Red-shifted trisaryl-1,3,5-triazine ultraviolet light absorbers

• US 6,348,591 B1
• Filed: 06/18/1999
• Issued: 02/19/2002
• Est. Priority Date: 06/22/1998
• Status: Expired due to Term

• Current Assignee: Cytec Technology Corp.
• Original Assignee: Cytec Technology Corp.
• Inventors: Jakiela, Dennis John, Gupta, Ram Baboo
• Primary Examiner(s): Raymond, Richard L.
• Assistant Examiner(s): Balasubramanian, Venkataraman
• Application Number:
  US09/335,883
• Time in Patent Office: 977 Days
• Field of Search: 544/215, 544/216
• US Class Current: 544/215
• CPC Class Codes: A61K 8/4966 Triazines or their condensed derivatives
• CPC Class Codes: A61Q 17/04 Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• CPC Class Codes: C07D 251/24 to three ring carbon atoms
• CPC Class Codes: C08K 5/3492 Triazines

Abstract

This invention relates generally to red-shifted trisaryl-1,3,5-triazines and the use thereof to protect against degradation by environmental forces, inclusive of ultraviolet light, actinic radiation, oxidation, moisture, atmospheric pollutants and combinations thereof. The new class of trisaryl-1,3,5-triazines comprises an aryl ring attached to the triazine ring [and preferably an aryl ring containing a hydroxyl group, either free or blocked to form a latent stabilizer, ortho- to the point of attachment to the triazine ring (2-position) and a hydroxyl group or a moiety joined by an ether linkage para- to the point of attachment to the triazine ring (4-position)] substituted at the 3-position or disubstituted at the 3- and 5-positions with a group comprising an amide and/or an amine. These materials may be incorporated into formulations comprising coatings, polymers, resins, organic compounds and the like. A method for stabilizing a material by incorporating such red-shifted trisaryl-1,3,5-triazines is also disclosed.

Claims

1. A triazine compound of formula (I), (II) or (III), as follows:

wherein

i is 1 or 2;

each X is independently selected from hydrogen, C₁-C₈ alkyl, halogen-substituted C₁-C₈ alkyl, allyl, —

COR^a, —

SO₂R^b, —

SiR^cR^dR^e, —

PR^fR^g and —

POR^fR^g;

each of Y and Z is independently selected from an aryl ring of the formula (IV)

 

each R is independently selected from a hydrogen, a hydrocarbyl group and a functional hydrocarbyl group;

each R^a is independently selected from C₁-C₈ alkyl, halogen-substituted C₁-C₈ alkyl, C₅-C₁₂ cycloalkyl, C₂-C₈ alkenyl, —

CH₂—

CO—

CH₃, C₇-C₁₂ aralkyl, C₁-C₁₂ alkoxy, or phenyl which is unsubstituted or substituted by C₁-C₁₂ alkyl, C₁-C₄ alkoxy, halogen and benzyl;

each R^b is independently selected from C₁-C₁₂ alkyl, C₆-C₁₀ aryl and C₇-C₁₈ alkylaryl;

each R^c, R^d and R^e is independently selected from C₁-C₁₈ alkyl, cyclohexyl, phenyl and C₁-C₁₈ alkoxy;

each R^f and R^g is independently selected from C₁-C₁₂ alkoxy, phenoxy, C₁-C₁₂ alkyl, C₅-C₁₂ cycloalkyl, benzyl, tolyl and phenyl;

when i is 1, R¹ is bonded to the 3-position of the ring bearing the —

OX group, R¹¹ is bonded to the 5-position of the ring bearing the —

OX group, and R¹¹ is R¹ and,

when i is 2, R¹ is bonded, independently, to either the 3-position or the 5-position of a first ring and a second ring bearing the —

OX group and R¹¹ is bonded, at a first end, to the position of the first ring bearing —

OX not bonded to R¹ and at a second end, to the position of the second ring bearing —

OX not bonded to R¹, and R¹¹ is a hydrocarbylene group of 1 to 24 carbon atoms;

each R¹, R², R⁴, R^4′

and R^4″

is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, —

O(hydrocarbyl), —

O(functional hydrocarbyl), —

SR, halogen, —

SO₂R, —

SO₃R, —

COOR, —

COR, —

OCOR, —

NRR and cyano; and

each R³ is independently selected from R, —

OR, —

SR, halogen, —

SO₂R, —

SO₃R, —

COOR, —

COR, —

NRR and cyano; and

further wherein at least one 3-position R¹ group is independently selected from a group of the formulae (V) and (VI)

 

wherein

R⁵ is independently selected from hydrogen, linear or branched hydrocarbyl group of 1 to 24 carbon atoms, phenyl, and aralkyl of 7 to 24 carbon atoms; and

each R⁶ and R⁷ is independently selected from hydrogen, a hydrocarbyl group and a functional hydrocarbyl group.

2. The compound of claim 1 selected from the group consisting of the compounds of formula (VII), (VIII), (IX), (XA), (XB), (XC), (XIA), (XIB), (XIC), (XIIA), (XIIB) or (XIIC)

wherein

each R is independently selected from a hydrogen, a hydrocarbyl group and a functional hydrocarbyl group;

each R¹ and R² is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, —

O(hydrocarbyl), —

O(functional hydrocarbyl), —

SR, halogen, —

SO₂R, —

SO₃R, —

COOR, —

COR, —

OCOR, —

NRR and cyano; and

each R³ is independently selected from R, —

OR, —

SR, halogen, —

SO₂R, —

SO₃R, —

COOR, —

COR, —

NRR and cyano; and

further wherein at least one 3-position R¹ group is independently selected from a group of the formulae (V) and (VI)

 

wherein

R⁵ is independently selected from hydrogen, linear or branched hydrocarbyl group of 1 to 24 carbon atoms, phenyl, and aralkyl of 7 to 24 carbon atoms; and

each R⁶ and R⁷ is independently selected from hydrogen, a hydrocarbyl group and a functional hydrocarbyl group.

3. The compound of claim 1 selected from the group consisting of the compounds of formula (XIII), (XIV) or (XV)

wherein

each R is independently selected from a hydrogen, a hydrocarbyl group and a functional hydrocarbyl group;

each R¹ and R² is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, —

O(hydrocarbyl), —

O(functional hydrocarbyl), —

SR, halogen, —

SO₂R, —

SO₃R, —

COOR, —

COR, —

OCOR, —

NRR and cyano; and

each R³ is independently selected from R, —

OR, —

SR, halogen, —

SO₂R, —

SO₃R, —

COOR, —

COR, —

NRR and cyano; and

further wherein at least one 3-position R¹ group is independently selected from a group of the formulae (V) and (VI)

 

wherein

R⁵ is independently selected from hydrogen, linear or branched hydrocarbyl group of 1 to 24 carbon atoms, phenyl, and aralkyl of 7 to 24 carbon atoms; and

each R⁶ and R⁷ is independently selected from hydrogen, a hydrocarbyl group and a functional hydrocarbyl group.

4. The compound of claim 1 of the following formula

wherein

each R is independently selected from a hydrogen, a hydrocarbyl group and a functional hydrocarbyl group;

each R¹ is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, —

O(hydrocarbyl), —

O(functional hydrocarbyl), —

SR, halogen, —

SO₂R, —

SO₃R, —

COOR, —

COR, —

OCOR, —

NRR and cyano; and

further wherein at least one 3-position R¹ group is independently selected from a group of the formulae (V) and (VI)

 

wherein

R⁵ is independently selected from hydrogen, linear or branched hydrocarbyl group of 1 to 24 carbon atoms, phenyl, and aralkyl of 7 to 24 carbon atoms; and

each R⁶ and R⁷ is independently selected from hydrogen, a hydrocarbyl group and a functional hydrocarbyl group.

5. The compound of claims 2, 3 or 4, wherein each R²is independently selected from hydrogen, an alkyl of 1 to 8 carbon atoms, an alkyloxy of 1 to 8 carbon atoms optionally containing an oxygen atom in the chain, a hydroxyalkyl of 1 to 8 carbon atoms group optionally containing an oxygen atom in the chain, a hydroxyalkyloxy of 1 to 8 carbon atoms group optionally containing an oxygen atom in the chain and an acyloxy of 2 to 12 carbon atoms;

each R³is independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing an oxygen atom in the chain, a hydroxyalkyl of 1 to 24 carbon atoms group optionally containing an oxygen atom in the chain and —

OR;

each R⁵ is independently selected from hydrogen and linear or branched alkyl groups of 1 to 24 carbon atoms; and

each of R⁶ and R⁷ is independently selected from hydrogen, an alkyl group of 1 to 24 carbon atoms which may optionally contain carbonyl and/or one or more oxygen atoms in the chain, and an aralkyl group of 7 to 24 carbon atoms, and at least one of which is substituted by a hydroxyl, —

CR⁹═

CHR¹⁰ or —

CO—

CR⁹═

CHR¹⁰, wherein R⁹ is independently selected from hydrogen and an alkyl of 1 to 4 carbon atoms and R¹⁰ is independently selected from hydrogen, a hydrocarbyl group of 1 to 8 carbon atoms, and phenyl.

6. The compound of claims 1, 2, 3 or 4, wherein the group of formula (V) contains at least one of the following structures

wherein R* is H, CH₃,

or

wherein n is 1-24, n1 is 0-23, n2 is 1-50 and n3 is 1-24;

7. The compound of claims 1, 2, 3 or 4, wherein the group of formula (VI) contains at least one of the following structures

8. The compound of claim 2 of formula (VII) wherein the 5-position R¹ group is hydrogen;

each R² group is independently selected from hydrogen, an alkoxy of 1 to 4 carbon atoms and an alkyl of 1 to 4 carbon atoms;

each R³ group is independently selected from hydrogen, an alkyl of 1 to 4 carbon atoms, and —

OR;

each R group is independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing an oxygen atom in the chain, and a hydroxyalkyl of 1 to 24 carbon atoms group optionally containing an oxygen atom in the chain; and

the 3-position R¹ group is a group of formula (V) where R⁵ is selected from hydrogen and an alkyl of 1 to 24 carbon atoms and R⁶ and R⁷ are allyl.

9. The compound of claim 2 of formula (VII) wherein R is hydrogen;

the 5-position R¹ group is hydrogen;

each R² group and each R³ group is methyl; and

the 3-position R¹ group is a group of formula (V) where R⁵ is hydrogen and R⁶ and R⁷ are allyl.

10. The compound of claim 2 of formula (VII) wherein the 5-position R¹ group is hydrogen;

each R² group is independently selected from hydrogen, an alkoxy of 1 to 4 carbon atoms and an alkyl of 1 to 4 carbon atoms;

each R³ group is independently selected from hydrogen, an alkyl of 1 to 4 carbon atoms, and —

OR;

each R group is independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing an oxygen atom in the chain, and a hydroxyalkyl of 1 to 24 carbon atoms group optionally containing an oxygen atom in the chain; and

the 3-position R¹ group is a group of formula (V) where R⁵ is selected from hydrogen and an alkyl of 1 to 24 carbon atoms and R⁶ and R⁷ are allyl.

11. The compound of claim 2 of formula (VII) wherein the 5-position R¹ group is hydrogen;

each R² group and each R³ group is methyl;

R is octyl; and

the 3-position R¹ group is a group of formula (V) where R⁵ is hydrogen and R⁶ and R⁷ are allyl.

12. The compound of claim 2 of formula (VII) wherein each R² group is independently selected from hydrogen, an alkoxy of 1 to 4 carbon atoms and an alkyl of 1 to 4 carbon atoms;

each R³ group is independently selected from hydrogen, an alkyl of 1 to 4 carbon atoms, and —

OR;

each R group is independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing an oxygen atom in the chain, and a hydroxyalkyl of 1 to 24 carbon atoms group optionally containing an oxygen atom in the chain; and

the 3-position and 5-position R¹ groups are a group of formula (V) where R⁵ is selected from hydrogen and an alkyl of 1 to 24 carbon atoms and R⁶ and R⁷ are allyl.

13. The compound of claim 2 of formula (VII) wherein each R² group and each R³ group is methyl;

R is hydrogen; and

the 3-position and 5-position R¹ groups are a group of formula (V) where R⁵ is hydrogen and R⁶ and R⁷ are allyl.

14. The compound of claim 2 of formula (XA) wherein each R² group is independently selected from hydrogen, an alkoxy of 1 to 4 carbon atoms and an alkyl of 1 to 4 carbon atoms;

each R³ group is independently selected from hydrogen, an alkyl of 1 to 4 carbon atoms, and —

OR;

each R group is independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing an oxygen atom in the chain, and a hydroxyalkyl of 1 to 24 carbon atoms group optionally containing an oxygen atom in the chain; and

the 3-position and 3′

-position R¹ groups are a group of formula (V) where R⁵ is selected from hydrogen and an alkyl of 1 to 24 carbon atoms and R⁶ and R⁷ are allyl.

15. The compound of claim 2 of formula (XA) wherein each R² group and each R³ group is methyl;

each R is hydrogen; and

the 3-position and 3′

-position R¹ groups are a group of formula (V) where R⁵ is hydrogen and R⁶ and R⁷ are allyl.

16. The compound of claim 2 of formula (XB) wherein each R² group is independently selected from hydrogen, an alkoxy of 1 to 4 carbon atoms and an alkyl of 1 to 4 carbon atoms;

each R³ group is independently selected from hydrogen, an alkyl of 1 to 4 carbon atoms, and —

OR;

each R group is independently selected from hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing an oxygen atom in the chain, and a hydroxyalkyl of 1 to 24 carbon atoms group optionally containing an oxygen atom in the chain; and

the 3-position and 5′

-position R¹ groups are a group of formula (V) where R⁵ is selected from hydrogen and an alkyl of 1 to 24 carbon atoms and R⁶ and R⁷ are allyl.

17. The compound of claim 2 of formula (XB) wherein each R² group and each R³ group is methyl;

each R is hydrogen; and

the 3-position and 5′

-position R¹ groups are a group of formula (V) where R⁵ is hydrogen and R⁶ and R⁷ are allyl.

18. A triazine compound of formula (I), (II) or (III), as follows:

wherein

i is 1 or 2;

each X is independently selected from hydrogen, C₁-C₈ alkyl, halogen-substituted C₁-C₈ alkyl, allyl, —

COR^a, —

SO₂R^b, —

SiR^cR^dR^e, —

PR^fR^g and —

POR^fR^g;

each of Y and Z is independently selected from an aryl ring of the formula (IV)

 

each R is independently selected from a hydrogen, a hydrocarbyl group and a functional hydrocarbyl group;

each R^a is independently selected from C₁-C₈ alkyl, halogen-substituted C₁-C₈ alkyl, C₅-C₁₂ cycloalkyl, C₂-C₈ alkenyl, —

CH₂—

CO—

CH₃, C₇-C₁₂ aralkyl, C₁-C₁₂ alkoxy, or phenyl which is unsubstituted or substituted by C₁-C₁₂ alkyl, C₁-C₄ alkoxy, halogen and benzyl;

each R^b is independently selected from C₁-C₁₂ alkyl, C₆-C₁₀ aryl and C₇-C₁₈ alkylaryl;

each R^c, R^d and R^e is independently selected from C₁-C₁₈ alkyl, cyclohexyl, phenyl and C₁-C₁₈ alkoxy;

each R^f and R^g is independently selected from C₁-C₁₂ alkoxy, phenoxy, C₁-C₁₂ alkyl, C₅-C₁₂ cycloalkyl, benzyl, tolyl and phenyl;

when i is 1, R¹ is bonded to the 3-position of the ring bearing the —

OX group, R¹¹ is bonded to the 5-position of the ring bearing the —

OX group, and R¹¹ is R¹ and,

when i is 2, R¹ is bonded, independently, to either the 3-position or the 5-position of a first ring and a second ring bearing the —

OX group and R¹¹ is bonded, at a first end, to the position of the first ring bearing —

OX not bonded to R¹ and at a second end, to the position of the second ring bearing —

OX not bonded to R¹, and R¹¹ is a hydrocarbylene group of 1 to 24 carbon atoms;

each R¹, R², R⁴, R^4′

and R^4″

is independently selected from hydrogen, hydrocarbyl, functional hydrocarbyl, —

O(hydrocarbyl), —

O(functional hydrocarbyl), —

SR, halogen, —

SO₂R, —

SO₃R, —

COOR, —

COR, —

OCOR, —

NRR and cyano; and

each R³ is independently selected from R, —

OR, —

SR, halogen, —

SO2R, —

SO₃R, —

COOR, —

COR, —

NRR and cyano; and

further wherein at least one 3-position or 5-position R¹ group is independently selected from a group of the formula (VI)

 

wherein

R⁵ is independently selected from hydrogen, linear or branched hydrocarbyl group of 1 to 24 carbon atoms, phenyl, and aralkyl of 7 to 24 carbon atoms; and

each R⁶ and R⁷ is independently selected from hydrogen, a hydrocarbyl group and a functional hydrocarbyl group.