Monomeric units useful for reducing the modulus of low water polymeric silicone compositions

• US 5,714,557 A
• Filed: 11/12/1996
• Issued: 02/03/1998
• Est. Priority Date: 12/07/1995
• Status: Expired due to Term

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Kunzler, Jay F., Ozark, Richard M.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): SAROFIM, NABIL F
• Application Number:
  US08/745,537
• Time in Patent Office: 448 Days
• Field of Search: 526/279, 351/160 R, 523/106
• US Class Current: 526/279
• CPC Class Codes: C07F 7/0838 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 Class Codes: C08F 30/08 containing silicon
• CPC Class Codes: C08L 43/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

Monomeric units useful in reducing the modulus of low water polymeric silicone compositions are disclosed. Low water compositions including the subject monomeric units are especially useful in the formation of biomedical articles such as low water silicone contact lenses. ##STR1## wherein: A is an activated unsaturated group;

R and D independently are alkyl, alkylene or haloalkyl groups having 1 to 10 carbon atoms wherein said carbon atoms may include ether linkages therebetween;

M is hydrogen, fluorine, or an alkyl group;

R₁, R₂, R₃ and R₄ are independently selected from: alkyl or haloalkyl groups wherein ether linkages may be included between carbon atoms; siloxane groups; and carbocyclic ring groups having from 6 to 18 carbon atoms;

m is an integer from 1 to 500; n is an integer from 1 to 20; x and y are 0 or 1;

z is 1 or 2; and x+y+z=3;

so long as at least one of R₁ or R₂ is an alkyl group having from 1 to 10 carbon atoms.

Claims

1. A low water polymeric silicone composition having a Young'"'"'s modulus of elasticity from about 20 g/mm² to about 150 g/mm² and formed by polymerizing a monomer mix comprising monomeric units represented by Formula I:

##STR21## wherein;

A is an activated unsaturated group;

R and D independently are alkyl, alkylene, or haloalkyl groups having 1 to 10 carbon atoms wherein said carbon atoms may include ether linkages therebetween;

M is hydrogen, fluorine, or an alkyl group;

R₁, R₂, R₃ and R₄ are independently selected from;

alkyl or haloalkyl groups wherein ether linkages may be included between carbon atoms;

siloxane groups; and

carbocyclic ring groups having from 6 to 18 carbon atoms;

m is an integer from 1 to 500;

n is an integer from 1 to 20;

x and y are 0 or 1;

z is 1 or 2; and

x+y+z=3;

so long as at least one of R₁ or R₂ is an alkyl group having from 1 to 10 carbon atoms.

2. The composition of claim 1 wherein z is 1;

R₁, R₂, R₃, and R₄ are independently selected from alkyl groups having from 1 to 10 carbon atoms;

A is a group selected from;

an ester or amide of acrylic acid or methacrylic acid;

R and D are alkyl groups having firm 1 to 6 carbon atoms wherein said carbon atoms may include ether linkages therebetween;

m is from 1 to 10; and

n is from 1 to 6.

3. The composition of claim 1 wherein the monomeric units represented by Formula I include monomeric units represented by at least one of Formulae II and III:

##STR22##

4. The composition of claim 1 formed by polymerizing comprising the following:

(a) from about 1 to about 99 weight percent of silicone-containing monomeric units other than those represented by Formula I; and

(b) from about 1 to about 50 weight percent of the monomeric units represented by Formula I.

5. The composition of claim 4 wherein said silicone-containing monomeric units comprise monomeric units represented by Formula IV:

##STR23## wherein;

A'"'"' and A" are activated unsaturated groups;

R'"'"' and R" independently are an alkyl or alkylene group having 1 to 10 carbon atoms wherein the carbon atoms may include ether linkages therebetween;

R₈ through R₁₇ are independently selected from the groups described with reference to R₁ though R₄ ;

a is an integer equal to or greater than 1;

b and c are integers equal to or greater than 0; and

a+b+c equals an integer from 1 to 1000.

6. The composition of claim 5 wherein A'"'"' and A" are groups selected from:

an ester or amide of acrylic acid or methacrylic acid;

R'"'"' and R" are selected from are alkyl groups having from 1 to 6 carbon atoms wherein said carbon atoms may include ether linkages therebetween;

R₈ through R₁₇ are independently selected from alkyl groups having from 1 to 10 carbon atoms, and at least one of R₈ through R₁₇ is a fluoroosubstituted alkyl group.

7. The composition of claim 5 wherein said monomeric units represented by Formula IV include monomeric units selected from those represented by Formulae V and VI, and combinations thereof:

##STR24## wherein;

d, e, f, and g, are integers from 0 to 1000;

d+e equals an integer from 2 to 1000;

f+g equals an integer from 2 to 1000; and

h is an integer from 1 to about 20.

8. A contact lens comprising a low water polymeric silicone composition having a Young'"'"'s modulus of elasticity from about 20 g/mm² to about 150 g/mm² and formed by polymerizing a monomer mix comprising monomeric units represented by Formula I:

##STR25## wherein;

A is an activated unsaturated group;

R and D independently are alkyl, alkylene, or haloalkyl groups having 1 to 10 carbon atoms wherein said carbon atoms may include ether linkages therebetween;

M is hydrogen, fluorine, or an alkyl group;

R₁, R₂, R₃ and R₄ are independently selected from;

alkyl or haloalkyl groups wherein ether linkages may be included between carbon atoms;

siloxane groups; and

carbocyclic ring groups having from 6 to 18 carbon atoms;

m is an integer from 1 to 500;

n is an integer from 1 to 20;

x and y are 0 or 1;

z is 1 or 2; and

x+y+z=3;

so long as at least one of R₁ or R₂ is an alkyl group having from 1 to 10 carbon atoms.

9. The contact lens of claim 8 wherein z is 1;

R₁, R₂, R₃, and R₄ are independently selected from alkyl groups having from 1 to 10 carbon atoms;

A is a group selected from;

an ester or amide of acrylic acid or methacrylic acid;

R and D are alkyl groups having from 1 to 6 carbon atoms wherein said carbon atoms may include ether linkages therebetween;

m is from 1 to 10; and

n is from 1 to 6.

10. The contact lens of claim 8 wherein the monomeric units represented by Formula I include monomeric units represented by at least one of Formulae II and III:

##STR26##

11. The contact lens of claim 8 wherein said composition is polymerized from a monomer mix comprising:

(a) from about 1 to about 99 weight percent of silicone-containing monomeric units other than those represented by Formula I; and

(b) from about 1 to about 50 weight percent of the monomeric units represented by Formula I.

12. The contact lens of claim 11 wherein said silicone-containing monomeric units comprise monomeric units represented by Formula IV:

##STR27## wherein;

A'"'"' and A" are activated unsaturated groups;

R'"'"' and R" independently are an alkyl or alkylene group having 1 to 10 carbon atoms wherein the carbon atoms may include ether linkages therebetween;

R₈ through R₁₇ are independently selected from the groups described with reference to R₁ though R₄ ;

a is an integer equal to or greater than 1;

b and c are integers equal to or greater than 0; and

a+b+c equals an integer from 1 to 1000.

13. The contact lens of claim 12 wherein A'"'"' and A" are groups selected from:

an ester or amide of acrylic acid or methacrylic acid;

R'"'"' and R" are selected from are alkyl groups having from 1 to 6 carbon atoms wherein said carbon atoms may include ether linkages therebetween;

R₈ through R₁₇ are independently selected from alkyl groups having from 1 to 10 carbon atoms, and at least one of R₈ through R₁₇ is a fluoro-substituted alkyl group.

14. The contact lens of claim 12 wherein said monomeric units represented by Formula IV include monomeric units selected from those represented by Formulae V and VI, and combinations thereof:

##STR28## wherein;

d, e, f, and g, are integers from 0 to 1000;

d+e equals an integer from 2 to 1000;

f+g equals an integer from 2 to 1000; and

h is an integer from 1 to about 20.

15. A method for making a low water polymeric silicone composition including the step of polymerizing a monomer mix comprising monomeric units represented by Formula I:

##STR29## wherein;

A is an activated unsaturated group;

R and D independently are alkyl, alkylene, or haloalkyl groups having 1 to 10 carbon atoms wherein said carbon atoms may include ether linkages therebetween;

M is hydrogen, fluorine, or an alkyl group;

R₁, R₂, R₃ and R₄ are independently selected from;

alkyl or haloalkyl groups wherein ether linkages may be included between carbon atoms;

siloxane groups; and

carbocyclic ring groups having from 6 to 18 carbon atoms;

m is an integer from 1 to 500;

n is an integer from 1 to 20;

x and y are 0 or 1;

z is 1 or 2; and

x+y+z=3;

so long as at least one of R₁ or R2 is an alkyl group having from 1 to 10 carbon atoms.

16. The method of claim 15 wherein z is 1;

R₁, R₂, R₃, and R₄ are independently selected from alkyl groups having from 1 to 10 carbon atoms;

A is a group selected from;

an ester or amide of acrylic acid or methacrylic acid;

R and D are alkyl groups having from 1 to 6 carbon atoms wherein said carbon atoms may include ether linkages therebetween;

m is from 1 to 10; and

n is from 1 to 6.

17. The method of claim 15 wherein the step of polymerizing a monomer mix is further characterized by preparing a monomer mix comprising:

(a) from about 1 to about 99 weight percent of silicone-containing monomeric units other than those represented by Formula I; and

(b) from about 1 to about 50 weight percent of the monomeric units represented by Formula I.

18. The method of claim 17 wherein said silicone-containing monomeric units comprise monomeric units represented by Formula IV:

##STR30## wherein;

A'"'"' and A" are activated unsaturated groups;

R'"'"' and R" independently are an alkyl or alkylene group having 1 to 10 carbon atoms wherein the carbon atoms may include ether linkages therebetween;

R₈ through R₁₇ are independently selected from the groups described with reference to R₁ though R₄ ;

a is an integer equal to or greater than 1;

b and c are integers equal to or greater than 0; and

a+b+c equals an integer from 1 to 1000.

19. The method of claim 18 wherein A'"'"' and A" are groups selected from:

an ester or amide of acrylic acid or methacrylic acid;

R'"'"' and R" are selected from are alkyl groups having from 1 to 6 carbon atoms wherein said carbon atoms may include ether linkages therebetween; and

R₈ through R₁₇ are independently selected from alkyl groups having from 1 to 10 carbon atoms.