Strong, silicone containing polymers with high oxygen permeability

• US 4,486,577 A
• Filed: 10/12/1982
• Issued: 12/04/1984
• Est. Priority Date: 10/12/1982
• Status: Expired due to Term

• Current Assignee: CIBA Vision Corporation (Bayer AG)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Mueller, Karl F., Heiber, Sonia J., Plankl, Walter L.
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US06/433,743
• Time in Patent Office: 784 Days
• Field of Search: 528/24, 528/26, 528/28, 525/474, 525/479, 351/160 R, 351/160 H
• US Class Current: 525/474
• CPC Class Codes: C08F 290/148 Polysiloxanes
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

Clear, strong, crosslinked polymers are described, which are obtained by copolymerization of (A) 8-70% of a linear or branched polysiloxane of 400-100,000 molecular weight (MW) containing at least two terminal or pendant, polymerizable, vinyl groups per each 5000 MW unit of polysiloxane and which are attached to the polysiloxane through at least two urethane, thiourethane, urea or amide linkages and (B) 30-92% of a mono- or divinyl compound or a mixture of such monomers consisting of 85 to 100% of water insoluble monomers. These polymers are useful in the preparation of hard or soft contact lenses.

Claims

1. A polymer, suitable for use in contact lenses, comprising the crosslinked copolymerization product of

(A) from about 15 to about 60% by weight of said polymer of a linear or branched polysiloxane macromer having a molecular weight from about 400 to about 100,000, as measured by end group analysis or gel permeation chromatography, said macromer containing at least two terminal or pendant, polymerizable olefinic groups per each 5000 molecular weight unit of polysiloxane, said groups being attached to the polysiloxane through at least two urethane, thiourethane, urea or amide linkages, said macromer having the structure A₁ or A₂, ##STR16## wherein:

R₁ is a linear or branched alkylene group with 2-6 carbon atoms or a polyoxyalkylene group of structure G ##STR17## wherein R₃ is hydrogen or methyl and n is an integer from 1-50 or R₂, R_a, R_b, R_c, R_d, R_e, F_f, R_g, R_h, R_i, R_j, and R_k are independently methyl or phenyl, x₁ and X₂ are integers from 1 to 500 with the provison that the sum of x₁ +x₂ is 7 to 1000, y₁ is 0 to 14 and y₂ is 1 to 13 with the proviso that the ratio of ##EQU3## is not greater than 70, E₁, E₂, E₃, T₁ and T₂ are each a direct bond,

m is 1 or 2,

x is a di- or tri-radical;

space="preserve" listing-type="equation">--Z.sub.1 --CO--NH--R.sub.4 --(NH--CO--).sub.v

wherein v=1 or 2, Z₁ is oxygen, sulfur or NR₅, wherein R₅ is hydrogen or lower (C₁ -C₄) alkyl, Z₁ is connected to R₁ ; and

R₄ is a di- or triradical obtained by removing the NCO-groups from an aliphatic, cycloaliphatic or aromatic di- or triisocyanate;

Y is;

##STR18## wherein;

R₆ is;

hydrogen, methyl, --COOR₅ or --COOR₇ OH with the proviso that if R₆ is other than hydrogen,

m and w₁ are each 1; and

R₈ is a direct bond;

Z₂ =oxygen or --NR₅ --

R₇ is a linear or branched alkylene of 2 to 10 carbon atoms, phenylene or phenylalkylene with 2 to 10 carbon atoms in the alkylene, or polyoxyalkylene of structure G,

R₈ is R₇ or a tri- or tetra radical residue with 2-4 carbon atoms;

w₁ is 1 to 3;

R₉ is an alkylene group of from 2 to 4 carbon atoms or a direct bond with the proviso that if w₁ =1, R₉ is a direct bond, and it follows that R₈ is a di-radical;

R₁₀ is hydrogen, methyl or --CH₂ COOH, with the proviso that if R₁₀ is --CH₂ COOH, R₆ is hydrogen;

R₁₁ is a direct bond or an aliphatic di-, tri- or tetra-radical with from 1-6 carbon atoms, and

w₂ is 1 to 3, with the proviso that if R₁₁ is a direct bond, w₂ is 1, and

(B) about 85 to about 40% by weight of said polymer of a mixture of water-soluble and water-insoluble monomers or water-insoluble monomers, said monomers being monoolefinic, diolefinic or a mixture of monoolefinic and diolefinic monmers, with from 85 to 100% by weight of the total monomers being water-insoluble, and with from 25 to 0% by weight of the total monomers being diolefinic.

2. A polymer according to claim 1 where in the polysiloxane of structure A₁ or A₂, R₁ is alkylene of 3 or 4 carbon atoms, R₂, R_a, R_b, R_c, R_d, R_e, R_f, R_g, R_h, R_i, R_j and R_k are each methyl, x₁ +x₂ is 10 to 100, y₁ is 0 to 2, y₂ is 1 to 3, m is 1, E₁, E₂, E₃, T₁ and T₂ are each a direct bond, X is --Z₁ --CONH--R₄ --NHCO-- where Z₁ is --O-- or --NH-- and R₄ is a diradical of an aliphatic or cycloaliphatic diisocyanate with 6 to 10 carbon atoms, and Y is ##STR19## wherein R₆ is hydrogen, R₈ is ethylene, R₉ is a direct bond, w₁ is 1 and Z₂ is --O-- or --NC(CH₃)₃ --.

3. A polymer according to claim 2 where the polysiloxane is of structure A₂, R₄ is the diradical derived from isophorone diisocyanate, Z₁ and Z₂ are each --O--, and y₂ is 1 or 2.

4. A polymer according to claim 1 wherein the component (B) is present at the 85 to 50% by weight level of the total polymer.

5. A polymer according to claim 1 wherein component B is a water insoluble monomer B₁ which is an acrylate or methacrylate of formula CH₂ ═

CR₃ COOR₁₂, an acrylamide or methacrylamide of formula CH₂ ═

CR₃ CONHR₁₂, a maleate or fumarate of formula R₁₂ OCOCH═

CHCOOR₁₂, an itaconate of formula R₁₂ OCOC(═

CH₂)CH₂ COOR₁₂, a vinyl ester of formula R₁₂ COOCH═

CH₂, a vinyl ether of formula CH₂ ═

CHOR₁₂, or a mixture of said monomers, wherein R₃ is hydrogen or methyl, and R₁₂ is a linear or branched aliphatic, cycloaliphatic or aromatic alkyl group with from 1 to 21 carbon atoms and which may contain ether or thioether linkages or a --CO-- group;

or is a heterocyclic alkyl group containing oxygen, sulfur or nitrogen atoms, or a polypropylene oxide or poly-n-butylene oxide group with from 2 to 50 repeating alkoxy units;

or is perfluorinated alkyl groups with from 1-12 carbon atoms;

or is alkyl containing siloxane groups with from one to six Si atoms;

or --SO-- and --SO₂ -- groups.

6. A polymer according to claim 5 wherein the water insoluble monomer B₁ is selected from the group consisting of methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, hexafluoroisopropyl methacrylate and mixtures thereof.

7. A polymer according to claim 6 wherein the water insoluble monomer B₁ is selected from the group consisting of methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, isobornyl methacrylate and mixtures thereof.

8. A polymer according to claim 1 wherein component (B) contains 1 to 25%, based on the total weight of monomer, of a diolefinic monomer.

9. A polymer according to claim 1 wherein diolefinic monomer (B_x) of component B is the acrylate or methacrylate of allyl alcohol, of a straight or branched chain alkylene glycol of 2 to 6 carbon atoms, of poly(ethylene oxide)glycol, of poly(propylene oxide)glycol, of poly(n-butylene oxide)glycol, of thiodiethylene glycol, of neopentylene glycol, of trimethylolpropane, or of pentaerthyritol;

or the reaction product obtained by reacting one mol of a di- or tri-isocyanate of structure OCN--R₄ --(NCO)_v, where R₄ is defined as in claim 1 and v is 1 or 2, with 2 or 3 moles of a hydroxyalkyl acrylate or methacrylate.

10. A polymer according to claim 1 wherein component B is a mixture of methyl methacrylate and 1 to 25% by weight of the total monomer of neopentylene glycol diacrylate, ethylene glycol dimethacrylate or the reaction product of one mol of isophorone diisocyanate and two moles of 2-hydroxyethyl methacrylate.

11. A polymer according to claim 5 wherein the water insoluble monomer B₁ is a mixture of vinyl acetate and dimethyl maleate in a 2/1 to 5/1 mol ratio plus methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate or hexafluoroisopropyl methacrylate or mixtures thereof.

12. A polymer according to claim 5 wherein the water insoluble monomer B₁ is selected from the group consisting of 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, perfluoroalkyl (C₆ -C₁₀) substituted alkyl acrylate or methacrylate;

and mixtures thereof.

13. A polymer according to claim 1 where in component B the water soluble monomer B₂ is an acrylate or methacrylate of formula CH₂ ═

CR₃ COOR₁₃, an acrylamide or metharylamide of formula CH₂ ═

CR₃ CONHR₁₄ or CH₂ ═

CR₃ CON(R₅)₂, a maleate or fumarate of formula R₁₃ OCOCH═

CHCOOR₁₃, a vinyl ether of formula CH₂ ═

CHOR₁₃, an N-vinyl lactam;

or a mixture of said monomers,

wherein R₃ is hydrogen or methyl, R₅ is hydrogen or lower (C₁ -C₄) alkyl, R₁₃ is a hydrocarbon residue of 1 to 10 carbon atoms substituted by one or more water solubilizing groups such as carboxy, hydroxy or tert.-amino, or a polyethylene oxide group with from 2-100 repeating units, or a group which contains sulfate, phosphate, sulfonate or phosphonate groups, and R₁₄ is defined as R₁₃ or as R₅.

14. A polymer according to claim 13 wherein the water soluble monomer B₂ is selected from the group consisting of 2-hydroxyethyl methacrylate, N,N-dimethylacrylamide, acrylic acid, methacrylic acid and N-vinyl-2-pyrrolidone.

15. A polymer according to claim 1 where component A is a polysiloxane structure of A₁ or A₂, R₁ is alkylene of 3 or 4 carbon atoms, R₂, R_a, R_b, R_c, R_d, R_e, R_f, R_g, R_h, R_i, R_j and R_k are each methyl, x₁ +x₂ is 10 to 100, y₁ is 0 to 2, y₂ is 1 to 3, m is 1, E₁, E₂, E₃, T₁ and T₂ are each a direct bond, X is --Z₁ --CONH--R₄ --NHCO-- where Z₁ is --O-- or --NH-- and R₄ is a diradical of an aliphatic or cycloaliphatic diisocyanate with 6 to 10 carbon atoms, and Y is ##STR20## wherein R₆ is hydrogen, R₈ is ethylene, R₉ is a direct bond, w₁ is 1 and Z₂ is --O-- or --NC(CH₃)₃ --, and

component B contains from 0 to 25% based on total monomer of a diolefinic monomer (B_x) which is the acrylate or methacrylate of allyl alcohol, of a straight or branched chain alkylene glycol of 2 to 6 carbon atoms, of poly(ethylene oxide)glycol, of poly(propylene oxide)glycol, of poly(n-butylene oxide)glycol, of thiodiethylene glycol, of neopentylene glycol, of trimethylolpropane, or of pentaerthyritol;

or the reaction product obtained by reacting one mol of a di- or tri-isocyanate of structure OCN--R₄ --(NCO)_v, where R₄ is defined as in claim 1 and v is 1 or 2, with 2 or 3 moles of a hydroxyalkyl acrylate or methacrylate.

16. A polymer according to claim 15 wherein B_x is neopentylene glycol diacrylate, ethylene glycol dimethacrylate or the reaction product of one mol of isophorone diisocyanate and two moles of 2-hydroxyethyl methacrylate.

17. A polymer according to claim 15 wherein component B contains the water insoluble monomer B₁ selected from the group consisting of methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, hexafluoroisopropyl methacrylate and mixtures thereof.

18. A polymer according to claim 17 wherein component B contains the water insoluble monomer B₁ selected from the group consisting of methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate isobornyl methacrylate and mixtures thereof.

19. A polymer according to claim 16 wherein component B contains as the water insoluble monomer B₁ methyl methacrylate, isobornyl methacrylate or mixtures thereof.

20. A polymer according to claim 15 wherein component B contains the water insoluble monomer B₁ which is a mixture of vinyl acetate and dimethyl maleate in a 2/1 to 5/1 mol ratio plus methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate or hexafluoroisopropyl methacrylate or mixtures thereof.

21. A polymer according to claim 15 wherein component B contains the water insoluble monomer B₁ selected from the group consisting of 2-ethylhexyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, perfluoroalkyl (C₆ -C₁₀) substituted alkyl acrylate or methacrylate;

and mixtures thereof.

22. A polymer according to claim 15 wherein component B contains the water soluble monomer B₂ selected from the group consisting of 2-hydroxyethyl methacrylate, N,N-dimethylacrylamide, acrylic acid, methacrylic acid and N-vinyl-2-pyrrolidone.

23. A polymer according to claim 15 which comprises

(A) from about 15 to about 35% by weight of a polysiloxane of structure A₂, R₄ is the diradical derived from isophorone diisocyanate, Z₁ and Z₂ are each --O--, and y₂ is 1 or 2, and

(B) from about 85 to about 65% by weight of a mixture of a water-insoluble monomer (B₁), of a water-soluble monomer (B₂), and of a diolefinic monomer (B_x), wherein, based on percent by weight of the total weight of monomers,

B₁ is from about 60 to about 95% of a water-insoluble monomer selected from the group consisting of methyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and mixtures thereof,

B₂ is from about 15 to about 0% of a water-soluble monomer selected from the group consisting of 2-hydroxyethyl methacrylate, N,N-dimethylacrylamide, acrylic acid, methacrylic acid, N-vinyl-2-pyrrolidone and mixtures thereof, and

B_x is from about 25 to about 5% of a diolefinic monomer selected from the group consisting of neopentylene glycol diacrylate, ethylene glycol dimethacrylate and the reaction product of one mol of isophorone diisocyanate and two moles of 2-hydroxyethyl methacrylate.

24. A polymer according to claim 15 which comprises

(A) from about 40 to about 60% by weight of a polysiloxane of structure A₂, R₄ is the diradical derived from isophorone diisocyanate, Z₁ and Z₂ are each --O--, and y₂ is 1 or 2, and

(B) from about 60 to about 40% by weight of a mixture of a water-insoluble monomer (B₁), of a water-soluble monomer (B₂), and of a diolefinic monomer (B_x), wherein, based on percent by weight of the total weight of monomers,

B₁ is from about 89 to about 100% of a water-insoluble monomer selected from the group consisting of ethyl acrylate or methacrylate, n-butyl acrylate or methacrylate, n-hexyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, n-octyl acrylate or methacrylate, n-decyl acrylate or methacrylate and mixtures thereof and with mixtures thereof with methyl or isobornyl methacrylate,

B₂ is from about 11 to about 0% of a water-soluble monomer selected from the group consisting of 2-hydroxyethyl methacrylate, N,N-dimethylacrylamide, acrylic acid, methacrylic acid, N-vinyl-2-pyrrolidone and mixtures thereof, and

B_x is from about 5 to about 0% of a diolefinic monomer selected from the group consisting of neopentylene glycol diacrylate, ethylene glycol dimethacrylate and the reaction product of one mol of isophorone diisocyanate and two moles of 2-hydroxyethyl methacrylate.

25. A hard contact lens prepared from the polymer according to claim 1.

26. A hard contact lens prepared from the polymer according to claim 23.

27. A soft contact lens prepared from the polymer according to claim 1.

28. A soft contact lens prepared from the polymer according to claim 24.