TRI-FUNCTIONAL UV-ABSORBING COMPOUNDS AND USE THEREOF

• US 20100168359A1
• Filed: 12/17/2009
• Published: 07/01/2010
• Est. Priority Date: 12/30/2008
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Winterton, Lynn Cook, Turek, Richard Charles, Holland, Troy Vernon, Domschke, Angelika Maria
• Granted Patent: US 8,324,256 B2
• Time in Patent Office: Days
• US Class Current: 526/259
• CPC Class Codes: C07D 249/20 with aryl radicals directly attached in position 2
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

Described herein are tri-functional compounds useful in the production of ophthalmic lenses. The compounds are composed of UV absorber having a polymerization initiator directly or indirectly bonded to the ultraviolet absorber, and an olefinic group directly or indirectly bonded to the ultraviolet absorber. Also described herein are polymers and ophthalmic lenses produced from the tri-functional compounds described herein.

Claims

1. A compound comprising an ultraviolet absorber, a polymerization initiator directly or indirectly bonded to the ultraviolet absorber, and an ethylenically unsaturated group directly or indirectly bonded to the ultraviolet absorber.

2. The compound of claim 1, wherein the compound comprises the formula I

Y-L²-Z-L¹-X  

 

I

wherein

Z is a divalent radical of formula (1a), (1b), (1 c) or (1d)

in which R^3a, R^3b, R^3c, R^2z, R^3z, R^4z, and R^1z, independent of another, are hydrogen, halogen, a C₁-C₁₂ linear or branched alkyl group, a C₁-C₁₂ linear or branched alkoxy group, or a C₆-C₂₄ aryl or substituted aryl group, PG is a protective labile group;

X is a monovalent radical comprising a polymerization initiator moiety selected from the group consisting of phosphine oxide

a peroxide group, an azide group, an α

-hydroxyketone, or an α

-aminoketone;

Y is a monovalent radical of formula (2)

in which Z₁ and Z₂ independent of each other are a covalent bond, a linear or branched C₁-C₁₂ alkylene divalent radical, a linear or branched C₁-C₁₂ alkylene divalent radical having one or more hydroxyl groups, a radical of —

(CH₂CH₂O)_d—

CH₂CH₂—

in which d is an integer of 1 to 10, unsubstituted phenylene divalent radical, C₁-C₄ alkyl or C₁-C₄ alkoxy substituted phenylene divalent radical, C₇-C₁₂ aralkylene divalent radical,

in which R′

is H or C₁-C₈ alkyl;

A₅ is a covalent bond,

in which R′

is H or C₁-C₈ alkyl;

q₁ and q₂ independent of each other are an integer of 0 or 1;

R₁₄ is hydrogen, C₁-C₄ alkyl or halogen;

R₁₅ and R₁₆ independent of each other are hydrogen, C₁-C₄ alkyl, phenyl, carboxy, halogen, or a radical of

in which X₃ is

as defined above or —

S— and

R₁₇ is C₁-C₁₂ alkyl, C₁-C₁₂ hydroxyalkyl, C₁-C₁₂ aminoalkyl, alkylaminoalkyl having up to 12 carbon atoms, or dialkylaminoalkyl having up to 12 carbon atoms; and

L¹ and L² independently of each other are a covalent bond or a linker.

3. The compound of claim 2, wherein the polymerization initiator comprises a phosphine oxide, a peroxide group, or an azide group.

4. The compound of claim 2, wherein the polymerization initiator moiety comprises a monovalent radical of formula IIa, IIb or XI

wherein R is oxygen, nitrogen, a linear or branched C₁-C₁₂ alkylene divalent radical, a divalent radical of —

OCH₂CH₂O—

, a divalent radical of

in which R^II is hydrogel or a C₁-C₁₂ alkyl radical and alk is C₁-C₁₂ alkylene divalent radical, or combinations thereof, R¹ and R² are, independently, hydrogen, a C₁-C₁₂ linear or branched alkyl group, a C₆-C₂₄ aryl or substituted aryl group, a C₇-C₂₄ aralkyl group; and

A comprises a hydroxyl group, a C₁-C₁₂ alkoxy group, a C₆-C₂₄ aryloxy group, or a primary, secondary or tertiary amino group,

wherein t1 and t2 independent of each other are 0 or 1 provided that at least one of t1 and t2 is 1, one of Q^1a and Q^1b is a covalent bond and the other is hydrogen, C₁-C₆ linear or branched alkyl group, or C₁-C₆ linear or branched alkoxy group, Q^2a, Q^2b, Q^3a, Q^3b independently of one another hydrogen are C₁-C₁₂ linear or branched alkyl group, or C₁-C₁₂ linear or branched alkoxy group.

5. The compound of claim 2, wherein the polymerization initiator moiety comprises a monovalent radical of formula III or Iva or b

in which Ph is phenyl group and Me is methyl group.

6. The compound of claim 2, wherein the polymerization initiator moiety comprises a monovalent radical of formula XII

wherein V is a covalent bond or oxygen, and R is a C₁-C₂₀ linear or branched alkyl group or phenyl.

7. The compound of claim 4, wherein L¹ and L² independent of each other are a covalent bond or a linker of a silicon group, a carbonyl group, a dicarbonyl group, an alkylene group, an alkylene oxide group, an alkylene amine group, or any combination thereof.

8. The compound of claim 4, wherein L¹ and L² independent of each other are a covalent bond or a divalent radical of

—

X_a-E₁-X_b-E₂-X_c—

in which;

X_a is a covalent bond, carbonyl

in which R^e and R^f independently of each other are a C₁-C₈-alkyl, phenyl or a C₁-C₄ alkyl- or C₁-C₄-alkoxy-substituted phenyl, a divalent radical of —

(R^aO)_n—

in which R^a is a linear or branched C₁-C₁₂-alkylene and n is from 1 to 10,

in which R″

is H or C₁-C₈ alkyl;

E₁ and E₂ independently of each other are a covalent bond, a divalent radical of —

(R^aO)_n—

in which R^a and n are defined above,

in which R″

is H or C₁-C₈ alkyl, a C₁ to C₁₂ linear or branched alkylene divalent radical, a cycloalkyl diradical with up to 40 carbon atoms, an alkylcycloalkyl diradical with up to 40 carbon atoms, an alkylaryl diradical with up to 40 carbon atoms, an arylalkylene divalent radical with up to 40 carbon atoms, or a dicarbonyl group having the formula —

C(O)L³C(O)—

in which L³ is a C₁ to C₁₂ linear or branched alkylene divalent radical or —

(R^e1—

O)_w1—

(R^e2—

O)_w2—

(R^e3—

O)_w3—

, wherein R^e1, R^e2, and R^e3 independently of one another are a linear or branched C₁-C₄-alkylene and w1, w2 and w3 independently of one another are a number from 0 to 20 provided that the sum of (n+m+p) is 1 to 60; and

X_b and X_c independently of each other are a covalent bond,

in which R″

is defined above.

9. The compound of claim 8, wherein the compound is defined by the formula V

wherein R³ is hydrogen, halogen, a C₁-C₁₂ linear or branched alkyl group, a C₁-C₁₂ linear or branched alkoxy group, or a C₆-C₂₄ aryl or substituted aryl group.

10. The compound of claim 9, wherein X is a monovalent radical of the formula VI

wherein:

R¹ and R² are, independently, hydrogen, a C₁-C₁₂ linear or branched alkyl group, a C₆-C₂₄ aryl or substituted aryl group, a C₇-C₂₄ aralkyl group;

A is a hydroxyl group, a C₁-C₁₂ alkoxy group, a C₆-C₂₄ aryloxy group, or an amino group; and

B is a silicon group, a carbonyl group, a dicarbonyl group, a C₁-C₁₂ linear or branched alkylene group, a C₁-C₁₂ linear or branched alkylene oxide group, a C₁-C₁₂ linear or branched alkylene amine group, or any combination thereof.

11. The compound of claim 8, wherein the compound has the formula VII

wherein R¹⁰ is hydrogen or methyl.

12. The compound of claim 11, wherein L¹ is a divalent radical of the formula

wherein o, p, q, r, s, u, and v are, independently, an integer from 1 to 5;

and

R¹¹ and R¹² independently of each other are hydrogen or a C₁-C₁₂ linear or branched alkyl group.

13. The compound of claim 8, wherein the compound comprises the formula VIII

wherein R³ is hydrogen, halogen, a C₁-C₁₂ linear or branched alkyl group, a C₁-C₁₂ linear or branched alkoxy group, or a C₆-C₂₄ aryl or substituted aryl group.

14. The compound of claim 8, wherein the compound has the formula IXa or b

wherein R⁵ is hydrogen, a C₁-C₁₂ linear or branched alkyl group, a C₁-C₁₂ linear or branched alkoxy group, or a C₆-C₂₄ aryl or substituted aryl group.

15. The compound of claim 8, wherein the compound has the formula X

wherein R⁶ comprises hydrogen, a C₁-C₁₂ linear or branched alkyl group, a C₁-C₁₂ linear or branched alkoxy group, or a C₆-C₂₄ aryl or substituted aryl group.

16. An ophthalmic lens comprising a polymer which is the copolymerization product of a polymerizable composition including one or more vinylic monomers and/or macromers and at least one compound of formula I

Y-L²-Z-L¹-X  

 

I

wherein

Z is a divalent radical of formula (1a), (1b), (1c) or (1d)

in which R^3a, R^3b, R^3c, R^2z, R^3z, R^4z, and R^1z, independent of another, are hydrogen, halogen, a C₁-C₁₂ linear or branched alkyl group, a C₁-C₁₂ linear or branched alkoxy group, or a C₆-C₂₄ aryl or substituted aryl group, PG is a protective labile group;

X is a monovalent radical comprising a polymerization initiator moiety selected from the group consisting of phosphine oxide

peroxide group, an azide group, an α

-hydroxyketone, or an α

-aminoketone;

Y is a monovalent radical of formula (2)

in which Z₁ and Z₂ independent of each other are a covalent bond, a linear or branched C₁-C₁₂ alkylene divalent radical, a linear or branched C₁-C₁₂ alkylene divalent radical having one or more hydroxyl groups, a radical of —

(CH₂CH₂O)_d—

CH₂CH₂—

in which d is an integer of 1 to 10, unsubstituted phenylene divalent radical, C₁-C₄ alkyl or C₁-C₄ alkoxy substituted phenylene divalent radical, C₇-C₁₂ aralkylene divalent radical,

in which R′

is H or C₁-C₈ alkyl;

A₅ is a covalent bond,

in which R′

is H or C₁-C₈ alkyl;

q₁ and q₂ independent of each other are an integer of 0 or 1;

R₁₄ is hydrogen, C₁-C₄ alkyl or halogen;

R₁₅ and R₁₆ independent of each other are hydrogen, C₁-C₄ alkyl, phenyl, carboxy, halogen, or a radical of

in which X₃ is

as defined above or —

S— and

R₁₇ is C₁-C₁₂ alkyl, C₁-C₁₂ hydroxyalkyl, C₁-C₁₂ aminoalkyl, alkylaminoalkyl having up to 12 carbon atoms, or dialkylaminoalkyl having up to 12 carbon atoms; and

L¹ and L² independently of each other are a covalent bond or a linker.

17. The ophthalmic lens of claim 16, wherein the polymerization initiator moiety comprises a monovalent radical of formula IIa, IIb or XI

wherein R is oxygen, nitrogen, a linear or branched C₁-C₁₂ alkylene divalent radical, a divalent radical of — OCH₂CH₂O—

, a divalent radical of

in which R^II is hydrogel or a C₁-C₁₂ alkyl radical and alk is C₁-C₁₂ alkylene divalent radical, or combinations thereof, R¹ and R² are, independently, hydrogen, a C₁-C₁₂ linear or branched alkyl group, a C₆-C₂₄ aryl or substituted aryl group, a C₇-C₂₄ aralkyl group; and

A comprises a hydroxyl group, a C₁-C₁₂ alkoxy group, a C₆-C₂₄ aryloxy group, or a primary, secondary or tertiary amino group,

wherein t1 and t2 independent of each other are 0 or 1 provided that at least one of t1 and t2 is 1, one of Q^1aand Q^1b is a covalent bond and the other is hydrogen, C₁-C₆ linear or branched alkyl group, or C₁-C₆ linear or branched alkoxy group, Q^2a, Q^2b, Q^3a, Q^3b independently of one another hydrogen are C₁-C₁₂ linear or branched alkyl group, or C₁-C₁₂ linear or branched alkoxy group

18. The ophthalmic lens of claim 17, wherein L¹ and L² independent of each other are a covalent bond or a divalent radical of

—

X_a-E₁-X_b-E₂-X_c—

in which;

X_a is a covalent bond, carbonyl

in which R^e and R^f independently of each other are a C₁-C₈-alkyl, phenyl or a C₁-C₄ alkyl- or C₁-C₄-alkoxy-substituted phenyl, a divalent radical of —

(R^aO)_n—

in which R^a is a linear or branched C₁-C₁₂-alkylene and n is from 1 to 10,

in which R″

is H or C₁-C₈ alkyl;

E₁ and E₂ independently of each other are a covalent bond, a divalent radical of —

(R^aO)_n—

in which R^a and n are defined above,

in which R″

is H or C₁-C₈alkyl, a C₁ to C₁₂ linear or branched alkylene divalent radical, a cycloalkyl diradical with up to 40 carbon atoms, an alkylcycloalkyl diradical with up to 40 carbon atoms, an alkylaryl diradical with up to 40 carbon atoms, an arylalkylene divalent radical with up to 40 carbon atoms, or a dicarbonyl group having the formula —

C(O)L³C(O)—

in which L³ is a C₁ to C₁₂ linear or branched alkylene divalent radical or —

(R^e1O)_w1—

(R^e2—

O)_w2—

(R^e3—

O)_w3—

, R^e2, and R^e3 independently of one another are a linear or branched C₁-C₄-alkylene and w1, w2 and w3 independently of one another are a number from 0 to 20 provided that the sum of (n+m+p) is 1 to 60; and

X_b and X_c independently of each other are a covalent bond,

in which R″

is defined above.

19. A method for making UV-absorbing ophthalmic lenses, comprising the steps of:

a. introducing into a mold a lens-forming material, wherein the lens-forming material comprises one or more vinylic monomers and/or macromers and at least one compound of formula I

Y-L²-Z-L¹-X  

 

I

wherein

Z is a divalent radical of formula (1a), (1b), (1c) or (1d)

in which R^3a, R^3b, R^3c, R^2z, R^3z, R^4z, and R^1z, independent of another, are hydrogen, halogen, a C₁-C₁₂ linear or branched alkyl group, a C₁-C₁₂ linear or branched alkoxy group, or a C₆-C₂₄ aryl or substituted aryl group, PG is a protective labile group;

X is a monovalent radical comprising a polymerization initiator moiety selected from the group consisting of phosphine oxide

a peroxide group, an azide group, an α

-hydroxyketone, or an α

-aminoketone;

Y is a monovalent radical of formula (2)

in which Z₁ and Z₂ independent of each other are a covalent bond, a linear or branched C₁-C₁₂ alkylene divalent radical, a linear or branched C₁-C₁₂ alkylene divalent radical having one or more hydroxyl groups, a radical of —

(CH₂CH₂O)_d—

CH₂CH₂—

in which d is an integer of 1 to 10, unsubstituted phenylene divalent radical, C₁-C₄ alkyl or C₁-C₄ alkoxy substituted phenylene divalent radical, C₇-C₁₂ aralkylene divalent radical,

in which R′

is H or C₁-C₈ alkyl;

A₅ is a covalent bond,

in which R′

is H or C₁-C₈ alkyl;

q₁ and q₂ independent of each other are an integer of 0 or 1;

R₁₄ is hydrogen, C₁-C₄ alkyl or halogen;

R₁₅ and R₁₆ independent of each other are hydrogen, C₁-C₄ alkyl, phenyl, carboxy, halogen, or a radical of

in which X₃ is

as defined above or —

S— and

R₁₇ is C₁-C₁₂ alkyl, C₁-C₁₂ hydroxyalkyl, C₁-C₁₂ aminoalkyl, alkylaminoalkyl having up to 12 carbon atoms, or dialkylaminoalkyl having up to 12 carbon atoms; and

L¹ and L² independently of each other are a covalent bond or a linker; and

b. curing the lens-forming material in the mold to form a UV-absorbing ophthalmic lens.

20. The method of claim 19, wherein the polymerization initiator moiety comprises a monovalent radical of formula IIa, IIb or XI

wherein R is oxygen, nitrogen, a linear or branched C₁-C₁₂ alkylene divalent radical, a divalent radical of — OCH₂CH₂O—

, a divalent radical of

in which R^II is hydrogel or a C₁-C₁₂ alkyl radical and alk is C₁-C₁₂ alkylene divalent radical, or combinations thereof, R¹ and R² are, independently, hydrogen, a C₁-C₁₂ linear or branched alkyl group, a C₆-C₂₄ aryl or substituted aryl group, a C₇-C₂₄ aralkyl group; and

A comprises a hydroxyl group, a C₁-C₁₂ alkoxy group, a C₆-C₂₄ aryloxy group, or a primary, secondary or tertiary amino group,

wherein t1 and t2 independent of each other are 0 or 1 provided that at least one of t1 and t2 is 1, one of Q^1aand Q^1b is a covalent bond and the other is hydrogen, C₁-C₆ linear or branched alkyl group, or C₁-C₆ linear or branched alkoxy group, Q^2a, Q^2b, Q^3a, Q^3b independently of one another hydrogen are C₁-C₁₂ linear or branched alkyl group, or C₁-C₁₂ linear or branched alkoxy group,

wherein L¹ and L² independent of each other are a covalent bond or a divalent radical of

—

X_a-E₁-X_b-E₂-X_c—

in which;

X_a is a covalent bond, carbonyl

in which R^e and R^f independently of each other are a C₁-C₈-alkyl, phenyl or a C₁-C₄ alkyl- or C₁-C₄-alkoxy-substituted phenyl, a divalent radical of —

(R^aO)_n—

in which R^a is a linear or branched C₁-C₁₂-alkylene and n is from 1 to 10,

in which R″

is H or C₁-C₈ alkyl;

E₁ and E₂ independently of each other are a covalent bond, a divalent radical of —

(R^aO)_n—

in which R^a and n are defined above,

in which R″

is H or C₁-C₈alkyl, a C₁ to C₁₂ linear or branched alkylene divalent radical, a cycloalkyl diradical with up to 40 carbon atoms, an alkylcycloalkyl diradical with up to 40 carbon atoms, an alkylaryl diradical with up to 40 carbon atoms, an arylalkylene divalent radical with up to 40 carbon atoms, or a dicarbonyl group having the formula —

C(O)L³C(O)—

in which L³ is a C₁ to C₁₂ linear or branched alkylene divalent radical or —

(R^e1—

O)_w1—

(R^e2—

O)_w2—

(R^e3—

O)_w3—

, wherein R^e1, R^e2, and R^e3 independently of one another are a linear or branched C₁-C₄-alkylene and w1, w2 and w3 independently of one another are a number from 0 to 20 provided that the sum of (n+m+p) is 1 to 60; and

X_b and X_c independently of each other are a covalent bond,

in which R″

is defined above.