Tris(trimethyl siloxy)silane vinylic monomers and uses thereof

Patent metadata

Field	Value
Publication number	US-9567352-B2
Application number	US-201615264624-A
Country	US
Kind code	B2
Filing date	Sep 14, 2016
Priority date	Dec 14, 2012
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

The invention provides a TRIS-containing vinylic monomer which comprises one sole (meth)acryloyloxy group and a tris(trimethylsiloxy)silyl group covalently linked to the ethylenically-unsaturated group through a polyoxyethylene linker. The present invention is also related to a polymer, an actinically-crosslinkable silicone-containing prepolymer, a silicone hydrogel polymeric material, or a silicone hydrogel contact lens, which comprises monomeric units derived from a TRIS-containing vinylic monomer of the invention. In addition, the invention provides a method for making a TRIS-containing vinylic monomer of the invention.

First claim

What is claimed is:

1. A method for preparing a silicone vinylic monomer, comprising the steps of: reacting a polyoxyethylene (meth)acrylate of formula (II) with an isocyanatoalkyl tris(trimethylsiloxy)silane of formula (III) in the presence or absence of a solvent and in the presence of a catalyst to form the silicone vinylic monomer of formula (I),

wherein R 1 is hydrogen or methyl, q1 is an integer of 6 to 20, and R 2 is a diradical of an alkane or cycloalkane which comprises up to 20 carbon atoms and may have one or more ether, thio, amine, carbonyl, or amido linkages in the main chain.

2. The method of claim 1 , wherein the step of reacting is carried out in a solvent that is a ketone solvent.

3. The method of claim 1 , wherein the catalyst is an amine catalysts, a tin catalyst, and/or an iron catalyst.

4. The method of claim 1 , wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).

5. The method of claim 1 , wherein the step of reacting is carried out by charging the polyoxyethylen (meth)acrylate of formula (II), the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) and a reaction solvent in a reactor and then adding a catalyst thereto to form a reaction mixture.

6. The method of claim 1 , wherein the step of reacting is carried out by charging the polyoxyethylen (meth)acrylate of formula (II), a reaction solvent and a catalyst in a reactor, whereupon the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) is added dropwise to form a reaction mixture, wherein the dropwise addition is started at a temperature of about −10° C. to about 30° C., and the internal temperature of the reaction mixture is controlled below 50° C. during dropwise addition.

7. The method of claim 1 , wherein the molar ratio of polyoxyethylene (meth)acrylate of formula (II) to isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) is from about 1.0 to about 1.2.

8. The method of claim 2 , wherein the step of reacting is carried out in a solvent that is a ketone solvent selected from methyl ethyl ketone and methyl isobutyl ketone.

9. The method of claim 1 , wherein the catalyst is selected from the group consisting of triethylamine, dibutyltin dilaurate, tris(2,4-pentanedionato)iron(III), and combinations thereof.

10. The method of claim 2 , wherein the catalyst is selected from the group consisting of triethylamine, dibutyltin dilaurate, tris(2,4-pentanedionato)iron(III), and combinations thereof.

11. The method of claim 8 , wherein the catalyst is selected from the group consisting of triethylamine, dibutyltin dilaurate, tris(2,4-pentanedionato)iron(III), and combinations thereof.

12. The method of claim 2 , wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).

13. The method of claim 3 , wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).

14. The method of claim 8 , wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).

15. The method of claim 9 , wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).

16. The method of claim 10 , wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).

17. The method of claim 11 , wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).

18. The method of claim 11 , wherein the step of reacting is carried out by charging the polyoxyethylene(meth)acrylate of formula (II), the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) and a reaction solvent in a reactor and then adding a catalyst thereto to form a reaction mixture.

19. The method of claim 11 , wherein the step of reacting is carried out by charging the polyoxyethylene(meth)acrylate of formula (II), a reaction solvent and a catalyst in a reactor, whereupon the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) is added dropwise to form a reaction mixture, wherein the dropwise addition is started at a temperature of about −10° C. to about 30° C., and the internal temperature of the reaction mixture is controlled below 50° C. during dropwise addition.

20. The method of claim 11 , wherein the molar ratio of polyoxyethylene (meth)acrylate of formula (II) to isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) is from about 1.0 to about 1.2.

Assignees

• Novartis Ag
• Shin-Etsu Chemical Company Ltd

Inventors

• Chang Frank
• Hagiwara Mamoru
• Ichinohe Shoji

Classifications

• G02B1/043 Primary

  Contact lenses · CPC title

• C07F7/0889 Primary

  Reactions not involving the Si atom of the Si-O-Si sequence · CPC title

• C07F7/0834

  Compounds having one or more O-Si linkage (for compounds with C-O-Si linkages see C07F7/18) · CPC title

• C08F287/00

  Macromolecular compounds obtained by polymerising monomers on to block polymers · CPC title

• C07F7/0838

  Compounds with one or more Si-O-Si sequences (compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21) · CPC title