IP Library › Granted Patent US 8,188,203

Granted Patent B2

US 8,188,203 · App. 12/026,294 · Granted May 29, 2012

Copolymerizable azo compounds and articles containing them

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Quick Facts

Patent No.: US 8,188,203
App. No.: 12/026,294
Granted: May 29, 2012
Kind: B2

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Abstract

Polymerizable light absorbing azo dyes are disclosed useful as monomers in the formation of devices such as, but not limited to ocular lenses. Specifically, intraocular lenses (IOL) are disclosed wherein one or more of the light absorbing dye is covalently bonded to other structural polymers though ethylene unsaturated groups. The resulting IOLs possess light absorbing properties without significant amounts of free (un-bound) azo dye molecules present in the final structural polymer matrix.

Claims (167)

1. A polymer comprising 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 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 selected from;

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-narhthyl; 1- or 2-narhthyl 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 rerresent 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; and

wherein the molecule comprises at least one ethylenically-unsaturated polymerizable group (Q), wherein when Z does not comprise at least one Q group, then m is 1 or 2.

2. A composition comprising the polymer of claim 1 .

3. An article comprising the polymer of claim 1 .

4. A method of making a polymer, comprising copolymerizing monomers wherein the monomers comprise a compound having the structure of Formula I:

A-N═N—Z I

wherein:

A is an optionally substituted aryl radical;

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 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 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 selected from;

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 11 and R 12 are, independently, hydrogen, C 1 -C 8 -alkyl, or aryl; or R 11 and R 12 are combined to rerresent 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; and

wherein the molecule comprises at least one ethylenically-unsaturated polymerizable group (Q), wherein when Z does not comprise at least one Q group, then m is 1 or 2.

5. The method of claim 4 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 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;

Q is an ethylenically-unsaturated polymerizable group;

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

6. The method of claim 4 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 selected from the one to three.

7. The method of claim 5 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 ′ 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 selected from the one to three.

8. The method of claim 4 wherein A has the structure of Formula XIII:

wherein

R is hydrogen or one or two 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 selected from

—COC(R 9 )═CH—R 10

wherein

R 9 is hydrogen or methyl;

R 10 is hydrogen; and

R 11 and R 12 are methyl.

9. The method of claim 8 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.

10. The method of claim 4 , 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;

n is 1, 2, or 3;

m is 1; 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

wherein

R 9 is hydrogen or methyl;

R 10 is hydrogen; and

R 11 and R 12 are methyl.

11. The method of claim 10 , wherein A is:

wherein

L 1 is C 1 -C 8 -alkylene;

Z is the 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.

12. The polymer of claim 1 , wherein if Q is —COC(R 9 )═CH—R 10 then A is not

13. The method of claim 4 , wherein if Q is —COC(R 9 )═CH—R 10 then A is not

14. The method of claim 5 , wherein if Q is —COC(R 9 )═CH—R 10 then A is not

15. The method of claim 6 , wherein if Q is —COC(R 9 )═CH—R 10 then A is not

16. The method of claim 7 , wherein if Q is —COC(R 9 )═CH—R 10 then A is not

17. The method of claim 8 , wherein if Q is —COC(R 9 )═CH—R 10 then A is not

18. The method of claim 9 , wherein if Q is —COC(R 9 )═CH—R 10 then A is not

19. The method of claim 10 , wherein if Q is —COC(R 9 )═CH—R 10 then A is not

20. A composition comprising the polymer of claim 12 .

21. An article comprising the polymer of claim 12 .

Assignments (1)

CHANGE OF NAME Recorded Sep 25, 2018

From: ABBOTT MEDICAL OPTICS INC.

To: JOHNSON & JOHNSON SURGICAL VISION, INC.

Reel/Frame 047150/0976 →