Copolymerizable azo compounds and articles containing them

1. An intraocular lens comprising a polymer, wherein the polymer comprises at least one residue of a molecule comprising a molecular structure depicted by Formula I:

A-N═N-Z  I

wherein A is an optionally substituted aryl radical and Z is the residue of a moiety selected from 2-pyrazolin-5-ones, dimedone (5,5-dimethyl-1,3-cyclohexanedione), acetoacetamides, malonamides, barbituric acid and 1,3-propanediones;

with the provision that when Z is 2-pyrazolin-5-one, A is selected from

wherein

B is a divalent linking group selected from —CON(R 1 )—, —O—, —S—, and —N(SO 2 R 2 )—;

L is selected from C 2 -C 8 -alkylene and —[CH 2 CH(R 3 )O] n —CH 2 CH(R 3 )—;

L 1 is a C 1 -C 8 -alkylene group;

m is selected from 0,1 and 2;

n is 1, 2, or 3;

R is hydrogen or one to three groups selected from C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen, cyano, nitro, thiocyano, trifluoromethyl, —COR 4 , —CO 2 R 5 , —SO 2 R 2 , —N(R 1 )COR 4 , —N(R 1 )SO 2 R 2 , arylazo, aryloxy, arylthio, heteroarylthio, —SO 2 N(R 1 )R 4 , —CON(R 1 )R 4 , succinimido, phthalimido, and phthalimidino;

R 1 is selected from hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -alkenyl and aryl;

R 2 is selected from C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl and aryl;

R 3 is hydrogen or methyl;

R 4 is selected from C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, aryl and hydrogen;

R 5 is selected from C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, aryl and [CH 2 CH(R 3 )O] n CH 2 CH(R 3 )OR 6 ;

R 6 is selected from hydrogen, C 1 -C 8 -alkyl, aryl, C 1 -C 8 -alkanoyloxy and C 1 -C 8 -alkoxycarbonyloxy; and

Q is an ethylenically-unsaturated polymerizable group;

wherein the molecule comprises at least one ethylenically-unsaturated polymerizable group (Q).

2. The intraocular lens of claim 1 , wherein A is:

wherein

B is a divalent linking group selected from —CON(R 1 )—, —O—, —S—, and —N(SO 2 R 2 )—;

L is selected from C 2 -C 8 -alkylene and —[CH 2 CH(R 3 )O] n —CH 2 CH(R 3 )—;

L 1 is a C 1 -C 8 -alkylene group;

m is selected from 0,1 and 2;

n is 1, 2, or 3;

R is hydrogen or one to three groups selected from C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen, cyano, nitro, thiocyano, trifluoromethyl, —COR 4 , —CO 2 R 5 , —SO 2 R 2 , —N(R 1 )COR 4 , —N(R 1 )SO 2 R 2 , arylazo, aryloxy, arylthio, heteroarylthio, —SO 2 N(R 1 )R 4 , —CON(R 1 )R 4 , succinimido, phthalimido, and phthalimidino;

R 1 is selected from hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -alkenyl and aryl;

R 2 is selected from C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl and aryl;

R 3 is hydrogen or methyl;

R 4 is selected from C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, aryl and hydrogen;

R 5 is selected from C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, aryl and [CH 2 CH(R 3 )O] n CH 2 CH(R 3 )OR 6 ;

R 6 is selected from hydrogen, C 1 -C 8 -alkyl, aryl, C 1 -C 8 -alkanoyloxy and C 1 -C 8 -alkoxycarbonyloxy; and

Q is an ethylenically-unsaturated polymerizable group;

wherein, when Z does not comprise at least one Q group, then m is one or two.

3. The intraocular lens of claim 1 , wherein Z is a residue of a structure selected from:

wherein

R 7 is selected from hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, aryl, arylene-(B-L-O-Q) p , arylene-(L 1 -O-Q) p and —C 2 -C 8 -alkylene-O-Q;

R 7 ′ is selected from C 1 -C 8 -alkyl, trifluoromethyl, C 3 -C 8 -cycloalkyl, C 1 -C 8 -alkoxycarbonyl and aryl;

R 8 is hydrogen, C 1 -C 8 -alkyl, -L 1 -O-Q, C 3 -C 8 -cycloalkyl, heteroaryl, aryl, or aryl substituted with one to three groups selected from C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen, -B-L-O-Q and L 1 -O-Q;

R 8 ′ and R 8 ″ are independently selected from C 1 -C 4 -alkyl and aryl;

p is one or two;

B is a divalent linking group selected from —CON(R 1 )—, —O—, —S—, and —N(SO 2 R 2 )—;

L is selected from C 2 -C 8 -alkylene and —[CH 2 CH(R 3 )O] n —CH 2 CH(R 3 )—;

L 1 is a C 1 -C 8 -alkylene group; and

n is one, two, or three.

4. The intraocular lens of claim 1 , wherein the ethylenically-unsaturated polymerizable group (Q) is:

1a —COC(R 9 )═CH—R 10 ,

2a —CONHCOC(R 9 )═CH—R 10 ,

3a —CONH—C 1 -C 8 -alkylene-OCOC(R 9 )═CH—R 10 ,

5a —COCH═CH—CO 2 R 13 ,

wherein:

R 9 is hydrogen or C 1 -C 8 -alkyl;

R 10 is: hydrogen; C 1 -C 8 -alkyl; phenyl; phenyl substituted with one or more groups selected from C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, —N(C 1 -C 8 -alkyl) 2 , nitro, cyano, C 1 -C 8 -alkoxycarbonyl, C 1 -C 8 -alkanoyloxy and halogen; 1- or 2-naphthyl; 1- or 2-naphthyl substituted with C 1 -C 8 -alkyl or C 1 -C 8 -alkoxy; 2- or 3-thienyl; 2- or 3-thienyl substituted with C 1 -C 8 -alkyl or halogen; 2- or 3-furyl; or 2- or 3-furyl substituted with C 1 -C 8 -alkyl;

R 11 and R 12 are, independently, hydrogen, C 1 -C 8 -alkyl, or aryl,; or R 11 , and R 12 are combined to represent a —(CH 2 ) 3-5 — radical;

R 13 is hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -cycloalkyl or aryl; and

R 14 is hydrogen, C 1 -C 8 -alkyl or aryl.

5. The intraocular lens of claim 2 wherein Z is a residue of a structure selected from:

wherein

R 1 is selected from hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -alkenyl and aryl;

R 2 is selected from C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl and aryl;

R 3 is hydrogen or methyl;

R 7 is selected from hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, aryl, arylene-(B-L-O-Q) p , arylene-(L 1 -O-Q) p and —C 2 -C 8 -alkylene-O-Q;

R 7 ′ is selected from C 1 -C 8 -alkyl, trifluoromethyl, C 3 -C 8 -cycloalkyl, C 1 -C 8 -alkoxycarbonyl and aryl;

R 8 is hydrogen, C 1 -C 8 -alkyl, -L 1 -O-Q, C 3 -C 8 -cycloalkyl, heteroaryl, aryl or aryl substituted with one to three groups selected from C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen, -B-L-O-Q and L 1 -O-Q;

R 8 ′ and R 8 ″ are independently selected from C 1 -C 4 -alkyl and aryl;

p is one or two;

B is a divalent linking group selected from —CON(R 1 )—, —O—, —S—, and —N(SO 2 R 2 )—;

L is selected from C 2 -C 8 -alkylene and —[CH 2 CH(R 3 )O] n —CH 2 CH(R 3 )—;

L 1 is a C 1 -C 8 -alkylene group; and

n is one, two or three.

6. The intraocular lens of claim 5 wherein the ethylenically-unsaturated polymerizable group is:

1a —COC(R 9 )═CH—R 10 ,

2a —CONHCOC(R 9 )═CH—R 10 ,

3a —CONH—C 1 -C 8 -alkylene-OCOC(R 9 )═CH—R 10 ,

5a —COCH═CH—CO 2 R 13 ,

wherein:

R 9 is hydrogen or C 1 -C 8 -alkyl;

R 10 is: hydrogen; C 1 -C 8 -alkyl; phenyl; phenyl substituted with one or more groups selected from C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, —N(C 1 -C 8 -alkyl) 2 , nitro, cyano, C 1 -C 8 -alkoxycarbonyl, C 1 -C 8 -alkanoyloxy and halogen; 1- or 2-naphthyl, 1- or 2-naphthyl substituted with C 1 -C 8 -alkyl or C 1 -C 8 -alkoxy; 2- or 3-thienyl; 2- or 3-thienyl substituted with C 1 -C 8 -alkyl or halogen; 2- or 3-furyl; 2- or 3-furyl substituted with C 1 -C 8 -alkyl;

R 11 and R 12 are, independently, hydrogen, C 1 -C 8 -alkyl, or aryl, or R 11 and R 12 are combined to represent a —(CH 2 ) 3-5 — radical;

R 13 is hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -cycloalkyl or aryl; and

R 14 is hydrogen, C 1 -C 8 -alkyl or aryl.

7. The intraocular lens of claim 1 , wherein A has the structure of Formula XIII:

wherein R is hydrogen or one, two or three groups selected from C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, halogen, nitro, cyano and —CO 2 C 1 -C 8 -alkyl, —CONHC 1 -C 8 -alkyl and —SO 2 C 1 -C 4 -alkyl;

Z is a residue of:

wherein

R 7 is: CH 2 CH 2 —O-Q,

R 7 ′ is selected from C 1 -C 4 -alkyl and aryl;

R 8 ′″ is -B-L-O-Q or -L 1 -O-Q;

B is —O—;

L is selected from C 2 -C 8 -alkylene and —[CH 2 CH(R 3 )O] n —CH 2 CH(R 3 )—;

n is an integer from one to three;

R 3 is hydrogen or methyl;

L 1 is C 1 -C 8 -alkylene; and

Q is:

—COC(R 9 )═CH—R 10 or

wherein

R 9 is hydrogen or methyl;

R 10 is hydrogen; and

R 11 and R 12 are methyl.

8. The intraocular lens of claim 7 wherein R is:

a —CO 2 C 1 -C 8 -alkyl group or a nitro group attached to the 2-position carbon in Formula XIII; wherein when nitro is attached to the 2-position a C 1 -C 4 -alkyl, a C 1 -C 4 -alkoxy or a halogen is optionally attached to the 4-position carbon in Formula XIII.

9. The intraocular lens of claim 1 , wherein A is:

wherein

R is hydrogen;

B is —O— or —CONH—;

L is C 2 -C 8 -alkylene or —[CH 2 CH(R 3 )O] n —CH 2 CH(R 3 )—;

L 1 is C 1 -C 8 -alkylene;

R 3 is hydrogen or methyl;

m is 1;

n is 1, 2 or 3; and

Z is a residue of:

wherein

R 7 is hydrogen, C 1 -C 4 -alkyl or aryl;

R 7 ′ is C 1 -C 4 -alkyl or aryl;

R 8 ′″ is hydrogen or one to three groups selected from C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and halogen; and

Q is:

—COC(R 9 )═CH—R 10 or

wherein

R 9 is hydrogen or methyl;

R 10 is hydrogen; and

R 11 and R 12 are methyl.

10. The intraocular lens of claim 9 wherein A is:

wherein

L 1 is C 1 -C 8 -alkylene;

Z is a residue of:

wherein

R 7 is hydrogen, C 1 -C 4 -alkyl or aryl;

R 7 ′ is C 1 -C 4 -alkyl or aryl;

Q is:

—COC(R 9 )═CH—R 10

wherein

R 9 is hydrogen or methyl; and

R 10 is hydrogen.