Stabilization of organic materials
The invention describes a process for stabilizing an organic material against oxidative, thermal or light-induced degradation, which comprises incorporating therein or applying thereto at least a compound of the formula (I) wherein the general symbols are as defined in claim 1 . The compounds of the formula I are especially useful as processing stabilizers for synthetic polymers.
1. A process for stabilizing an organic material against oxidative, thermal or light-induced degradation, which process comprises incorporating therein or applying thereto at least one compound of formula I and at least one further additive selected from the group consisting of phenolic antioxidants, light stabilizers and organic phosphites or phosphonites,
—S—R 12 , —SO—R 12 , —SO 2 —R 12 or —CN; or R 1 and R 2 form together
R 2 is hydrogen, —S—R 13 , —SO—R 13 , —SO 2 —R 13 , unsubstituted or C 1 -C 4 alkyl substituted phenyl;
hydroxy or C 1 -C 25 alkanoyloxy,
R 3 , R 4 , R 5 , R 6 and R 7 independently of each other are hydrogen, C 1 -C 25 alkyl, halogen, trifluoromethyl, nitro, C 1 -C 25 alkoxy,
C 1 -C 25 phenylalkyl, phenyl or
or
each pair of substituent R 3 and R 4 or R 4 and R 5 or R 5 and R 6 or R 6 and R 7 , together with the linking carbon atoms, forms a benzene ring; and with the proviso that at least one of the radicals from the groups of R 3 to R 7 is hydrogen;
R 6 is hydrogen, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
R 9 is hydrogen, alkali metal, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 25 alkyl which is interrupted by oxygen or sulfur;
benzhydryl or
R 10 and R 11 independently of one another are hydrogen, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 8 cycloalkyl; or R 10 and R 11 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring which is unsubstituted or is substituted by C 1 -C 4 alkyl or is interrupted by oxygen, sulfur or
R 12 is hydrogen, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; or unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
R 13 is hydrogen, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; or unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
R 14 is C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; or unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
R 15 is C 1 -C 25 alkyl or C 7 -C 9 phenylalkyl,
R 16 is
halogen or nitro,
R 17 is C 2 -C 18 alkylene, C 4 -C 18 alkylene which is interrupted by oxygen, sulfur or
C 2 -C 18 alkenylene, C 2 -C 20 alkylidene, C 7 -C 20 phenylalkylidene, C 5 -C 8 cycloalkylene, C 7 -C 8 bicycloalkylene, unsubstituted or C 1 -C 4 alkyl-substituted phenylene;
R 18 is hydrogen, C 1 -C 8 alkyl or benzyl,
R 19 is C 1 -C 25 alkyl or C 7 -C 9 phenylalkyl,
X is a direct bond, —SO— or —SO 2 — and
when R 1 is
R 2 is hydrogen, R 0 is
X is a direct bond and R 3 , R 4 , R 5 , R 6 and R 7 are each hydrogen, R 9 is selected from the group consisting of propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2- ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl and docosyl, and
where the organic material is selected from the group consisting of lubricants, polypropylene, polyethylene, ethylene/propylene copolymers, polyacetals, polyurethanes, polycarbonates and polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, and
where the compound of formula I is present in an amount of from 0.0005 to 10% based on the weight of the organic material.
2. A process according to claim 1 , wherein
R 0 is
R 1 is
—S—R 12 , —SO—R 12 , —SO 2 —R 12 or —CN;
or R 1 and R 2 form together
R 2 is hydrogen, —S—R 13 , —SO—R 13 , —SO 2 —R 13 , unsubstituted or C 1 -C 4 alkyl substituted phenyl; or
R 3 , R 4 , R 5 , R 6 and R 7 independently of each other are hydrogen, C 1 -C 25 alkyl, halogen, trifluoromethyl, C 1 -C 25 alkoxy,
C 7 -C 9 phenylalkyl, phenyl or
or each pair of substituent R 3 and R 4 or R 4 and R 5 or R 5 and R 6 or R 6 and R 7 , together with the linking carbon atoms, forms a benzene ring; and with the proviso that at least one of the radicals from the group of R 3 to R 7 is hydrogen;
R 8 is hydrogen, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
R 9 is hydrogen, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; unsubstituted or C 1 C 4 alkyl-substituted C 5 -C 8 cycloalkyl; C 3 -C 25 alkyl which is interrupted by oxygen or sulfur;
benzhydryl or
R 10 and R 11 independently of one another are hydrogen, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; unsubstituted or C 1 -C 4 alkyl-substituted C 5 C 8 cycloalkyl; or R 10 and R 11 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring which is unsubstituted or is substituted by C 1 -C 4 alkyl or is interrupted by oxygen, sulfur or
R 12 is hydrogen, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; or unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
R 13 is hydrogen, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; or unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 8 cycloalklyl;
R 14 is C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; or unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 8 cycloalkyl;
R 15 is C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl,
R 16 is
halogen or nitro,
R 17 is C 2 -C 18 alkylene, C 4 -C 18 alkylene which is interrupted by oxygen, sulfur or
C 2 -C 18 alkenylene, C 2 -C 20 alkylidene, C 7 -C 20 phenylalkylidene, C 5 -C 8 cycloalkylene, C 7 -C 8 bicycloalkylene, unsubstituted or C 1 -C 4 alkyl-substituted phenylene;
R 18 is hydrogen, C 1 -C 8 alkyl or benzyl,
R 19 is C 1 -C 25 alkyl or C 7 -C 9 phenylalkyl and
X is a direct bond, —SO— or —SO 2 —.
3. A process according to claim 2 , wherein R 3 , R 4 , R 6 and R 7 are hydrogen.
4. A process according to claim 2 , wherein
R 5 is hydrogen, trifluoromethyl,
R 14 is C 1 -C 18 alkyl and
R 15 is C 1 -C 18 alkyl.
5. A process according to claim 1 , wherein
R 0 is
R 1 is
—S—R 12 , —SO—R 12 , —S 2 —R 12 or —CN,
R 2 is hydrogen, —S—R 13 , —SO— 13 , —S 2 —R 13 , unsubstituted or C 1 -C 4 alkyl substituted phenyl; or
R 3 , R 4 , R 5 , R 6 and R 7 independently of each other are hydrogen, C 1 -C 18 alkyl, chloro, bromo, nitro, trifluoromethyl, C 1 -C 18 alkoxy,
benzyl, phenyl or
and with the proviso that at least one of the radicals from the group of R 3 to R 7 is hydrogen;
R 8 is hydrogen, C 1 -C 18 alklyl, C 7 -C 9 phenylalkyl, phenyl or C 5 -C 8 cycloalkyl,
R 9 is hydrogen, C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, phenyl, cyclohexyl, C 3 -C 18 alkyl which
is interrupted by oxygen;
benzhydryl or
R 10 and R 11 independently of one another are hydrogen, C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, phenyl or C 5 -C 8 cycloalkyl; or R 10 and R 11 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring which is unsubstituted or is substituted by C 1 -C 4 alkyl;
R 12 is C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, phenyl or C 5 -C 8 cycloalkyl,
R 13 is C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, phenyl or C 5 -C 8 cycloalkyl,
R 14 is C 1 -C 18 alkyl, benzyl, phenyl or C 5 -C 8 cycloalkyl,
R 15 is C 1 -C 18 alkyl or benzyl,
R 16 is
chloro, bromo or nitro,
R 17 is C 2 -C 18 alkylene, C 4 -C 18 alkylene which is interrupted by oxygen or sulfur; C 2 -C 18 alkenylene, C 2 -C 12 alkylidene, C 7 -C 20 phenylalkylidene, C 5 -C 8 cycloalkylene, C 7 -C 8 bicycloalkylene or phenylene,
R 19 is C 1 -C 18 alkyl or benzyl,
X is a direct bond, —SO— or —SO 2 — and
when R 1 is
R 2 is hydrogen, X is a direct bond and R 3 , R 4 , R 5 , R 6 and R 7 are each hydrogen, R 9 is selected from the group consisting of propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1 -methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1 -methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1 -methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
6. A process according to claim 1 , wherein
R 0 is
R 1 is
—S—R 12 , —SO—R 12 , —SO 2 —R 12 or —CN,
R 2 is hydrogen, —S—R 13 , —SO—R 13 , —SO 2 R 13 , phenyl or
R 3 , R 4 , R 5 , R 6 and R 7 independently of each other are hydrogen, C 1 -C 12 alkyl, chloro, nitro trifluoromethyl, C 1 -C 12 alkoxy,
benzyl, phenyl or
and with the proviso that at least one of the radicals from the group of R 3 to R 7 is hydrogen;
R 8 is C 1 -C 12 alklyl, benzyl, phenyl or cyclohexyl,
R 9 is C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, phenyl, cyclohexyl, C 4 -C 12 alkyl which is interrupted by oxygen;
benzhydryl or
R 10 and R 11 independently of one another are hydrogen, C 2 -C 12 alkyl, benzyl or cyclohexyl, or R 10 and R 11 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring;
R 12 is C 1 -C 12 alkyl, benzyl, phenyl or cyclohexyl,
R 13 is C 1 -C 12 alkyl, benzyl, phenyl or cyclohexyl,
R 14 is C 1 -C 12 alkyl, benzyl, phenyl or cyclohexyl,
R 15 is C 1 -C 12 alkyl or benzyl, R 16 is
chloro or nitro,
R 17 is C 2 -C 12 alkylene, C 4 -C 18 alkylene which is interrupted by oxygen; C 2 -C 12 alkenylene, C 2 -C 12 alkylidene, C 5 -C 8 cycloalkylene or phenylene
R 19 is C 1 -C 12 alkyl or benzyl,
X is a direct bond, —SO— or —SO 2 — and
when R 1 is
R 2 is hydrogen, X is a direct bond and R 3 , R 4 , R 5 , R 6 and R 7 are each hydrogen, R 9 is selected from the group consisting of propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3 -dimethylbutyl, n-hexyl, 1 -methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1 -methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3- trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1 -methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
7. A process according to claim 1 , wherein
R 0 is
R 1 is
—S—R 12 , —SO—R 12 , —SO 2 —R 12 or —CN
R 2 is hydrogen, —S—R 13 , —SO—R 13 , —SO 2 —R 13 , phenyl of
R 3 , R 4 , R 5 , R 6 and R 7 independently of each other are hydrogen, C 1 -C 8 alklyl, trifluoromethyl, C 1 -C 8 alkoxy,
phenyl,or
and with the proviso that at least one of the radicals from the group of R 3 to R 7 is hydrogen;
R 9 is C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, cyclohexyl,
benzhydryl or
R 10 and R 11 independently of one another are hydrogen, C 2 -C 10 alkyl, benzyl or cyclohexyl; or R 10 and R 11 , together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring;
R 12 is benzyl, phenyl or cyclohexyl,
R 13 is benzyl, phenyl or cyclohexyl,
R 14 is C 1 -C 8 alkyl, benzyl or cyclohexyl,
R 15 is C 1 C 8 alkyl or benzyl,
R 16 is
or nitro,
R 17 is C 2 -C 12 alklylene, C 4 -C 12 alkylene which is interrupted by oxygen, cyclohexylene or phenylene,
R 19 is C 1 -C 8 alkyl or benzyl,
X is a direct bond, —SO— or —SO 2 — and
when R 1 is
R 2 is hydrogen, X is a direct bond and R 3 , R 4 , R 5 , R 6 and R 7 are each hydrogen, R 9 is selected from the group consisting of propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
8. A process according to claim 1 , wherein
R 0 is
R 1 is
—S—R 12 , —SO—R 12 , SO 2 R 12 or —CN
R 2 is hydrogen, —SO—R 13 , —SO 2 R 13 , phenyl or
R 3 is hydrogen,
R 4 is hydrogen,
R 5 is hydrogen, trifluoromethyl,
R 6 is hydrogen,
R 7 is hydrogen,
R 9 is C 1 -C 18 alkyl, benzyl, phenylethyl, cyclohexyl,
benzhydryl or
R 10 and R 11 independently of one another are hydrogen, C 4 -C 8 alkyl, benzyl or cyclohexyl; or R 10 and R 11 , together with the nitrogen atom to which they are attached, form a 5- or 6-membered heterocyclic ring
R 12 is phenyl,
R 13 is phenyl,
R 14 is C 1 -C 4 alkyl,
R 15 is C 1 -C 4 alkyl,
R 16 is
or nitro,
R 17 is C 2 -C 8 alkylene,
R 19 is C 1 -C 4 alkyl,
X is a direct bond or —SO— and
when R 1 is
R 2 is hydrogen, X is a direct bond and R 3 , R 4 , R 5 , R 6 and R 7 are each hydrogen, R 9 is selected from the group consisting of propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
9. A process according to claim 1 , where the organic material is a polyurethane.
10. A process according to claim 1 , where the organic material is a polyacetal or a polycarbonate.
11. A process according to claim 1 , where the organic material is selected from the group consisting of polypropylene, polyethylene and ethylene/propylene copolymers.
12. A process according to claim 1 , in which the compound of the formula is present in an amount of from 0.001 to 2%, based on the weight of the organic material.
13. A process according to claim 1 , comprising incorporating therein or applying thereto an organic phosphite or phosphonite.
14. A process according to claim 13 , comprising incorporating therein or applying thereto a phenolic antioxidant or a light stabilizer.
15. A process according to claim 1 wherein the stabilization of the organic material takes place during processing of the organic material.
16. A process according to claim 1 where the organic material is a lubricant.
17. A process according to claim 1 where the organic material is a polyester.