Modified hydrocarbylphenol-aldehyde resins for use as tackifiers and rubber compositions containing them
View Patent ↗The invention relates to a modified hydrocarbylphenol-aldehyde resin prepared by reacting a hydrocarbylphenol-aldehyde resin with a primary or secondary amine and further with an epoxide. The invention also provides a process for preparing a modified, hydrocarbylphenol-aldehyde resin and a rubber composition containing such resin.
1. A modified, hydrocarbylphenol-aldehyde resin prepared by reacting an epoxide with a resin of Formula (I) in the presence of a basic catalyst and at a basic pH,
wherein
R 1 is a straight or branched C 1 -C 30 alkyl;
R 2 is —CH 2 R 5 ,
wherein R 5 is an amine of formula (i)
wherein R′ and R″ are independently H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, aryl, or wherein R′ and R″, together with the N carrying them, form a 5-7 membered heterocyclic ring;
R 3 is R 2 or —CH(R 5 )OH;
R 4 is H or C 1 -C 4 alkyl; and
m plus n is at least 1.
2. The modified, hydrocarbylphenol-aldehyde resin of claim 1 , wherein said resin is prepared by reacting about 1 to about 25 weight percent the epoxide with the resin of Formula (I).
3. The modified, hydrocarbylphenol-aldehyde resin of claim 1 , wherein R 5 is morpholinyl.
4. The modified, hydrocarbylphenol-aldehyde resin of claim 1 , wherein R 1 is a straight or branched C 1 -C 15 alkyl.
5. The modified, hydrocarbylphenol-aldehyde resin of claim 4 , wherein R 1 is tertiary butyl or tertiary octyl.
6. A process for preparing a modified, hydrocarbylphenol-aldehyde resin comprising the step of:
(a) reacting an epoxide with a resin of Formula (I) in the presence of a basic catalyst and at a basic pH,
wherein
R 1 is a straight or branched C 1 -C 30 alkyl;
R 2 is —CH 2 R 5 ,
wherein R 5 is an amine of formula (i)
wherein R′ and R″ are independently H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, aryl, or wherein R′ and R″, together with the N carrying them, form a 5-7 membered heterocyclic ring;
R 3 is R 2 or —CHR 5 OH;
R 4 is H or C 1 -C 4 alkyl; and
m plus n is at least 1.
7. The process for preparing a modified, hydrocarbylphenol-aldehyde resin according to claim 6 , wherein step (a) comprises reacting about 1 to about 25 weight percent of the epoxide.
8. The process for preparing a modified, hydrocarbylphenol-aldehyde resin of claim 6 , wherein R 5 is morpholinyl.
9. The process for preparing a modified, hydrocarbylphenol-aldehyde resin of claim 6 , wherein R 1 is a straight or branched C 1 -C 15 alkyl.
10. The process for preparing a modified, hydrocarbylphenol-aldehyde resin of claim 9 , wherein R 1 is tertiary butyl or tertiary octyl.
11. A rubber composition having improved tack, comprising
a rubber or mixtures of rubbers, and
0.5 to 7 phr of a modified, hydrocarbylphenol-aldehyde resin of claim 1 .
12. The rubber composition of claim 11 , wherein R 5 is morpholinyl.
13. The rubber composition of claim 11 , wherein R 1 is a straight or branched C 1 -C 15 alkyl.
14. The rubber composition of claim 13 , wherein R 1 is tertiary butyl or tertiary octyl.
15. The rubber composition of claim 11 , wherein said rubber composition is a 30/70 natural rubber/butadiene rubber composition, a 70/30 styrene butadiene rubber/butadiene rubber composition, or a natural rubber composition.
16. A modified, hydrocarbylphenol-aldehyde resin prepared by reacting a C 16 alkyl epoxide with a resin of Formula (I) in the presence of a basic catalyst and at a basic pH,
wherein
R 1 is a straight or branched C 1 -C 30 alkyl;
R 2 is —CH 2 R 5 , wherein R 5 is a morpholinyl group;
R 3 is R 2 or —CH(R 5 )OH;
R 4 is H or C 1 -C 4 alkyl; and
m plus n is at least 1.
17. The modified, hydrocarbylphenol-aldehyde resin of claim 16 , wherein R 1 is tertiary butyl or tertiary octyl.
18. A rubber composition having improved tack, comprising
a rubber or mixtures of rubbers, and
0.5 to 7 phr of a modified, hydrocarbylphenol-aldehyde resin of claim 16 .
19. A process for preparing a modified, hydrocarbylphenol-aldehyde resin comprising the step of:
(a) reacting a C 16 alkyl epoxide with a resin of Formula (I) in the presence of a basic catalyst and at a basic pH,
wherein
R 1 is a straight or branched C 1 -C 30 alkyl;
R 2 is —CH 2 R 5 , wherein R 5 is a morpholinyl group;
R 3 is R 2 or —CHR 5 OH;
R 4 is H or C 1 -C 4 alkyl; and
m plus n is at least 1.
20. The process preparing a modified, hydrocarbylphenol-aldehyde resin of claim 19 , wherein R 1 is tertiary butyl or tertiary octyl.
21. The modified, hydrocarbylphenol-aldehyde resin of claim 1 , wherein the aldehyde is formaldehyde.