group, a monovalent hydrocarbon radical having from about 1 to about 40 carbon atoms that optionally contains a heteroatom and hydroxyl group, or Y; Y is a free radical polymerizable group subject to the limitation that at least one of R 1 and R 5 is Y; R 19 is independently selected from linear, branched, or cyclic mono-valent radicals with 1 to 100 carbon atoms that may contain a heteroatom chosen from halogens, oxygen, nitrogen, or siloxane radicals containing 1 to 50 Si—O linear or cyclic linkages; a and d are non-zero integers such that 2≦a+d≧1000.

8. The composition of claim 1 , wherein the hydrophilic macromer is of the formula:

wherein R 1 is independently selected from —OH, —OC(O)R 15 , —OR 15 , or Y; R 5 is independently selected from hydrogen or a —C(O)R 15 group or a monovalent hydrocarbon radical having from about 1 to about 40 carbon atoms that optionally contains a heteroatom and a hydroxyl group, or Y; Y is a free radical polymerizable group subject to the limitation that at least one of R 1 and R 5 is Y; R 19 is independently selected from linear, branched, or cyclic mono-valent radicals with 1 to 100 carbon atoms that optionally contain heteroatoms chosen from halogens, oxygen, nitrogen, or siloxane radicals containing 1 to 50 Si—O linear or cyclic linkages; a and d are non-zero integers such that 2≦a+e≧1000.

9. The composition of claim 1 , wherein Y is chosen from a polymerizable group having the general structure:

wherein R 16 , R 17 and R 18 can be selected from hydrogen, a monovalent alkyl group with 1 to 10 carbon atoms and may optionally contain heteroatoms; —COOH; and —CH 2 COOH; and the linking group B is chosen from a divalent radical containing 1 to 20 carbon atoms that can optionally contain heteroatoms.

10. The composition of claim 9 , where the linking group B is chosen from the following functional moieties:

11. The composition of claim 1 , wherein the composition is a hydrogel forming composition.

12. The composition of claim 11 , wherein the hydrogel forming composition further comprises a monomer chosen from a vinylic monomer, an acrylide monomer, an acrylic monomer, or a combination of two or more thereof; a free radical initiator; and optionally a cross-linker.

13. The composition of claim 12 , wherein the vinylic monomer is chosen from N-vinyl-pyrrolidone (NVP), N-vinyl-caprolactam, N-vinyl-acetamide, N-vinyl-formamide and N-vinyl-isopropylamide, vinyl benzene, vinyl naphthalene, vinyl pyridine, vinyl alcohol, a vinyl containing silicone, or a combination of two or more thereof.

14. The composition of claim 12 , wherein the acrylic monomers are 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 (DMA), N-isopropylacrylamide, acrylamide, methacrylamide, acrylic acid, methacrylic acid, or a combination of two or more thereof.

15. The composition of claim 12 , wherein the initiator can be 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, an acylphosphine oxide, or a combination of two or more thereof.

16. The composition of claim 12 , wherein the cross-linker can be selected from ethylene glycol dimethacrylate and trimethyloylpropane trimethacrylate, diethyleneglycol dimethacrylate, bisphenol A dimethacrylate, diglycidyl bisphenol A dimethacrylate and dimethacrylate-terminated polyethylene glycol an

Assignees

• Phukan Monjit
• Saxena Anubhav
• Bhat Shreedhar
• Momentive Performance Mat Inc

Inventors

• Phukan Monjit
• Saxena Anubhav
• Bhat Shreedhar

Classifications

• C08F290/068

  Polysiloxanes · CPC title

• C09D151/08

  grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• G02B1/043 Primary

  Contact lenses · CPC title

• C09J151/08

  grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• C08F220/281

  and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate · CPC title