Granted Patent B2

US 8,980,972 · App. 13/601,211 · Granted Mar 17, 2015

Abstract

Claims (66)

1. A polymerisable material of formula (I) or (II):

(X—Y 1 ) m —W(Y 2 —Z) n   (I)

[(X) m —Y 3 (Z) p ] v —W—R 1   (II)

wherein

X is a polymerisable group;

Y 1 and Y 2 are each independently a linker group selected from the group consisting of a bond, C 1-12 alkylene, C 2-12 alkenylene, C 2-12 alkynylene, C 3-12 cycloalkylene, C 3-12 cycloalkenylene, C 2-12 heteroalkenylene, C 2-12 heteroalkynylene, arylene, heteroarylene, —C(O)—C 1-12 alkylene, —C(S)—C 1-12 alkylene, —C(O)O—C 1-12 alkylene, —C(O)S—C 1-12 alkylene, —C(O)N(R M )—C 1-12 alkylene, —C(S)—C 1-12 alkylene, —C(S)O—C 1-12 alkylene, —C(S)S—C 1-12 alkylene, —C(S)N(R M )—C 1-12 alkylene, —(CH 2 ) q (OCH 2 CH 2 ) r — and —(CH 2 CH 2 O) r (CH 2 ) q —, wherein R M is hydrogen or C 1-4 alkyl, q is an integer from 1 to 10, r is an integer from 1 to 10, wherein one or more carbon atoms in the C 1-12 alkylene group may be optionally replaced with a heteroatom selected from the group consisting of S and O and the alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, heteroalkenylene, heteroalkynylene, arylene and heteroarylene groups may be optionally substituted with one or more R N , wherein each R N is independently selected from the group consisting of —H, —OH, —CN, —NO 2 , —CF 3 , —OCF 3 , —CO 2 H, —NH 2 , C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —O(C 1 -C 10 alkyl), —O(C 2 -C 10 alkenyl), —O(C 2 -C 10 alkynyl), halogen, —C(O)H, —C(O)—(C 1 -C 10 alkyl), —C(O)—O(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl), —N(C 1 -C 10 alkyl) 2 , —C(O)—NH(C 1 -C 10 alkyl), —C(O)—N(C 1 -C 10 alkyl) 2 , —NH—C(O)—(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl)-C(O)—(C 1 -C 10 alkyl), —NH—S(O) 2 —(C 1 -C 10 alkyl), —NH—(C 1 -C 10 alkyl)-S(O) 2 —(C 1 -C 10 alkyl), —(C 0 -C 10 )—SH, —S(O)—(C 1 -C 10 alkyl), —S(O) 2 —(C 1 -C 10 alkyl), —S(O) 2 —NH 2 , —S(O) 2 —NH—(C 1 -C 10 alkyl), —S(O) 2 —N(C 1 -C 10 alkyl) 2 and ═O;

Y 3 is a linker group;

R 1 is a C 1-12 alkyl group, optionally substituted with one or more R N ;

W is a siloxane group-containing component;

Z is a zwitterionic group;

m is an integer from 1 to 10;

n is an integer from 1 to 3;

p is an integer from 1 to 3;

v is an integer from 1 to 3:

wherein W is a siloxane group of formula

wherein each R is independently selected from hydrogen or a C 1-12 alkylene, C 2 - 12 alkenylene, C 2-12 alkynylene, C 3-12 cycloalkylene, C 3-12 cycloalkenylene, C 1-12 heteroalkylene, C 2-12 heteroalkenylene, C 2-12 heteroalkynylene, arylene, heteroarylene group, optionally substituted with one or more R N , wherein each R N is independently selected from the group consisting of -H, -OH, -CN, -NO 2 , -CF 3 , -OCF 3 , -CO 2 H, -NH 2 , C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, -O(C 1 -C 10 alkyl), -O(C 2 -C 10 alkenyl), halogen, -C(O)H, -C(O) -(C 1 - 10 alkyl), -C(O)-O(C 1 -C 10 alkyl), -NH(C 1 -C 10 alkyl), -N(C 1 -C 10 alkyl) 2 , -C(O)-NH(C 1 -C 10 alkyl), -C(O)-N(C 1 -C 10 alkyl) 2 , -NH-C(O)-(C 1 -C 10 alkyl), -NH(C 1 -C 10 alkyl)-C(O)-(C 1 -C 10 alkyl), -NH-S(O) 2 -(C 1 -C 10 alkyl), -NH-(C 1 -C 10 alkyl)-S(O) 2 -(C 1 -C 10 alkyl), -(C 0 -C 10 )-SH, -S(O)-(C 1 -C 10 alkyl), -S(O) 2 -(C 1 -C 10 alkyl), -S(O) 2 -NH 2 , -S(O) 2 -NH-(C 1 -C 10 alkyl), -S(O) 2 -N(C 1 -C 10 alkyl) 2 and =O; and w, w 3 , w 4 ,w 5 ,w 6 ,w 7 ,w 8 , and w 9 , are each independently an integer in the range from 1 to 500.

2. The polymerisable material of claim 1 , wherein X is a polymerisable group selected from the group consisting of acrylates, methacrylates, styrenes, vinyls and multi-functionalised derivatives.

3. The polymerisable material of claim 2 , wherein X is a methacrylate group.

4. The polymerisable material of claim 1 , wherein Y 3 is selected from the group consisting of a bond, C 1-12 alkylene, C 2-12 alkenylene, C 2-12 alkynylene, C 3-12 cycloalkylene, C 3-12 cycloalkenylene, C 1-12 heteroalkylene C 2-12 heteroalkenylene, C 2-12 heteroalkynylene, arylene, heteroarylene, —C(O)—C 1-12 alkylene, —C(S)—C 1-12 alkylene, —C(O)O—C 1-12 alkylene, —C(O)S—C 1-12 alkylene, —C(O)N(R M )—C 1-12 alkylene, —C(S)—C 1-12 alkylene, —C(S)O—C 1-12 alkylene, —C(S)S—C 1-12 alkylene, —C(S)N(R M )—C 1-12 alkylene, wherein R M is hydrogen or C 1-4 alkyl, wherein the alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, heteroalkenylene, heteroalkynylene, arylene and heteroarylene groups may be optionally substituted with one or more R N , wherein each R N is independently selected from the group consisting of —H, —OH, —CN, —NO 2 , —CF 3 , —OCF 3 , —CO 2 H, —NH 2 , C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —O(C 1 -C 10 alkyl), —O(C 2 -C 10 alkenyl), —O(C 2 -C 10 alkynyl), halogen, —C(O)H, —C(O)—(C 1 -C 10 alkyl), —C(O)—O(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl), —N(C 1 -C 10 alkyl) 2 , —C(O)—NH(C 1 -C 10 alkyl), —C(O)—N(C 1 -C 10 alkyl) 2 , —NH—C(O)—(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl)-C(O)—(C 1 -C 10 alkyl), —NH—S(O) 2 —(C 1 -C 10 alkyl), —NH—(C 1 -C 10 alkyl)-S(O) 2 —(C 1 -C 10 alkyl), —(C 0 -C 10 )—SH, —S(O)—(C 1 -C 10 alkyl), —S(O) 2 —(C 1 -C 10 alkyl), —S(O) 2 —NH 2 , —S(O) 2 —NH—(C 1 -C 10 alkyl), —S(O) 2 —N(C 1 -C 10 alkyl) 2 and ═O.

5. The polymerisable material of claim 4 , wherein the monomer is of formula (II) and wherein Y 3 is C 1-12 heteroalkylene.

6. The polymerisable material of claim 5 , wherein the monomer is of formula (II) and wherein Y 3 is —(CH 2 ) 3 —O—(CH 2 ) 3 —.

7. The polymerisable material of claim 1 , wherein the monomer is of formula (I) and wherein Y 1 and Y 2 are both C 1-12 alkylene, wherein one or more carbon atoms of the alkylene group have been replaced with a heteroatom selected from the group consisting of O and S.

8. The polymerisable material of claim 1 , wherein Y 1 is -(CH 2 CH 2 O) r -(CH 2 ) 3 - and Y 2 is -(CH 2 ) 3 (CH 2 CH 2 O) r -, wherein r is an integer in the range from 1 to 10.

9. The polymerisable material of claim 1 , wherein W is a siloxane group of formula (IIIA):

wherein each R is independently selected from hydrogen or a C 1-12 alkylene, C 2-12 alkenylene, C 2-12 alkynylene, C 3-12 cycloalkylene, C 3-12 cycloalkenylene, C 1-12 heteroalkylene, C 2-12 heteroalkenylene, C 2-12 heteroalkynylene, arylene, heteroarylene group, optionally substituted with one or more R N , wherein each R N is independently selected from the group consisting of —H, —OH, —CN, —NO 2 , —CF 3 , —OCF 3 , —CO 2 H, —NH 2 , C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —O(C 1 -C 10 alkyl), —O(C 2 -C 13 alkenyl), —O(C 2 -C 10 alkynyl), halogen, —C(O)H, —C(O)—(C 1 -C 10 alkyl), —C(O)—O(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl), —N(C 1 -C 10 alkyl) 2 , —C(O)—NH(C 1 -C 10 alkyl), —C(O)—N(C 1 -C 10 alkyl) 2 , —NH—C(O)—(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl)-C(O)—(C 1 -C 10 alkyl), —NH—S(O) 2 —(C 1 -C 10 alkyl), —NH—(C 1 -C 10 alkyl)-S(O) 2 —(C 1 -C 10 alkyl), —(C 0 -C 10 )—SH, —S(O)—(C 1 -C 10 alkyl), —S(O) 2 —(C 1 -C 10 alkyl), —S(O) 2 —NH 2 , —S(O) 2 —NH—(C 1 -C 10 alkyl), —S(O) 2 —N(C 1 -C 10 alkyl) 2 and ═O and w is an integer from 1 to 500.

10. The polymerisable material of claim 1 , wherein W is a siloxane group of formula (IIIC):

wherein each R is independently selected from hydrogen or a C 1-12 alkylene, C 2-12 alkenylene, C 2-12 alkynylene, C 3-12 cycloalkylene, C 3-12 cycloalkenylene, C 1-12 heteroalkylene, C 2-12 heteroalkenylene, C 2-12 heteroalkynylene, arylene, heteroarylene group, optionally substituted with one or more R N , wherein each R N is independently selected from the group consisting of —H, —OH, —CN, —NO 2 , —CF 3 , —OCF 3 , —CO 2 H, —NH 2 , C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —O(C 1 -C 10 alkyl), —O(C 2 -C 10 alkenyl), —O(C 2 -C 10 alkynyl), halogen, —C(O)H, —C(O)—(C 1 -C 10 alkyl), —C(O)—O(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl), —N(C 1 -C 10 alkyl) 2 , —C(O)—NH(C 1 -C 10 alkyl), —C(O)—N(C 1 -C 10 alkyl) 2 , —NH—C(O)—(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl)-C(O)—(C 1 -C 10 alkyl), —NH—S(O) 2 —(C 1 -C 10 alkyl), —NH—(C 1 -C 10 alkyl)-S(O) 2 —(C 1 -C 10 alkyl), —(C 0 -C 10 )—SH, —S(O)—(C 1 -C 10 alkyl), —S(O) 2 —(C 1 -C 10 alkyl), —S(O) 2 —NH 2 , —S(O) 2 —NH—(C 1 -C 10 alkyl), —S(O) 2 —N(C 1 -C 10 alkyl) 2 and ═O and w 3 , w 4 and w 5 are each independently an integer in the range from 1 to 500.

11. The polymerisable material of claim 1 , wherein W is a siloxane group of formula (IIID):

wherein each R is independently selected from hydrogen or a C 1-12 alkylene, C 2-12 alkenylene, C 2-12 alkynylene, C 3-12 cycloalkylene, C 3-12 cycloalkenylene, C 1-12 heteroalkylene, C 2-12 heteroalkenylene, C 2-12 heteroalkynylene, arylene, heteroarylene group, optionally substituted with one or more R N , wherein each R N is independently selected from the group consisting of —H, —OH, —CN, —NO 2 , —CF 3 , —OCF 3 , —CO 2 H, —NH 2 , C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —O(C 1 -C 10 alkyl), —O(C 2 -C 10 alkenyl), —O(C 2 -C 10 alkynyl), halogen, —C(O)H, —C(O)—(C 1 -C 10 alkyl), —C(O)—O(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl), —N(C 1 -C 10 alkyl) 2 , —C(O)—NH(C 1 -C 10 alkyl), —C(O)—N(C 1 -C 10 alkyl) 2 , —NH—C(O)—(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl)-C(O)—(C 1 -C 10 alkyl), —NH—S(O) 2 —(C 1 -C 10 alkyl), —NH—(C 1 -C 10 alkyl)-S(O) 2 —(C 1 -C 10 alkyl), —(C 0 -C 10 )—SH, —S(O)—(C 1 -C 10 alkyl), —S(O) 2 —(C 1 -C 10 alkyl), —S(O) 2 —NH 2 , —S(O) 2 —NH—(C 1 -C 10 alkyl), —S(O) 2 —N(C 1 -C 10 alkyl) 2 and ═O and w 6 , w 7 , w 8 and w 9 are each independently an integer in the range from 1 to 500.

12. The polymerisable material of claim 1 , wherein Z is a zwitterionic group selected from the group consisting of (IVA), (IVB), (IVC), (IVD) and (IVE), wherein group (IVA) has the formula:

wherein each R 3 and R 3A is independently selected from hydrogen and C 1-4 alkyl and a is an integer from 2 to 4;

group (IVB) has the formula:

wherein each R 4 and R 4A is independently selected from hydrogen and C 1-4 alkyl and b is an integer from 1 to 4;

group (IVC) has the formula:

wherein each R 5 and R 5C is independently selected from hydrogen and C 1-4 alkyl; R 5A is hydrogen or a group —C(O)B 1 R 5B , wherein R 5B is hydrogen or methyl, B 1 is selected from the group consisting of a bond; C 1-10 alkylene, C 2-10 alkenylene, C 2-10 alkynylene, C 3-10 cycloalkylene, C 3-10 cycloalkenylene, C 1-10 heteroalkylene, C 2-10 heteroalkenylene, C 2-10 heteroalkynylene, arylene, heteroarylene, —C(O)R M —, —C(O)OR M —, wherein R M is selected from the group consisting of C 1-10 alkylene, C 2-10 alkenylene and C 2-10 alkynylene, and wherein the alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene and heteroarylene groups may be optionally substituted with one or more R N , wherein each R N is independently selected from the group consisting of —H, —OH, —CN, —NO 2 , —CF 3 , —OCF 3 , —CO 2 H, —NH 2 , C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —O(C 1 -C 10 alkyl), —O(C 2 -C 10 alkenyl), —O(C 2 -C 10 alkynyl), halogen, —C(O)H, —C(O)—(C 1 -C 10 alkyl), —C(O)—O(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl), —N(C 1 -C 10 alkyl) 2 , —C(O)—NH(C 1 -C 10 alkyl), —C(O)—N(C 1 -C 10 alkyl) 2 , —NH—C(O)—(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl)-C(O)—(C 1 -C 10 alkyl), —NH—S(O) 2 —(C 1 -C 10 alkyl), —NH—(C 1 -C 10 alkyl)-S(O) 2 —(C 1 -C 10 alkyl), —(C 0 -C 10 )—SH, —S(O)—(C 1 -C 10 alkyl), —S(O) 2 —(C 1 -C 10 alkyl), —S(O) 2 —NH 2 , —S(O) 2 —NH—(C 1 -C 10 alkyl), —S(O) 2 —N(C 1 -C 10 alkyl) 2 and ═O, and c is an integer from 1 to 4, wherein if Z is directly bonded to an O or N atom, z is 0 and otherwise z is 1;

group (IVD) has the formula:

wherein each R 6 and R 6C is independently selected from hydrogen and C 1-4 alkyl; R 6A is hydrogen or a group —C(O)B 2 R 6B , wherein R 6B is hydrogen or methyl, B 2 is selected from the group consisting of a bond; C 1-10 alkylene, C 2-10 alkenylene, C 2-10 alkynylene, C 3-10 cycloalkylene, C 3-10 cycloalkenylene, C 1-10 heteroalkylene, C 2-10 heteroalkenylene, C 2-10 heteroalkynylene, arylene, heteroarylene, —C(O)R M —, —C(O)OR M —, wherein R M is selected from the group consisting of C 1-10 alkylene, C 2-10 alkenylene and C 2-10 alkynylene, and wherein the alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene and heteroarylene groups may be optionally substituted with one or more R N , wherein each R N is independently selected from the group consisting of —H, —OH, —CN, —NO 2 , —CF 3 , —OCF 3 , —CO 2 H, —NH 2 , C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —O(C 1 -C 10 alkyl), —O(C 2 -C 10 alkenyl), —O(C 2 -C 10 alkynyl), halogen, —C(O)H, —C(O)—(C 1 -C 10 alkyl), —C(O)—O(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl), —N(C 1 -C 10 alkyl) 2 , —C(O)—NH(C 1 -C 10 alkyl), —C(O)—N(C 1 -C 10 alkyl) 2 , —NH—C(O)—(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl)-C(O)—(C 1 -C 10 alkyl), —NH—S(O) 2 —(C 1 -C 10 alkyl), —NH—(C 1 -C 10 alkyl)-S(O) 2 —(C 1 -C 10 alkyl), —(C 0 -C 10 )—SH, —S(O)—(C 1 -C 10 alkyl), —S(O) 2 —(C 1 -C 10 alkyl), —S(O) 2 —NH 2 , —S(O) 2 —NH—(C 1 -C 10 alkyl), —S(O) 2 —N(C 1 -C 10 alkyl) 2 and ═O, and d is an integer from 1 to 4, wherein if Z is directly bonded to an O or N atom, z is 0 and otherwise z is 1;

group (IVE) has the formula:

wherein each R 7 and R 7C is independently selected from hydrogen and C 1-4 alkyl; R 7A is hydrogen or a group —C(O)B 2 R 7B , wherein R 7B is hydrogen or methyl, B 2 is selected from the group consisting of a bond; C 1-10 alkylene, C 2-10 alkenylene, C 2-10 alkynylene, C 3-10 cycloalkylene, C 3-10 cycloalkenylene, C 1-10 heteroalkylene, C 2-10 heteroalkenylene, C 2-10 heteroalkynylene, arylene, heteroarylene, —C(O)R M —, —C(O)OR M —, wherein R M is selected from the group consisting of C 1-10 alkylene, C 2-10 alkenylene and C 2-10 alkynylene, and wherein the alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene and heteroarylene groups may be optionally substituted with one or more R N , wherein each R N is independently selected from the group consisting of —H, —OH, —CN, —NO 2 , —CF 3 , —OCF 3 , —CO 2 H, —NH 2 , C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —O(C 1 -C 10 alkyl), —O(C 2 -C 10 alkenyl), —O(C 2 -C 10 alkynyl), halogen, —C(O)H, —C(O)—(C 1 -C 10 alkyl), —C(O)—O(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl), —N(C 1 -C 10 alkyl) 2 , —C(O)—NH(C 1 -C 10 alkyl), —C(O)—N(C 1 -C 10 alkyl) 2 , —NH—C(O)—(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl)-C(O)—(C 1 -C 10 alkyl), —NH—S(O) 2 —(C 1 -C 10 alkyl), —NH—(C 1 -C 10 alkyl)-S(O) 2 —(C 1 -C 10 alkyl), —(C 0 -C 10 )—SH, —S(O)—(C 1 -C 10 alkyl), —S(O) 2 —(C 1 -C 10 alkyl), —S(O) 2 —NH 2 , —S(O) 2 —NH—(C 1 -C 10 alkyl), —S(O) 2 —N(C 1 -C 10 alkyl) 2 and ═O, and e is an integer from 1 to 4, wherein if Z is directly bonded to an O or N atom, z is 0 and otherwise z is 1.

13. The polymerisable material of claim 12 , wherein Z is a zwitterionic group of formula (IVB).

14. The polymerisable material of claim 13 , wherein R 4 is methyl and b is 2.

15. The polymerisable material of claim 1 of formula (II), having the structure:

wherein “OPC” is a zwitterionic group of formula (IVB),

wherein each R 4A is independently selected from hydrogen and C 1-4 alkyl; all R 4 groups are methyl; and b is 2.

16. The polymerisable material of claim 1 of formula (II), having the structure:

wherein “OPC” is a zwitterionic group of formula (IVB), wherein all R 4 groups are methyl and b is 2. Wherein “OPC” is a zwitterionic group of formula (IVB),

wherein each R 4A is independently selected from hydrogen and C 1 - 14 alkyl; all R 4 groups are methyl; and b is 2.

17. The polymerisable material of claim 1 of formula (II), having the structure:

wherein “OPC” is a zwitterionic group of formula (IVB),

wherein each R 4A is independently selected from hydrogen and C 1-4 alkyl; all R 4 groups are methyl; b is 2, and w is an integer from 1 to 500.

18. A method for producing a polymer comprising polymerising the polymerisable material of claim 1 .

19. A polymer obtained by polymerising the polymerisable material of claim 1 .

20. A xerogel comprising the polymer of claim 19 , which is free from water.

21. A silicone hydrogel comprising the polymer of claim 19 , and water in an amount of 30 to 80% by weight of hydrogel.

22. The polymer of claim 19 , which has an equilibrium water content in the range from 30 to 50%.

23. The polymer of claim 19 , which has a modulus in the range from 0.5 to 1.0 MPa.

24. An article comprising the polymer of claim 19 .

25. The article of claim 24 , which is a contact lens.

26. The contact lens of claim 25 , which has an oxygen permeability of about 30 barriers or more.

27. The contact lens of claim 25 , which has an equilibrium water content in the range from 30 to 50%.

28. An article comprising a surface having coated thereon the polymer of claim 19 .

29. The article of claim 28 , which is a contact lens.

30. A method of coating an article having a surface comprising applying the polymer of claim 19 to the surface of the article.

31. A polymerisable material having the structure:

wherein “OPC” is a zwitterionic group of formula (IVB),

wherein each R 4A is independently selected from hydrogen and C 1-4 alkyl; all R 4 groups are methyl; b is 2; and w is from 0 to 15.

Assignments (19)