Amphiphilic block copolymers

• US 8,071,696 B2
• Filed: 04/28/2011
• Issued: 12/06/2011
• Est. Priority Date: 03/14/2000
• Status: Expired due to Term

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Hirt, Thomas, Schremmer, Jacalyn Marie, Holland, Troy Vernon, Lohmann, Dieter
• Primary Examiner(s): Peng, Kuo-Liang
• Application Number:
  US13/095,954
• Publication Number:
  US 20110201761A1
• Time in Patent Office: 222 Days
• Field of Search: 525/474, 568/615, 523/107
• US Class Current: 525/474
• CPC Class Codes: C08G 77/42 Block-or graft-polymers containing polysiloxane sequences polymerising aliphatic unsaturated monomers on to a polysiloxane C08F283/12

Abstract

The invention relates to novel crosslinkable copolymers of formula

wherein the variables are as defined in the claims. The copolymers of the invention are especially useful for the manufacture of biomedical moldings, for example ophthalmic moldings such as in particular contact lenses.

Claims

1. An amphiphilic block copolymer of formula (1)

2. The amphiphilic block copolymer of claim 1, wherein t is the number 2, p and q is the number zero, wherein the amphiphilic block copolymer is defined by formula (1a)

3. The amphiphilic block copolymer of claim 1, wherein t is the number zero, wherein the amphiphilic block copolymer is defined by formula (1b)

4. The amphiphilic block copolymer of claim 1, wherein A is a polysiloxane segment of formula

5. The amphiphilic block copolymer of claim 1, wherein L₁, L₂ and L₃ are each independently of the other a bivalent linking group of formula

—

X₁—

C(O)—

NH—

R₁₀—

NH—

C(O)—

X₂—

 

 

(4a),

—

X₁—

C(O)—

R₁₀—

C(O)—

X₂—

 

 

(4b),

—

X₁—

C(O)—

 

 

(4c),

—

C(O)—

X₂—

 

 

(4d), or

—

X₁—

C(O)—

X₂—

 

 

(4e),

wherein X₁ and X₂ are each independently of the other a group —

O—

, —

S—

or —

NR₀—

, R₀ is hydrogen or C₁-C₄-alkyl, and R₁₀ is linear or branched C₁-C₁₈-alkylene or unsubstituted or C₁-C₄-alkyl- or C₁-C₄-alkoxy-substituted C₆-C₁₀-arylene, C₇-C₁₈-aralkylene, C₆-C₁₀-arylene-C₁-C₂-alkylene-C₆-C₁₀-arylene, C₃-C₈-cycloalkylene, C₃-C₈-cycloalkylene-C₁-C₆-alkylene, C₃-C₈-cycloalkylene-C₁-C₂-alkylene-C₃-C₈-cycloalkylene or C₁-C₆-alkylene-C₃-C₈-cycloalkylene-C₁-C₆-alkylene.

6. The amphiphilic block copolymer of claim 5, wherein L₁ is a linking group of formula (4a), (4c) or (4e), L₂ is a linking group of formula (4a), and L₃ is a linking group of formula (4b) or (4c).

7. The amphiphilic block copolymer of claim 1, wherein B is a non-ionic segment selected from the group consisting of polysaccharide, polypeptide, poly(vinylpyrrolidone), polyhydroxyalkylacrylate, polyhydroxyalkylmethacrylate, polyacyl alkylene imine, polyacryl amide, polyvinyl alcohol, polyvinyl ether and a polyol.

8. The amphiphilic block copolymer of claim 1, wherein Q is a radical Q₁ of formula

9. The amphiphilic block copolymer of claim 1, wherein Q is a polyoxyalkylene, poly(vinylpyrrolidone), poly(hydroxyethylacrylate), poly(hydroxyethylmethacrylate), polyacrylamide, poly(N,N-dimethylacrylamide), polyacrylic acid, polymethacrylic acid, polyacyl alkylene imine or a copolymeric mixture of two or more of the above-mentioned polymers which in each case comprises one or more ethylenically unsaturated bond and has a weight average molecular weight of ≧

100.

10. The amphiphilic block copolymer of claim 9, wherein Q is a hydrophilic segment of formula

11. The amphiphilic block copolymer of claim 1, wherein A is a polysiloxane segment of formula

12. The amphiphilic block copolymer of claim 2, wherein A is a polysiloxane segment of formula

13. The amphiphilic block copolymer of claim 3, wherein

p and q are each independently of the other an integer 2 to 15,

A is a polysiloxane segment of formula

14. The amphiphilic block copolymer of claim 2, wherein L₁, L₂ and L₃ are each independently of the other a bivalent linking group of formula

—

X₁—

C(O)—

NH—

R₁₀—

NH—

C(O)—

X₂—

 

 

(4a),

—

X₁—

C(O)—

R₁₀—

C(O)—

X₂—

 

 

(4b),

—

X₁—

C(O)—

 

 

(4c),

—

C(O)—

X₂—

 

 

(4d), or

—

X₁—

C(O)—

X₂—

 

 

(4e),

wherein X₁ and X₂ are each independently of the other a group —

O—

, —

S—

or —

NR₀—

, R₀ is hydrogen or C₁-C₄-alkyl, and R₁₀ is linear or branched C₁-C₁₈-alkylene or unsubstituted or C₁-C₄-alkyl- or C₁-C₄-alkoxy-substituted C₆-C₁₀-arylene, C₇-C₁₈-aralkylene, C₆-C₁₀-arylene-C₁-C₂-alkylene-C₆-C₁₀-arylene, C₃-C₈-cycloalkylene, C₃-C₈-cycloalkylene-C₁-C₆-alkylene, C₃-C₈-cycloalkylene-C₁-C₂-alkylene-C₃-C₈-cycloalkylene or C₁-C₈-alkylene-C₃-C₈-cycloalkylene-C₁-C₈-alkylene.

15. The amphiphilic block copolymer of claim 14, wherein L₁ is a linking group of formula (4a), (4c) or (4e), L₂ is a linking group of formula (4a), and L₃ is a linking group of formula (4b) or (4c).

16. The amphiphilic block copolymer of claim 2, wherein B is a non-ionic segment selected from the group consisting of polysaccharide, polypeptide, poly(vinylpyrrolidone), polyhydroxyalkylacrylate, polyhydroxyalkylmethacrylate, polyacyl alkylene imine, polyacryl amide, polyvinyl alcohol, polyvinyl ether and a polyol.

17. The amphiphilic block copolymer of claim 2, wherein Q is a radical Q₁ of formula

18. The amphiphilic block copolymer of claim 2, wherein Q is a polyoxyalkylene, poly(vinylpyrrolidone), poly(hydroxyethylacrylate), poly(hydroxyethylmethacrylate), polyacrylamide, poly(N,N-dimethylacrylamide), polyacrylic acid, polymethacrylic acid, polyacyl alkylene imine or a copolymeric mixture of two or more of the above-mentioned polymers which in each case comprises one or more ethylenically unsaturated bond and has a weight average molecular weight of ≧

100.

19. The amphiphilic block copolymer of claim 18, wherein Q is a hydrophilic segment of formula

20. The amphiphilic block copolymer of claim 3, wherein L₁, L₂ and L₃ are each independently of the other a bivalent linking group of formula

—

X₁—

C(O)—

NH—

R₁₀—

NH—

C(O)—

X₂—

 

 

(4a),

—

X₁—

C(O)—

R₁₀—

C(O)—

X₂—

 

 

(4b),

—

X₁—

C(O)—

 

 

(4c),

—

C(O)—

X₂—

 

 

(4d), or

—

X₁—

C(O)—

X₂—

 

 

(4e),

wherein X₁ and X₂ are each independently of the other a group —

O—

, —

S—

or —

NR₀—

, R₀ is hydrogen or C₁-C₄-alkyl, and R₁₀ is linear or branched C₁-C₁₈-alkylene or unsubstituted or C₁-C₄-alkyl- or C₁-C₄-alkoxy-substituted C₆-C₁₀-arylene, C₇-C₁₈-aralkylene, C₆-C₁₀-arylene-C₁-C₂-alkylene-C₆-C₁₀-arylene, C₃-C₈-cycloalkylene, C₃-C₈-cycloalkylene-C₁-C₆-alkylene, C₃-C₈-cycloalkylene-C₁-C₂-alkylene-C₃-C₈-cycloalkylene or C₁-C₆-alkylene-C₃-C₈-cycloalkylene-C₁-C₆-alkylene.