Organo-modified silicone polymers and hydrogels comprising the same

Patent metadata

Field	Value
Publication number	US-9890234-B2
Application number	US-201414492646-A
Country	US
Kind code	B2
Filing date	Sep 22, 2014
Priority date	Mar 22, 2012
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

A hydrophilic silicone polymer composition suitable for use in producing hydrogel polymer films disclosed. In one aspect, a hydrophilic silicone monomer is of the Formula 1:

w A m B n w   (1)

where A is a divalent block comprising a silicone-containing pendant group. In one embodiment, the silicone-containing pendant group comprises polyalkylene oxide groups. The structure of the polymer can be controlled and tuned to provide a material with excellent wettability and oxygen permeability. The polymers are suitable for use in a variety of applications including in providing a film for forming contact lenses.

First claim

What is claimed is:

1. A hydrogel composition comprising a siloxane pre-polymer of the formula:
w A m B n w

where m is a positive integer from 2 to about 100, and n is a positive integer from 0 to about 100; A is a divalent block having a formula:

where, R 1 , R 2 , and R 3 are independently selected from hydrogen and a monovalent radical with 1 to 50 carbon atoms optionally containing one or more heteroatoms; E is a mono-valent group having a general structure of F-L-G, where F is a divalent linkage selected from an alkyl, an ester, an ether, an amine, an amide, a carbonate, and a carbamate; L is a divalent moiety chosen from a substituted or unsubstituted, linear, branched, cyclic, aliphatic, or aromatic hydrocarbon of 1-100 carbon atom optionally containing one or more heteroatoms; and G is a siloxane unit having the general structure M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q g , where, M 1 =R 5 R 6 R 7 SiZ 1/2 , M 2 =R 8 R 9 R 10 SiZ 1/2 , D 1 =R 11 R 12 SiZ 2/2 , D 2 =R 13 R 14 SiZ 2/2 , T 1 =R 15 SiZ 3/2 , T 2 =R 16 SiZ 3/2 , Q=SiZ 4/2 ; R 5 , R 6 , R 7 , R 9 , R 10 , R 11 , R 12 , R 14 , and R 15 are independently chosen from a monovalent hydrocarbon radical having 1 to about 50 carbon atoms optionally containing one or more heteroatoms; R 8 , R 13 , and R 16 are independently selected from a divalent residue of a non-isomerizable hydrosilylation effective terminal olefin having a structure:

where, R 18 , R 19 , and R 20 are independently selected from hydrogen and a hydrocarbon radical with 1 to 10 carbon atoms optionally containing one or more heteroatoms, the integer q is 0 to 10, and R 17 is a hydrocarbon radical with 1 to 5 carbon atoms or a hydrogen atom such that R 17 is hydrogen when q=0 and L is a cyclic residue; a, c, e, and g are zero or a positive integer such that 0<a+b+c+d+e+f+g<500; subscripts b, d, and f have values of 0 or 1 such that b+d+f=1; and Z is chosen from O or a CH 2 group subject to the limitation that the molecule contains an even number of O 1/2 and an even number of (CH 2 ) 1/2 groups, and the O 1/2 and the (CH 2 ) 1/2 groups both are all paired in the molecule;
B is a divalent radical having a formula:

 where R 25 , R 26 , R 27 , and R 28 are independently selected from hydrogen, a halogen, hydroxyl, and a hydrocarbon radical comprising aromatic, aliphatic, and/or aralkyl moieties optionally having heteroatoms; W includes at least one reactive group X and, optionally, a chain stopper group Y, wherein:
X is a free radical polymerizable group having a formula:

 where R 21 , R 22 , and R 23 can be selected from hydrogen or a monovalent hydrocarbon radical with 1 to 5 carbon atoms, which may optionally contain one or more heteroatoms; H can be O or NR 24 , where R 24 can be hydrogen or a monovalent hydrocarbon radical with 1-5 carbons; J is a divalent moiety chosen from a substituted or unsubstituted aliphatic or aromatic hydrocarbon having of 1-10 carbon atoms and may optionally contain one or more heteroatoms; and
Y can be independently selected from hydrogen, hydroxyl, thiol, amine or a monovalent hydrocarbon radical having 1 to 10 carbon atoms, which may optionally contain one or more heteroatoms.

2. The pre-polymer in the composition of claim 1 , wherein L is a hydrophilic residue chosen from a polyalkyleneoxide, optionally a polyalkyleneoxide chosen from —CH 2 CH 2 O—, —CH 2 CH(CH 3 )O—, —CH 2 CH 2 CH 2 O—, and their analogues with up to 6 carbon atoms.

3. The pre-polymer in the composition of claim 1 , wherein L is a cyclic hydrocarbon residue with the structure:

4. The pre-polymer in the composition of claim 1 wherein R 9 , R 10 , R 11 , R 13 , R 14 , R 15 , R 16 , R 18 , and R 20 in the unit G of group E are independently selected from a hydrocarbon radical chosen from methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, phenyl, naphthyl, an aralkyl radical with 8 to 20 carbon atoms, trifluoromethylpropyl, and combinations of two or more thereof.

5. The pre-polymer in the composition of claim 1 , wherein the mono-functional group E has a structure chosen from any of the formulas:

6. The pre-polymer in the composition of claim 1 , where R 25 and R 26 are hydrogen, R 27 is chosen from hydrogen or a methyl radical, and R 28 is a part of an ethylenically-unsaturated hydrophilic monomer or a hydrophobic monomer.

7. The composition of claim 1 , wherein the siloxane pre-polymer has at least one terminal reactive group.

8. The composition of claim 1 where the siloxane pre-polymer is (a) a homopolymer or (b) a copolymer.

9. The composition of claim 8 , wherein the pre-polymer is a copolymer further comprising a free-radical polymerizable organic monomer chosen from a vinylic monomer, an acrylide monomer, an acrylic monomer, or a combination of two or more thereof.

10. The copolymer of claim 8 , wherein the vinylic monomer is chosen from N-vinyl-pyrrolidone, N-vinyl-caprolactam, N-vinyl-acetamide, N-vinyl-formamide and N-vinyl-isopropylamide, vinyl benzene, vinyl naphthalene, vinyl pyridine, vinyl alcohol, vinyl containing silicones, or a combination of two or more thereof.

11. The copolymer of claim 8 , 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, N-isopropylacrylamide, acrylamide, methacrylamide, acrylic acid, methacrylic acid, acrylated hydrophilic or hydrophobic organo-silicones, or c combination of two or more thereof.

12. The copolymer of claim 8 optionally comprises a cross-linker selected from ethylene glycol dimethacrylate, trimethyloylpropane trimethacrylate, diethyleneglycol dimethacrylate, bisphenol A dimethacrylate, diglycidyl bisphenol A dimethacrylate and dimethacrylate-terminated polyethylene glycol and reactive linear or pendant polyether modified silicones.

13. The composition of claim 1 , wherein the initiator is 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 such as benzoyl peroxide, benzoin methyl ether, diethoxyacetophenone, a benzoylphosphine oxide, 2-hydroxy-2-methyl propiophenone (HMPP), 1-hydroxycyclohexyl phenyl ketone, an α-hydroxyketone type, a phenylglyoxylate type, a benysldimethyl-ketal type, an α-aminoketone type, a mono-acyl phosphine type, a bis-acyl phosphine type, a phosphine oxide, a metallocene type, and an iodonium salt.

14. A contact lens comprising the hydrogel film of claim 1 .

15. The contact lens according to claim 14 comprising a limited extraction protocol that further comprises a green or aqueous solvent chosen from water, an organic or inorganic salt solution, a buffer, an emulsion, a commercial

Assignees

• Saxena Anubhav
• Naik Sandeep Shashikant
• Phukan Monjit
• Bhat Shreedhar
• Momentive Performance Mat Inc

Inventors

• Saxena Anubhav
• Naik Sandeep Shashikant
• Phukan Monjit
• Bhat Shreedhar

Classifications

• C08F283/124 Primary

  on to polysiloxanes having carbon-to-carbon double bonds · CPC title

• C08G77/50

  by carbon linkages · CPC title

• C07F7/1856

  Chemistry & Metallurgy · mapped topic

• C07F7/1852

  Chemistry & Metallurgy · mapped topic

• C08L71/00

  Compositions of polyethers obtained by reactions forming an ether link in the main chain (of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06); Compositions of derivatives of such polymers · CPC title