Ethylenically unsaturated polymerizable groups comprising polycarbosiloxane monomers
View Patent ↗The present application relates to novel monomers comprising polycarbosiloxane monomers useful in certain specific embodiments in the manufacture of devices. More particularly, the present application relates to certain ethylenically unsaturated free radical polymerizable monomers comprising polycarbosiloxane monomers. Even more particularly, the present application pertains to monomers comprising polycarbosiloxane monomers which further comprise at least two ethylenically unsaturated free radical polymerizable groups.
1. An article of manufacture selected from the group consisting of contact lenses, phakic and aphakic intraocular lenses and corneal implants; wherein the article is formed from polymerizing a monomer mixture including an ethylenically unsaturated free radical polymerizable polycarbosiloxane monomer of formula (I) and at least a second free radical copolymerizable monomer, wherein the polycarbosiloxane monomer of formula (I) is present at from about 0.1 to about 30 percent by weight of the monomer mixture:
wherein R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently a monovalent atom or group selected from H, alkyl, halo alkyl, heteroalkyl, cyclo alkyl, heterocyclo alkyl, alkenyl, halo alkenyl, or aromatic; wherein R 3 is a monovalent atom or group selected from H, alkyl, halo alkyl, heteroalkyl, cyclo alkyl, heterocyclo alkyl, alkenyl, halo alkenyl, aromatic or methacryloxypropyl; wherein at least one of R 9 or R 10 is hydrogen, and the other of R 9 and R 10 may not be present when monomers of formula (I) comprise -[silyl-alkenyl-siloxy]- units, and when present in a monomer comprising -[silyl-alkyl-siloxy]- units is independently a monovalent atom or group selected from H, alkyl, alkene, alkyne; y is 2-7; n is 1-100; n 1 is greater than zero and up to 10; L is the same or different and is a divalent linker group or a bond; and V is an ethylenically unsaturated free radical polymerizable monovalent group.
2. An article of manufacture of claim 1 , wherein y is 2.
3. An article of manufacture of claim 2 , wherein n is 2-80.
4. An article of manufacture of claim 2 , wherein n is 3-20.
5. An article of manufacture of claim 2 , wherein n is 5-15.
6. The article of manufacture of claim 1 wherein the article is a contact lens.
7. The article of manufacture of claim 6 wherein the article is a hydrogel contact lens.
8. The article of manufacture of claim 1 and the monomer mixture comprises at least second and third copolymerizable monomers.
9. The article of manufacture of claim 8 , wherein the monomer mixture comprises from 0.1 to 75.8 percent by weight of a second copolymerizable silicone comprising hydrophobic monomer, 0 to 60 percent by weight of non-silicone comprising hydrophobic monomers, and 0.1 to 75.8 percent by weight of hydrophilic monomers.
10. The article of manufacture of claim 9 wherein the monomer mixture comprises a bulky monomer selected from the group consisting of methacryloxypropyl tris(trimethylsiloxy)silane (“TRIS”), pentamethyldisiloxy methylmethacrylate, tris(trimethylsiloxy) methacryloxy propylsilane, phenyltretramethyl-disloxanylethyl acrylate, methyldi(trimethylsiloxy) methacryloxymethyl silane, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyol allyl carbamate, and 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate and mixtures thereof.
11. The article of manufacture of claim 10 wherein the bulky monomer is present at about 25 to about 41 percent by weight of the monomer mixture.
12. An article of manufacture of claim 1 , wherein the polycarbosiloxane monomer is of formula (III), (XXVI), (XXVII), (XXVIII), (XXIX), (XXX), (XXXIV), or (XXXV):
wherein n 2 is 0 to 10.
13. An article of manufacture of claim 1 , wherein the polycarbosiloxane monomer is of formula (III):
14. An article of manufacture of claim 1 , wherein the polycarbosiloxane monomer is of formula (XXVI), (XXVII), or (XXVIII):
wherein n 2 is 0 to 10.
15. An article of manufacture of claim 1 , wherein the polycarbosiloxane monomer is of formula (XXIX) or (XXX):
16. An article of manufacture of claim 1 , wherein the polycarbosiloxane monomer is of formula (XXXIV) or (XXXV):
wherein n 2 is 0 to 10.
17. An article of manufacture of claim 1 , wherein the polycarbosiloxane monomer is of formula (IX):
18. An article of manufacture of claim 1 , wherein n is 2-80.
19. An article of manufacture of claim 1 , wherein n is 3-20.
20. An article of manufacture of claim 1 , wherein n is 5-15.