Hydrophilic macromers and hydrogels comprising the same

• US 10,101,499 B2
• Filed: 09/22/2014
• Issued: 10/16/2018
• Est. Priority Date: 03/22/2012
• Status: Active Grant

• Current Assignee: Momentive Performance Materials Incorporated
• Original Assignee: Momentive Performance Materials Incorporated
• Inventors: Saxena, Anubhav, Phukan, Monjit, Bhat, Shreedhar, Lewis, Kenrick M., Umapathy, Senthilkumar
• Primary Examiner(s): Moore, Margaret G
• Application Number:
  US14/492,722
• Publication Number:
  US 20150011667A1
• Time in Patent Office: 1,485 Days
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/46 containing polyether sequences
• CPC Class Codes: C08L 2201/10 Transparent films; Clear coatings; Transparent materials
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C08L 83/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• CPC Class Codes: G02B 1/043 Contact lenses

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(R¹)(R²)O—(Si(R³)(R⁴)O)_a—Si(R⁵)(R⁶)—Y  (1)
wherein R¹, R², R³ R⁴, R⁵ and R⁶ 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 —CH₂—C(R^bR⁷)—(CR⁸R⁹)_n, the subscript n is selected from integers from 1 to 10; R⁷, R⁸, and R⁹ 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.

Claims

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

R—

Si(R¹)(R²)O—

(Si(R³)(R⁴)O)_a—

Si(R⁵)(R⁶)—

Y 

 

(1)

wherein R¹, R², R³ R⁴, R⁵, and R⁶ 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 —

CH₂—

C(R^bR⁷)—

(CR⁸R⁹)_n, n is selected from integers from 1 to 10;

R⁷, R⁸ and R⁹ 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 R¹, R², R³ R⁴, R⁵, or R⁶ contains an I group where R^p is a hydrophilic organic radical.

2. The composition of claim 1, where R¹, R², R³, R⁴, R⁵, and R⁶ are independently selected from methyl, ethyl, propyl, isopropyl, phenyl, polyether, and —

CH₂CH₂CF₃ 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;

R⁷, R⁸ and R⁹ are hydrogen atoms;

the subscript n is selected from 1 to 6;

R^p includes a polyether group with the general formula;

—

O(CH₂CH₂O)_b(CH₂CH(CH₃)O)_c(CH₂CH₂CH₂CH₂O)_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(R¹⁰)═

C(R¹¹)(R¹²)

where R¹⁰, R¹¹, and R¹² are independently selected from hydrogen and a monovalent alkyl group with 1 to 10 carbon atoms, that optionally contain a heteroatom, —

COOH, and —

CH₂COOH.

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:

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 to claim 23, wherein the composition is a film forming additive in a textile, paper, leather, personal care, health care, home care, coating, painting or seed treatment formulation.