Non-yellowing para-tertiary-alkyl phenyl substituted triazine and pyrimidine ultraviolet light absorbers

• US 6,239,276 B1
• Filed: 06/18/1999
• Issued: 05/29/2001
• Est. Priority Date: 06/22/1998
• Status: Expired due to Fees

• Current Assignee: Cytec Technology Corp.
• Original Assignee: Cytec Technology Corp.
• Inventors: Gupta, Ram B., Jakiela, Dennis J.
• Primary Examiner(s): Shah, Mukund J.
• Assistant Examiner(s): Balasubramanian, Venkataraman
• Application Number:
  US09/335,885
• Time in Patent Office: 711 Days
• Field of Search: 544/213, 544/214, 544/215
• US Class Current: 544/213
• CPC Class Codes: C07D 251/24 to three ring carbon atoms
• CPC Class Codes: C08K 5/3492 Triazines
• CPC Class Codes: C09K 15/30 containing heterocyclic ring with at least one nitrogen atom as ring member

Abstract

This invention relates generally to para-tertiary alkyl phenyl substituted pyrimidines and 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 para-tertiary alkyl phenyl substituted pyrimidines and triazines includes two tertiary alkylated phenyl groups, and a resorcinol or substituted resocinol group attached to the triazine or pyrimidine ring. These materials may, under the appropriate circumstances, be bonded to formulations comprising coatings, polymers, resins, organic compounds and the like via reaction of the bondable functionality with the materials of the formulation. A method for stabilizing a material by incorporating such para-tertiary alkyl phenyl substituted pyrimidines and triazines is also disclosed.

Claims

1. A compound of formula (II) wherein:

wherein X is hydrogen or a blocking group;

each R is independently a hydrocarbyl group of 1 to 21 carbon atoms;

R¹ is C₁-C₂₄ alkyl, C₁-C₂₄ branched alkyl, C₂-C₂₄ alkenyl, a cycloalkyl from 5-24 carbon atoms, an araalkyl from 7-24 carbon atoms, —

COR⁹, —

CO₂R⁹, —

CONHR⁹, —

SO₂R⁹, C₁-C₁₈ alkyl substituted with at least one hydroxy, C₁-C₁₈ alkoxy, C₃-C₁₈ alkenoxy, halogen, phenoxy, C₁-C₁₈ alkyl-substituted phenoxy, C₁-C₁₈ alkoxy-substituted phenoxy, halogen-substituted phenoxy, —

COOH, —

COOR⁹, —

CONH₂, —

CONHR⁹, —

CON(R⁹)(R¹⁰), —

NH₂, —

NHR⁹, —

N(R⁹)(R¹⁰), —

NHCOR¹¹, —

N(R⁹)COR¹¹, —

NHCOOR¹¹, —

N(R⁹)COOR¹¹, —

CN, —

OCOR¹¹, —

OC(O)NHR⁹, —

OC(O)N(R⁹)(R¹⁰), glycidyloxy, glycidyl, cyclohexyl optionally substituted with hydroxyl or —

OCOR¹¹, and C₂-C₅₀ alkyl interrupted by at least one oxygen atom or carbonyl group and optionally substituted by one or more substituents selected from the group consisting of hydroxy or C₁-C₁₂ alkoxy;

wherein R⁹ and R¹⁰ independently of one another are C₁-C₁₂ alkyl, C₃-C₁₂ alkoxyalkyl, C₄-C₁₆ dialkylaminoalkyl, C₅-C₁₂ cycloalkyl, or R⁹ and R¹⁰ taken together are C₃-C₉ alkylene, C₃-C₉ oxoalkylene or C₃-C₉ azaalkylene; and

R¹¹ is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, or phenyl; and

R³ and R⁴ are each hydrogen, hydrocarbyl group of 1 to 21 carbon atoms, halogen, hydroxyl, cyano, —

O(hydrocarbyl), —

O(functional hydrocarbyl), —

N(hydrocarbyl)(hydrocarbyl) and mixtures thereof.

2. The compound according to claim 1, wherein at least two of the R groups are methyl and the other R group is methyl, ethyl, butyl, 2,2-dimethylpropyl, or phenyl.

3. The compound according to claim 2, wherein each R group is methyl.

4. The compound according to claim 1, wherein R¹ is selected from the group consisting of

an alkyl of 1 to 24 carbon atoms optionally substituted by one or more hydroxyl, carboxyl, carboalkoxy, amide, epoxy or amino groups and optionally containing one or more carbonyl groups, oxygen atoms or nitrogen atoms in the chain;

an alkenyl of 2 to 24 carbon atoms optionally substituted by at least one hydroxyl, carboxyl, epoxy or amino group and optionally containing one or more carbonyl groups, oxygen or nitrogen atoms in the chain;

a cycloalkyl of 5 to 24 carbon atoms optionally substituted by at least one hydroxyl, carboxyl, or amino group and optionally containing carbonyl, oxygen, or nitrogen in the ring; and

an aralkyl of 7 to 24 carbon atoms optionally substituted by at least one hydroxyl, carboxyl or amino group and may contain carbonyl, oxygen or nitrogen in the ring;

a polyoxyalkylene radical of the formula XII

5. A compound of formula (III):

wherein

R, R³, R⁴, and X, are defined as in claim 1;

r is an integer between 2 and 4; and

D, when r is 2, is selected from the group consisting of C₂-C₁₆ alkylene, C₄-C₁₂ alkenylene, xylylene, C₄-C₂₀ alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C₃-C₂₀ alkyl which is interrupted by one or more oxygen atoms, —

CH₂CH(OH)CH₂O—

R¹⁵—

OCH₂CH(OH)CH₂—

, —

CO—

R¹⁶CO—

, —

CO—

NH—

R¹⁷—

NH—

CO—

, —

(CH₂)_s—

COO—

R¹⁸—

OCO—

(CH₂)_s—

 

a polyoxyalkylene bridge member of the formula XX

6. A compound of formula (IV):

wherein

R, R³, and R⁴, are defined as in claim 1;

L is hydrogen, C₁-C₂₄ alkyl, C₁-C₂₄ branched alkyl, C₃-C₆ alkenyl, —

COR¹², —

COOR¹², —

CONHR¹², —

SO₂R¹³, C₁-C₁₈ alkyl which is substituted with at least one hydroxy, C₁-C₁₈ alkoxy, C₃-C₁₈ alkenoxy, halogen, phenoxy, C₁-C₁₈ alkyl-substituted phenoxy, C₁-C₁₈ alkoxy-substituted phenoxy, halogen-substituted phenoxy, —

COOH, —

COOR⁹, —

CONH₂, —

CONHR⁹, —

CON(R⁹)(R¹⁰), —

NH₂, —

NHR⁹, —

N(R⁹)(R¹⁰), —

NHCOR¹¹, —

N(R⁹)COR¹¹, —

NHCOOR¹¹, —

N(R⁹)COOR¹¹, —

CN, —

OCOR¹¹, —

OC(O)NHR⁹, —

OC(O)N(R⁹)(R¹⁰), glycidyloxy, glycidyl, cyclohexyl optionally substituted with hydroxyl or —

OCOR¹¹ or C₂-C₅₀ alkyl optionally interrupted by at least one oxygen atom or carbonyl group and optionally substituted by at least one substituents selected from the group consisting of hydroxy and C₁-C₁₂ alkoxy,

wherein R⁹ and R¹⁰ independently of one another are C₁-C₁₂ alkyl, C₃-C₁₂ alkoxyalkyl, C₄-C₁₆ dialkylaminoalkyl, C₅-C₁₂ cycloalkyl, or R⁹ and R¹⁰ taken together are C₃-C₉ alkylene, C₃-C₉ oxoalkylene, C₃-C₉ azaalkylene;

R¹¹ is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl;

R¹² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, phenyl, C₁-C₁₂ alkoxy, phenoxy, C₁-C₁₂ alkylamino, phenylamino, tolylamino or naphthylamino; and

R¹³ is C₁-C₁₂ alkyl, phenyl, naphthyl or C₇-C₁₄ alkylphenyl;

r is an integer between 2 and 4; and

X′

, when r is 2, is selected from the group consisting of C₂-C₁₆ alkylene, C₄-C₁₂ alkenylene, xylylene, C₄-C₂₀ alkylene which is interrupted by one or more oxygen atoms, hydroxy-substituted C₃-C₂₀ alkyl which is interrupted by one or more oxygen atoms, —

CH₂CH(OH)CH₂O—

R¹⁵—

OCH₂CH(OH)CH₂—

, —

CO—

R¹⁶—

CO—

, —

CO—

NH—

R¹⁷—

NH—

CO—

, —

(CH₂)_s—

COO—

R¹⁸—

OCO—

(CH₂)_s—

 

a polyoxyalkylene bridge member of the formula XX

7. The compound of formula (V):

wherein

X, R, and R³ are defined as in claim 1;

R⁴ is selected from the group consisting of straight chain alkyl of 1 to 12 carbon atoms, branched chain alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl substituted by cyclohexyl, alkyl interrupted by cyclohexyl, alkyl substituted by phenylene, alkyl interrupted by phenylene, benzylidene, —

S—

, —

S—

S—

, —

S—

E—

S—

, —

SO—

, —

SO₂—

, —

SO—

E—

SO—

, —

SO₂—

E—

SO₂—

, —

CH₂—

NH—

E—

NH—

CH₂—

, and

 

wherein E is selected from the group consisting of alkyl of 2 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted by cyclohexyl of 8 to 12 carbon atoms, alkyl terminated by cyclohexyl of 8 to 12 carbon atoms;

r is an integer between 2 and 4; and

L is selected from a hydrogen, hydrocarbyl, halogen, hydroxyl, cyano, —

O(hydrocarbyl), —

O(functional hydrocarbyl), —

N(hydrocarbyl)(hydrocarbyl), —

N(functional hydrocarbyl)(functional hydrocarbyl), —

S(hydrocarbyl), —

S(functional hydrocarbyl), —

SO₂(hydrocarbyl), —

SO₃(hydrocarbyl), —

SO₂(functional hydrocarbyl), —

SO₃(functional hydrocarbyl), —

COO(hydrocarbyl), —

COO(functional hydrocarbyl), —

CO(hydrocarbyl), —

CO(functional hydrocarbyl), —

OCO(hydrocarbyl), —

OCO(functional hydrocarbyl), —

CONH₂, —

CONH(hydrocarbyl), —

CONH(functional hydrocarbyl), —

CON(hydrocarbyl)(hydrocarbyl), —

CON(functional hydrocarbyl)(hydrocarbyl), —

CON(functional hydrocarbyl)(functional hydrocarbyl), or a hydrocarbyl group substituted by any of the above groups.

8. The compound according to claim 1, wherein R¹ is an alkyl group containing between 4 and 24 carbon atoms, X is hydrogen, each R is alkyl, and one of R₃ and R₄ is an alkyl group containing between 4 and about 24 carbon atoms while the other is hydrogen.

9. The compound according to claim 1, wherein R¹ is an alkyl group containing between 4 and 24 carbon atoms, X is hydrogen, each R is alkyl and R₃ and R₄ are hydrogen.

10. The compound according to claim 1, wherein X is independently selected from hydrogen and a blocking group and L is independently selected from —

S(hydrocarbyl), —

S(functional hydrocarbyl), —

SO₂(hydrocarbyl), —

SO₃(hydrocarbyl), —

SO₂(functional hydrocarbyl), and —

SO₃(functional hydrocarbyl).