4-nitrosodiphenylamine derivatives and their use as coupling agents for filled rubber compounds
View Patent ↗A composition of matter is disclosed that comprises a compound of the formula A n R, wherein: A is R 1 is hydrocarbyl; m is 0 or 1; n is 1, 2, or 3; R is selected from the group consisting of: mono-, di-, and trivalent aliphatic groups; mono-, di-, and trivalent aromatic groups; five- and six-membered heterocyclic rings comprising n carbon atoms bonded to A, at least one nitrogen atom, and, optionally, at least one sulfur atom; and wherein R 2 and R 3 are independently selected from the group consisting of hydrogen and hydrocarbyl. These compounds are useful as coupling agents in filled elastomer compositions.
1. A composition of matter comprising a compound of the formula A n R, wherein:
A is
R 1 is hydrocarbyl;
m is 0 or 1;
n is 1, 2, or 3;
R is selected from the group consisting of:
mono-, di-, and trivalent aliphatic groups; mono-, di-, and trivalent aromatic groups; five- and six-membered heterocyclic rings comprising n carbon atoms bonded to A, at least one nitrogen atom, and, optionally, at least one sulfur atom; and
wherein R 2 and R 3 are independently selected from the group consisting of hydrogen and hydrocarbyl.
2. The composition of claim 1 wherein m is zero and R is selected from the group consisting of five- and six-membered heterocyclic rings comprising n carbon atoms bonded to A, at least one nitrogen atom, and, optionally, at least one sulfur atom; and
wherein R 2 and R 3 are independently selected from the group consisting of hydrogen and hydrocarbyl.
3. The composition of claim 2 wherein R 1 is selected from the group consisting of phenyl, alkyl-substituted phenyl, alkoxy substituted phenyl, alkyl amino-substituted phenyl, aryl amino-substituted phenyl, naphthyl, alkyl-substituted naphthyl, alkyl, and cyclic alkyl.
4. The composition of claim 3 wherein R 1 is phenyl.
5. The composition of claim 2 wherein R is selected from the group consisting of 1,3,5-triazinyl, 2-imidazolyl, 2-pyridinyl, 2-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 2-thiazolyl, 2-quinolyl, 2-quinoxalinyl, 2-quinazolinyl, 2-benzimidazolyl, and 2-benzothiazolyl.
6. The composition of claim 5 wherein R is 1,3,5-triazinyl, n is 1 or 2, and the triazine is substituted with hydroxy, alkoxy, halo, alkylamino, or phenylamino.
7. The composition of claim 3 wherein R is selected from the group consisting of 1,3,5-triazinyl, 2-imidazolyl, 2-pyridinyl, 2-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 2-thiazolyl, 2-quinolyl, 2-quinoxalinyl, 2-quinazolinyl, 2-benzimidazolyl, and 2-benzothiazolyl.
8. The composition of claim 7 wherein R is 1,3,5-triazinyl, n is 1 or 2, and the triazine is substituted with hydroxy, alkoxy, halo, alkylamino, or phenylamino.
9. The composition of claim 4 wherein R is selected from the group consisting of 1,3,5-triazinyl, 2-imidazolyl, 2-pyridinyl, 2-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 2-thiazolyl, 2-quinolyl, 2-quinoxalinyl, 2-quinazolinyl, 2-benzimidazolyl, and 2-benzothiazolyl.
10. The composition of claim 9 wherein R is 1,3,5-triazinyl, n is 1 or 2, and the triazine is substituted with hydroxy, alkoxy, halo, alkylamino, or phenylamino.
11. The composition of claim 2 wherein the compound is 2,4,6-tris(N-phenyl-p-benzoquinonediiminoxy)-1,3,5-triazine.
12. The composition of claim 1 wherein m is 1 and R is selected from the group consisting of mono-, di-, and trivalent aliphatic groups and mono-, di-, and trivalent aromatic groups.
13. The composition of claim 12 wherein R 1 is selected from the group consisting of phenyl, alkyl-substituted phenyl, alkoxy substituted phenyl, alkyl amino-substituted phenyl, aryl amino-substituted phenyl, naphthyl, alkyl-substituted naphthyl, alkyl, and cyclic alkyl.
14. The composition of claim 13 wherein R 1 is phenyl.
15. The composition of claim 12 wherein R is selected from the group consisting of alkyl, substituted alkyl, alkenyl, alkylidene, alkylene, phenyl, and substituted phenyl.
16. The composition of claim 13 wherein R is selected from the group consisting of alkyl, substituted alkyl, alkenyl, alkylidene, alkylene, phenyl, and substituted phenyl.
17. The composition of claim 14 wherein R is selected from the group consisting of alkyl, substituted alkyl, alkenyl, alkylidene, alkylene, phenyl, and substituted phenyl.
18. The composition of claim 12 wherein the compound is N-{4[(benzoyloxy)imino]-2,5-cyclohexadien-1-ylidene}aniline.
19. The composition of claim 12 wherein the compound is N-{4[(acetyloxy)imino]-2,5-cyclohexadien-1-ylidene}aniline.
20. A composition of matter comprising an elastomer, a filler, and a compound of the formula A n R, wherein:
A is
R 1 is hydrocarbyl;
m is 0 or 1;
n is 1, 2, or 3;
R is selected from the group consisting of:
mono-, di-, and trivalent aliphatic groups; mono-, di-, and trivalent aromatic groups; five- and six-membered heterocyclic rings comprising n carbon atoms bonded to A, at least one nitrogen atom, and, optionally, at least one sulfur atom; and
wherein R 2 and R 3 are independently selected from the group consisting of hydrogen and hydrocarbyl.
21. The composition of claim 20 wherein the filler is carbon black.
22. The composition of claim 21 wherein m is zero and R is selected from the group consisting of five- and six-membered heterocyclic rings comprising n carbon atoms bonded to A, at least one nitrogen atom, and, optionally, at least one sulfur atom; and
wherein R 2 and R 3 are independently selected from the group consisting of hydrogen and hydrocarbyl.
23. The composition of claim 22 wherein R 1 is selected from the group consisting of phenyl, alkyl-substituted phenyl, alkoxy substituted phenyl, alkyl amino-substituted phenyl, aryl amino-substituted phenyl, naphthyl, alkyl-substituted naphthyl, alkyl, and cyclic alkyl.
24. The composition of claim 23 wherein R 1 is phenyl.
25. The composition of claim 22 wherein R is selected from the group consisting of 1,3,5-triazinyl, 2-imidazolyl, 2-pyridinyl, 2-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 2-thiazolyl, 2-quinolyl, 2-quinoxalinyl, 2-quinazolinyl, 2-benzimidazolyl, and 2-benzothiazolyl.
26. The composition of claim 25 wherein R is 1,3,5-triazinyl, n is 1 or 2, and the triazine is substituted with hydroxy, alkoxy, halo, alkylamino, or phenylamino.
27. The composition of claim 23 wherein R is selected from the group consisting of 1,3,5-triazinyl, 2-imidazolyl, 2-pyridinyl, 2-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 2-thiazolyl, 2-quinolyl, 2-quinoxalinyl, 2-quinazolinyl, 2-benzimidazolyl, and 2-benzothiazolyl.
28. The composition of claim 27 wherein R is 1,3,5-triazinyl, n is 1 or 2, and the triazine is substituted with hydroxy, alkoxy, halo, alkylamino, or phenylamino.
29. The composition of claim 24 wherein R is selected from the group consisting of 1,3,5-triazinyl, 2-imidazolyl, 2-pyridinyl, 2-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 2-thiazolyl, 2-quinolyl, 2-quinoxalinyl, 2-quinazolinyl, 2-benzimidazolyl, and 2-benzothiazolyl.
30. The composition of claim 29 wherein R is 1,3,5-triazinyl, n is 1 or 2, and the triazine is substituted with hydroxy, alkoxy, halo, alkylamino, or phenylamino.
31. The composition of claim 22 wherein the compound is 2,4,6-tris(N-phenyl-p-benzoquinonediiminoxy)-1,3,5-triazine.
32. The composition of claim 21 wherein m is 1 and R is selected from the group consisting of mono-, di-, and trivalent aliphatic groups and mono-, di-, and trivalent aromatic groups.
33. The composition of claim 32 wherein R 1 is selected from the group consisting of phenyl, alkyl-substituted phenyl, alkoxy substituted phenyl, alkyl amino-substituted phenyl, aryl amino-substituted phenyl, naphthyl, alkyl-substituted naphthyl, alkyl, and cyclic alkyl.
34. The composition of claim 33 wherein R 1 is phenyl.
35. The composition of claim 32 wherein R is selected from the group consisting of alkyl, substituted alkyl, alkenyl, alkylidene, alkylene, phenyl, and substituted phenyl.
36. The composition of claim 33 wherein R is selected from the group consisting of alkyl, substituted alkyl, alkenyl, alkylidene, alkylene, phenyl, and substituted phenyl.
37. The composition of claim 34 wherein R is selected from the group consisting of alkyl, substituted alkyl, alkenyl, alkylidene, alkylene, phenyl, and substituted phenyl.
38. The composition of claim 32 wherein the compound is N-{4[(benzoyloxy)imino]-2,5-cyclohexadien-1-ylidene}aniline.
39. The composition of claim 32 wherein the compound is N-{4[(acetyloxy)imino]-2,5-cyclohexadien-1-ylidene}aniline.
40. The composition of claim 19 in which the elastomer is selected from the group consisting of an emulsion polymerized styrene-butadiene rubber, a solution polymerized styrene-butadiene rubber, a polybutadiene, a natural rubber, a polyisobutylene, a polyisoprene, and mixtures of the foregoing.
41. The composition of claim 19 in which the compound is added at a level of 0.1 to 10 parts per hundred of elastomer.
42. An article of manufacture comprising a cured mixture comprising an elastomer, a filler, and a compound of the formula A n R, wherein:
A is
R 1 is hydrocarbyl;
m is 0 or 1;
n is 1, 2, or 3;
R is selected from the group consisting of:
mono-, di-, and trivalent aliphatic groups; mono-, di-, and trivalent aromatic groups; five- and six-membered heterocyclic rings comprising n carbon atoms bonded to A, at least one nitrogen atom, and, optionally, at least one sulfur atom; and
wherein R 2 and R 3 are independently selected from the group consisting of hydrogen and hydrocarbyl.
43. The article of claim 42 wherein said article is a tire tread.