Polysiloxane hydrogels

• US 4,136,250 A
• Filed: 07/20/1977
• Issued: 01/23/1979
• Est. Priority Date: 07/20/1977
• Status: Expired due to Term

• Current Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Mueller, Karl F., Kleiner, Eduard K.
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US05/817,405
• Time in Patent Office: 552 Days
• Field of Search: 71/DIG. 1, 424/184, 252/522, 351/160, 260/46.5 UA, 260/46.5 Y, 260/827, 260/46.5 E
• US Class Current: 528/29
• CPC Class Codes: A01N 25/04 Dispersions, emulsions, suspoemulsions, suspension concentrates or gels foams A01N25/16
• CPC Class Codes: A01N 25/10 Macromolecular compounds
• CPC Class Codes: A61K 47/34 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers A61K47/10 takes precedence
• CPC Class Codes: A61L 9/048 air treating gels
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08F 290/148 Polysiloxanes
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/671 Unsaturated compounds having only one group containing active hydrogen takes precedence on groups C08G18/675 - C08G18/69
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

A water-insoluble hydrophilic gel comprising (A) about 20 to about 90% by weight of a hydrophilic (a) polymer of identical or different water-soluble monoolefinic monomers, or (b) copolymer of said water-soluble monomers with 1 to 80% (of total monomers) of water-insoluble, identical or different monoolefinic monomers; which polymer or copolymer is cross-linked with (B) about 10 to about 80% by weight of a terminal polyolefinic siloxane macromer having a molecular weight from about 400 to about 8500.

Claims

1. A water-insoluble hydrophilic gel comprising the crosslinked copolymerization product of

(A) about 20 to about 90% by weight of said gel of (a) a water-soluble monoolefinic monomer, or mixture of said monomers, or (b) a water-soluble monomer, or mixture of said monomers, with 1 to 80% by weight of total monomers of a water-insoluble monoolefinic monomer, or mixture of said water-insoluble monomers, with

(B) about 10 to about 80% by weight of said gel of a terminal polyolefinic hydrophobic siloxane macromer having a molecular weight from about 400 to about 8500, said macromer having the formula ##STR13## wherein R₁ is a polysiloxane chain having a molecular weight from about 200 to about 8000, and is of the formula ##STR14## R₂ is hydrogen or methyl, R₃ is hydrogen or --COOR₄,

R₄ is hydrogen or alkyl of 1 to 10 carbon atoms, and with the proviso that at least one of R₂ and R₃ is hydrogen,

X is oxa, --COO-- or --CONR₅ --,

R₅ is hydrogen or alkyl of 1 to 5 carbon atoms,

R₆ is a branched or linear alkylene of 1 to 7 carbon atoms or --CH₂ CH₂ O--_n where n is 1 to 20,

x is an integer of 3 to 120,

y is an integer of 2 to 3,

z is an integer of 1 to 2,

Y is the direct bond, the diradical

--R₇ Z₁ --CONH--R₈ --NHCO--Z₂ --, or --R₇ OCOCH₂ CH₂ S--,

R₇ is a linear or branched alkylene of 2 to 5 carbon atoms connected to X,

R₈ is a diradical obtained by removing the NCO groups from an aliphatic, cycloaliphatic or aromatic diisocyanate,

Z₁ is oxa or --NR₅ --,

Z₂ is Z₁ or thia and is connected to R₆, with the proviso that if X is oxa, Y is different from a direct bond and R₂ and R₃ are hydrogen.

2. A gel according to claim 1 wherein the water-soluble monomer is selected from the group consisting of acrylic acid, methacrylic acid and the water-soluble esters, amides and imides of said acids, salts of monoolefinic sulfonic acids and monoolefinic monocyclic azacyclic compounds.

3. A gel according to claim 1 wherein the water-soluble monomer is acrylic acid, methacrylic acid, a hydroxyalkyl or dialkylaminoalkyl ester of said acids in which alkyl is 2 to 4 carbon atoms.

4. A gel according to claim 1 wherein the water-soluble monomer is an acrylic acid or methacrylic acid ester of an alcohol of the formula

5. A gel according to claim 1 wherein the water-soluble monomer is an amide or imide of acrylic or methacrylic acid in which the N-substituent is hydroxyalkyl, oxaalkyl or dialkylaminoalkyl where alkyl is 2 to 4 carbon atoms.

6. A gel as claimed in claim 1 wherein the water-soluble monomer is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate or N-vinyl-2-pyrrolidone.

7. A gel according to claim 1 wherein the water-soluble monomer is 2-hydroxyethyl methacrylate.

8. A gel according to claim 1 wherein the water-soluble monomer is N-vinyl-2-pyrrolidone.

9. A gel according to claim 1 wherein the water-soluble monomer is a hydroxyalkyl maleate or fumarate where alkyl is 2 to 4 carbon atoms.

10. A gel according to claim 1 wherein the water-soluble monomer is a hydroxyalkyl vinyl ether where alkyl is 2 to 4 carbon atoms.

11. A gel according to claim 1 wherein the water-insoluble monomer is selected from the group consisting of the alkyl acrylates of methacrylates where alkyl is 1 to 18 carbon atoms, vinyl esters of alkanoic acids of 1 to 5 carbon atoms, vinyl benzoate, acrylonitrile, styrene and vinyl alkyl ethers where alkyl is 1 to 5 carbon atoms.

12. A gel according to claim 1 wherein the water-insoluble monomer is an alkyl acrylate or methacrylate where alkyl is 1 to 5 carbon atoms, vinyl acetate, styrene or acrylonitrile.

13. A gel according to claim 1 wherein the siloxane macromer with a molecular weight of about 600 to about 8500, and which comprises a polysiloxane polyol or dithiol of molecular weight of about 400 to about 8000 first endcapped with isophorone diisocyanate or tolylene-2,4-diisocyanate and then reacted with a hydroxy compound selected from the group consisting of the hydroxyalkyl esters, where alkyl is 2 to 4 carbon atoms, of acrylic acid, methacrylic acid, maleic acid and fumaric acid, the hydroxy esters of said acids with a alcohol of the formula

14. A gel according to claim 13 wherein the hydroxy compound is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate or 2,3-dihydroxypropyl methacrylate.

15. A gel according to claim 13 wherein the hydroxy compound is 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.

16. A gel according to claim 13 wherein the polysiloxane polyol or dithiol is endcapped with isophorone diisocyanate and the hydroxy compound is 2-hydroxyethyl methacrylate.

17. A gel according to claim 1 wherein about 15 to about 60% by weight of said gel is the siloxane macromer.

18. A pharmaceutical composition, comprising a gel as claimed in claim 1, together with a pharmacologically effective compound.

19. A fragrance composition, comprising a gel as claimed in claim 1, together with an odorant.

20. A pesticidal composition, comprising a gel as claimed in claim 1, together with a pesticide.

21. A herbicidal composition, comprising a gel as claimed in claim 1, together with a herbicide.

22. A gel according to claim 1 which is formed into a contact lens.