Aromatic sulfonic acids, amines and nitrophenols in combination with nitroxyl radical-containing compounds or C-nitrosoanilines as polymerization inhibitors
View Patent ↗Disclosed herein is a method for inhibiting and retarding the premature polymerization and the polymer growth of vinyl aromatic monomers wherein the method comprises adding to said monomers an effective amount of an inhibitor and retarder blend comprising: (A) at least one aromatic sulfonic acid; (B) at least one amine; (C) at least one nitrophenol; and (D) at least one member of the group consisting of nitroxy radical-containing compounds and nitrosoanilines.
1. A composition comprising a blend of:
(A) from about 50 ppm to about 500 ppm by weight, based on the weight of the monomers, of at least one aromatic sulfonic acid;
(B) at least one amine;
(C) at least one nitrophenol; and
(D) at least one member of the group consisting of nitroxy radical-containing compounds and C-nitrosoanilines.
2. The composition of claim 1 wherein the aromatic sulfonic acid is a compound of the structure:
wherein R represents an alkylphenyl or an alkylnaphthyl group each having at least one straight or branched chain alkyl group having 1-32 carbon atoms.
3. The composition of claim 1 wherein the amine is selected from the group consisting of N-methyl-2-pyrrolidinone, α-naphthylamine, thiodiarylamines, p-phenylenediamine, o-phenylenediamine, 2,4-diamino diphenylamine, cyclohexyl naphthyl amine, polybutyl amines, methyl aniline, diphenyl-p-phenylene diamine, phenyl-β-naphthylamine, isopropoxydiphenylamine, aldol-α-naphthyl amine, symmetrical di-β-naphthyl-p-phenylenediamine, trimethyl dihydroquinoline, ditolylamines, phenyl-α-naphthylamine, phenyl-β-naphthylamine, diaminophenol, 4-cyclohexylaminophenol, p-aminophenol, o-aminophenol, and 5-amino-2-hydroxytoluene.
4. The composition of claim 1 wherein the nitrophenol is selected from the group consisting of 2,6-dinitro-4-methylphenol, 2-nitro-4-methylphenol, 2,4-dinitro-1-naphthol, 2,4,6-trinitrophenol (picric acid), 2,4-dinitro-6-methylphenol, 2,4-dinitrophenol, 2,4-dinitro-6-sec-butylphenol, 4-cyano-2-nitrophenol, 3-iodo-4-cyano-5-nitrophenol, m-nitro-p-cresol, and 2,6-dinitro-p-cresol.
5. The composition of claim 1 wherein (D) is a stable hindered nitroxyl compound having the structural formula:
wherein R 4 and R 7 are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R 5 and R 6 are independently selected from the group consisting of alkyl and heteroatom-substituted alkyl; and X 1 and X 2 (1) are independently selected from the group consisting of halogen, cyano, —COOR 10 , —S—COR 10 , —OCOR 10 , (wherein R 10 is alkyl or aryl), amino, —S—C 6 H 5 , carbonyl, alkenyl, or alkyl of 1 to 15 carbon atoms, or (2) taken together, form a ring structure with the nitrogen.
6. The composition of claim 1 wherein (D) is a nitrosoaniline having the structure:
wherein either
(i) R 31 , and R 32 are independently selected from the group consisting of hydrogen, alkyl, aryl, acyl, hydroxyl, alkoxy, nitroso, and sulfonyl, or
(ii) R 31 and R 32 can form a cyclic ring that is aryl, cycloalkyl, polyaryl, or heterocyclic; and
wherein either
(i) R 33 through R 37 are independently selected from the group consisting of hydrogen, alkyl, aryl, acyl, hydroxyl, alkoxy, acyloxy, NR 38 (R 39 ), nitro, nitroso, halogen, and sulfonyl, provided that at least one of R 33 through R 37 must be a nitroso group, or
(ii) any two adjacent R's can form a cyclic ring that is aryl, cycloalkyl, polyaryl, or heterocyclic, provided that at least one of R 33 through R 37 must be a nitroso group; and
R 38 and R 39 are independently selected from the group consisting of hydrogen, alkyl, aryl, acyl, and nitroso.
7. A composition comprising a vinyl aromatic monomer and a polymerization inhibiting and retarding amount of a blend comprising:
(A) from about 50 ppm to about 500 ppm by weight, based on the weight of the monomers, of at least one aromatic sulfonic acid;
(B) at least one amine;
(C) at least one nitrophenol; and
(D) at least one member of the group consisting of nitroxy radical-containing compounds and C-nitrosoanilines.
8. The composition of claim 7 wherein the aromatic sulfonic acid is a compound of the structure:
wherein R represents an alkylphenyl or an alkylnaphthyl group each having at least one straight or branched chain alkyl group having 1-32 carbon atoms.
9. The composition of claim 7 wherein the amine is selected from the group consisting of N-methyl-2-pyrrolidinone, α-naphthylamine, thiodiarylamines, p-phenylenediamine, o-phenylenediamine, 2,4-diamino diphenylamine, cyclohexyl naphthyl amine, polybutyl amines, methyl aniline, diphenyl-p-phenylene diamine, phenyl-β-naphthylamine, isopropoxydiphenylamine, aldol-α-naphthyl amine, symmetrical di-β-naphthyl-p-phenylenediamine, trimethyl dihydroquinoline, ditolylamines, phenyl-α-naphthylamine, phenyl-β-naphthylamine, diaminophenol, 4-cyclohexylaminophenol, p-aminophenol, o-aminophenol, and 5-amino-2-hydroxytoluene.
10. The composition of claim 7 wherein the nitrophenol is selected from the group consisting of 2,6-dinitro-4-methylphenol, 2-nitro-4-methylphenol, 2,4-dinitro-1-naphthol, 2,4,6-trinitrophenol (picric acid), 2,4-dinitro-6-methylphenol, 2,4-dinitrophenol, 2,4-dinitro-6-sec-butylphenol, 4-cyano-2-nitrophenol, 3-iodo-4-cyano-5-nitrophenol, m-nitro-p-cresol, and 2,6-dinitro-p-cresol.
11. The composition of claim 7 wherein (D) is a stable hindered nitroxyl compound having the structural formula:
wherein R 4 and R 7 are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R 5 and R 6 are independently selected from the group consisting of alkyl and heteroatom-substituted alkyl; and X 1 and X 2 (1) are independently selected from the group consisting of halogen, cyano, —COOR 10 , —S—COR 10 , —OCOR 10 , (wherein R 10 is alkyl or aryl), amido, —S—C 6 H 5 , carbonyl, alkenyl, or alkyl of 1 to 15 carbon atoms, or (2) taken together, form a ring structure with the nitrogen.
12. The composition of claim 7 wherein (D) is a nitrosoaniline having the structure:
wherein either
(i) R 31 , and R 32 are independently selected from the group consisting of hydrogen, alkyl, aryl, acyl, hydroxyl, alkoxy, nitroso, and sulfonyl, or
(ii) R 31 and R 32 can form a cyclic ring that is aryl, cycloalkyl, polyaryl, or heterocyclic; and
wherein either
(i) R 33 through R 37 are independently selected from the group consisting of hydrogen, alkyl, aryl, acyl, hydroxyl, alkoxy, acyloxy, NR 38 (R 39 ), nitro, nitroso, halogen, and sulfonyl, provided that at least one of R 33 through R 37 must be a nitroso group, or
(ii) any two adjacent R's can form a cyclic ring that is aryl, cycloalkyl, polyaryl, or heterocyclic, provided that at least one of R 33 through R 37 must be a nitroso group; and
R 38 and R 39 are independently selected from the group consisting of hydrogen, alkyl, aryl, acyl, and nitroso.
13. The composition of claim 1 wherein (A) is dodecylbenzenesulfonic acid, (B) is N-methyl-2-pyrrolidinone, (C) is 2,4-dinitro-6-sec-butylphenol, and (D) is 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy or 4-nitroso-N-(1,4-dimethylpentyl)-aniline.
14. The composition of claim 7 wherein (A) is dodecylbenzenesulfonic acid, (B) is N-methyl-2-pyrrolidinone, (C) is 2,4-dinitro-6-sec-butylphenol, and (D) is 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy or 4-nitroso-N-(1,4-dimethylpentyl)-aniline.