Synergistic combination for inhibiting polymerization of vinyl monomers
The present invention provides a method for inhibiting unwanted polymerization of reactive monomers within a liquid. The method comprises the combined usage of a quinone methide with a quinone diimide to the liquid monomer. This combination has an unexpected synergistic effect. Thus, in some ratios, the combination results in practically 100% inhibition.
1. A method of inhibiting polymerization of vinyl monomers in a liquid, comprising adding to said liquid a composition comprising Compound A and Compound B, wherein:
Compound A is a quinone methide compound with the formula:
wherein R 1 and R 2 may be the same or different and each of R 1 and R 2 is selected from the group consisting of H, C 4 to C 18 alkyl, C 5 to C 12 cycloalkyl, C 7 to C 15 phenylalkyl, and any combination thereof, and R 3 is an aryl, an aryl substituted with C 1 to C 6 alkyl, an alkoxy, a nitro, an amino, a carboxy, a nitrile, a methoxy, 4-hydroxy-3,5-di-tert-butylphenyl, an acetylenic group, a phenyl-substituted acetyleno, a phenyl-substituted acetyleno substituted with C 1 to C 6 alkyl, alkoxy, nitro, amino, carboxy, and any combination thereof;
Compound B is a quinone diimide compound of the formula:
wherein R 1 and R 2 may be the same or different and each of R1 and R2 is selected from the group consisting of an alkyl, an aryl, an alkaryl, and an aralkyl; wherein the weight ratio of Compound A to Compound B is from about 9:1 to about 1:9, and the polymerization is inhibited within an anaerobic environment.
2. The method of claim 1 , wherein Compound A is a stable quinone methide selected from the group consisting of: 2-(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)acetonitrile; 2,6-di-tert-butyl-7-cyano quinone methide; 4 benzylidene-2,6-di-tert-butyl-cyclohexa-2,5-dienone; 2,6-di-tert-butyl-4-(methoxymethylene)cyclohexa-2,5-dienone; 2,6-di-tert-butyl-4-(3,5-di-tert-butyl-4-hydroxybenzylidene)cyclohexa-2,5-dienone; and any combination thereof.
3. The method of claim 1 , wherein Compound B is benzoquinonediimide compound N,N′-(cyclohexa-2,5-diene-1,4-diylidene)dibutan-1-amine.
4. The method of claim 1 , wherein Compound B is benzoquinonediimide compound (E)-N-((E)-4-(4-methylpentan-2-ylimino)cyclohexa-2,5-dienylidene)aniline.
5. The method of claim 1 , wherein said composition is added to the liquid in an amount of from about 1 to about 10,000 parts per million of said monomer.
6. The method of claim 1 , wherein the weight proportion of Compound A to Compound B is about 1:1.
7. The method of claim 1 , wherein the weight proportion of Compound A to Compound B ranges from about 6:4 to about 4:6.
8. The method of claim 1 , wherein the polymerization is substantially inhibited.
9. The method of claim 1 , wherein the inhibition is more effective than the linear combination of the effectiveness of an inhibitor consisting essentially of Compound B with the effectiveness of an inhibitor consisting essentially of Compound A.
10. The method of claim 1 , wherein said composition is added to the liquid in an amount of from about 1 to about 1000 parts per million of said monomers.
11. The method of claim 1 , wherein the weight ratio of Compound A to Compound B is from about 9:1 to about 3:7.
12. The method of claim 1 , wherein, when R 1 is not H, R 1 is selected from the group consisting of tert-butyl, tert-amyl, tert-octyl, cyclohexyl, α-methylbenzyl, α,α-dimethylbenzyl, and any combination thereof.
13. The method of claim 1 , wherein, when R 2 is not H, R 2 is selected from the group consisting of tert-butyl, tert-amyl, tert-octyl, cyclohexyl, α-methylbenzyl, α,α-dimethylbenzyl, and any combination thereof.
14. A method of inhibiting polymerization of vinyl monomers in a liquid comprising adding to said liquid a composition comprising Compound A and Compound B, wherein:
Compound A is a quinone methide compound with the formula:
wherein R 1 and R 2 may be the same or different and each of R 1 and R 2 is selected from the group consisting of H, C 4 to C 18 alkyl, C 5 to C 12 cycloalkyl, C 7 to C 15 phenylalkyl, and any combination thereof, and, R 3 is aryl, or aryl substituted with C 1 to C 6 alkyl, alkoxy, nitro, amino and carboxy, nitrile, methoxy, 4-hydroxy-3,5-di-tert-butylphenyl, an acetylenic group, or phenyl-substituted acetyleno, phenyl-substituted acetyleno substituted with C 1 to C 6 alkyl, alkoxy, nitro, amino, carboxy, and any combination thereof;
Compound B is a quinone diimide compound selected from the group consisting of: a N,N′-dialkyl-p-benzoquinonediimide, a N-phenyl-N′-alkyl-p-benzoquinonediimide, and combinations thereof; wherein the weight ratio of Compound A to Compound B is from about 9:1 to about 1:9, and the polymerization is inhibited within an anaerobic environment.
15. The method of claim 14 , wherein said composition is added to the liquid in an amount of from about 1 to about 10,000 parts per million of said monomer.
16. The method of claim 14 , wherein said composition is added to the liquid in an amount of from about 1 to about 1000 parts per million of said monomer.
17. The method of claim 14 , wherein the weight proportion of Compound A to Compound B ranges from about 9:1 to about 3:7.
18. The method of claim 14 , wherein wherein the weight proportion of Compound A to Compound B ranges from about 6:4 to about 4:6.
19. The method of claim 14 , wherein the weight proportion of Compound A to Compound B is about 1:1.
20. A method of inhibiting polymerization of vinyl monomers in a liquid comprising adding to said liquid a composition comprising Compound A and Compound B, wherein:
Compound A is a quinone methide compound with the formula:
wherein R 1 and R 2 may be the same or different and each of R 1 and R 2 is selected from the group consisting of H, C 4 to C 18 alkyl, C 5 to C 12 cycloalkyl, C 7 to C 15 phenylalkyl, and any combination thereof, and R 3 is aryl, or aryl substituted with C 1 to C 6 alkyl, alkoxy, nitro, amino and carboxy, nitrile, methoxy, 4-hydroxy-3,5-di-tert-butylphenyl, an acetylenic group, or phenyl-substituted acetyleno, phenyl-substituted acetyleno substituted with C 1 to C 6 alkyl, alkoxy, nitro, amino, carboxy, and any combination thereof;
Compound B is a quinone diimide compound selected from the group consisting of: N,N′-di-sec-butyl-p-benzoquinonediimide, N-phenyl-N′-methyl-p-benzoquinonediimide, N-phenyl-N′-ethyl-p-benzoquinonediimide, N-phenyl-N′-propyl-p-benzoquinonediimide, N-phenyl-N′-n-butyl-p-benzoquinonediimide, N-phenyl-N′-iso-butyl-p-benzoquinonediimide, N-phenyl-N′-sec-butyl-p-benzoquinonediimide, N-phenyl-N′-tert-butyl-p-benzoquinonediimide, N-phenyl-N′-n-pentyl-p-benzoquinonediimide, N-phenyl-N′-(1-methylhexyl)-p-benzoquinonediimide, N-phenyl-N′-(1,3-dimethylhexyl)-p-benzoquinonediimide, N,N′-bis(1,4-dimethylpentyl)-p-benzoquinonediimide, N-phenyl-N′-(1,4-dimethylpentyl)-p-benzoquinonediimide and N-phenyl-N′-(1,4-dimethylbutyl)-p-benzoquinonediimide, and combinations thereof; wherein the weight ratio of Compound A to Compound B is from about 9:1 to about 1:9, and the polymerization is inhibited within an anaerobic environment.