Substituted 1-hydroxy-2,6-diaryl-4-piperidone ketals and polymer compositions stabilized therewith

Claim 2

A compound of formula I, II or III ##STR6## wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 are independently aryl of 6 to 10 carbon atoms or said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOR 15 where R 15 is hydrogen or alkyl of 1 to 20 carbon atoms, --COR 16 where R 16 is alkyl of 1 to 20 carbon atoms, --NR 17 R 18 where R 17 and R 18 are independently hydrogen or alkyl of 1 to 20 carbon atoms, --SR 19 where R 19 is aryl of 6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms, --OH, --OCH 3 , --CN, --CF 3 , --NO 2 , --F, --Cl, --Br and --I; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogen, a linear or branched alkyl of 1 to 30 carbon atoms, said alkyl terminated with --OR 20 , --NR 21 R 22 , --SR 23 , --COOR 24 or --CONR 25 R 26 , where R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are independently hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 3 to 18 carbon atoms, said alkyl interrupted by one or more --O--, --S--, --SO--, --SO 2 --, --CO--, --COO--, --OCO--, --CONR 27 --, --NR 27 CO-- or --NR 28 -- where R 27 and R 28 independently have the same meaning as R 20 , alkenyl of 3 to 20 carbon atoms, aryl of 6 to 10 carbon atoms, said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOR 29 where R 29 is hydrogen or alkyl of 1 to 20 carbon atoms, --COR 30 where R 30 is alkyl of 1 to 20 carbon atoms, --NR 31 R 32 where R 31 and R 32 are independently hydrogen or alkyl of 1 to 20 carbon atoms, --SR 33 where R 33 is aryl of 6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms, --OH, --OCH 3 , --CN, --CF 3 , --NO 2 , --F, --Cl, --Br and --I; T is a direct bond or --CR 34 R 35 -- where R 34 and R 35 independently have the same meaning as R 1 ; and X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are independently --O--, --S-- or --NR 36 -- where R 36 has the same meaning as R 20 .

Claim 3

A compound according to claim 1 wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 or Ar 6 is phenyl.

Claim 4

A compound according to claim 1 wherein R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogen or methyl.

Claim 5

A compound according to claim 1 where in formula I, R 5 and R 6 are hydrogen and T is a direct bond; or R 5 is hydrogen and R 6 is tetradecyl, and T is a direct bond; or R 5 and R 6 are hydrogen and T is --C(CH 3 ) 2 --.

Claim 6

A compound according to claim 1 where in formula III, R 5 and R 6 are alkyl of 6 to 12 carbon atoms.

Claim 7

A compound according to claim 1 wherein X 1 , X 2 , X 3 , X 4 , X 5 or X 6 is --O--.

Claim 8

The compound according to claim 1 which is 1-hydroxy-2,6-diphenyl-4-piperidone ethylene ketal; 1-hydroxy-2,6-diphenyl-4-piperidone 1,2-hexadecylene ketal; 3,15-diaza-3,15-dihydroxy-7,11,18,21-tetraoxa-2,4,14,16-tetraphenyl-trispiro[5.2.2.5.2.2]henicosane; 3,15-diaza-3,15-dihydroxy-1,13-dimethyl-7,11,18,21-tetraoxa-2,4,14,16-tetraphenyl-trispiro[5.2.2.5.2.2]henicosane; 9-aza-9-hydroxy-3,3,7-trimethyl-1,5-dioxa-8,10-diphenylspiro[5,5]undecane; 1-hydroxy-2,6-diphenyl-4,4-dimethoxypiperidine; 1-hydroxy-2,6-diphenyl-4,4-dihexyloxypiperidine; or 1-hydroxy-2,6-diphenyl-4,4-dioctyloxypiperidine.

Claim 9

A stabilized composition which comprises (a) an organic polymer subject to thermal and oxidative degradation; and (b) an effective stabilizing amount of a compound of formula I, II or III ##STR7## wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 are independently aryl of 6 to 10 carbon atoms or said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOR 15 where R 15 is hydrogen or alkyl of 1 to 20 carbon atoms, --COR 16 where R 16 is alkyl of 1 to 20 carbon atoms, --NR 17 R 18 where R 17 and R 18 are independently hydrogen or alkyl of 1 to 20 carbon atoms, --SR 19 where R 19 is aryl of 6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms, --OH, --OCH 3 , --CN, --CF 3 , --NO 2 , --F, --Cl, --Br and --I; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogen, a linear or branched alkyl of 1 to 30 carbon atoms, said alkyl terminated with --OR 20 , --NR 21 R 22 , --SR 23 , --COOR 24 or --CONR 25 R 26 , where R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are independently hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 3 to 18 carbon atoms, said alkyl interrupted by one or more --O--, --S--, --SO--, --SO 2 --, --CO--, --COO--, --OCO--, --CONR 27 --, --NR 27 CO-- or --NR 28 -- where R 27 and R 28 independently have the same meaning as R 20 , alkenyl of 3 to 20 carbon atoms, aryl of 6 to 10 carbon atoms, said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOR 29 where R 29 is hydrogen or alkyl of 1 to 20 carbon atoms, --COR 30 where R 30 is alkyl of 1 to 20 carbon atoms, --NR 31 R 32 where R 31 and R 32 are independently hydrogen or alkyl of 1 to 20 carbon atoms, --SR 33 where R 33 is aryl of 6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms, --OH, --OCH 3 , --CN, --CF 3 , --NO 2 , --F, --Cl, --Br and --I; T is a direct bond or --CR 34 R 35 -- where R 34 and R 35 independently have the same meaning as R 1 ; and X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are independently --O--, --S-- or --NR 36 -- where R 36 has the same meaning as R 20 .

Claim 10

A stabilized composition which comprises (a) an organic polymer subject to thermal and oxidative degradation; and (b) an effective stabilizing amount of a compound of formula I, II or III ##STR7## wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 are independently aryl of 6 to 10 carbon atoms or said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOR 15 where R 15 is hydrogen or alkyl of 1 to 20 carbon atoms, --COR 16 where R 16 is alkyl of 1 to 20 carbon atoms, --NR 17 R 18 where R 17 and R 18 are independently hydrogen or alkyl of 1 to 20 carbon atoms, --SR 19 where R 19 is aryl of 6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms, --OH, --OCH 3 , --CN, --CF 3 , --NO 2 , --F, --Cl, --Br and --I; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogen, a linear or branched alkyl of 1 to 30 carbon atoms, said alkyl terminated with --OR 20 , --NR 21 R 22 , --SR 23 , --COOR 24 or --CONR 25 R 26 , where R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are independently hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 3 to 18 carbon atoms, said alkyl interrupted by one or more --O--, --S--, --SO--, --SO 2 --, --CO--, --COO--, --OCO--, --CONR 27 --, --NR 27 CO-- or --NR 28 -- where R 27 and R 28 independently have the same meaning as R 20 , alkenyl of 3 to 20 carbon atoms, aryl of 6 to 10 carbon atoms, said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOR 29 where R 29 is hydrogen or alkyl of 1 to 20 carbon atoms, --COR 30 where R 30 is alkyl of 1 to 20 carbon atoms, --NR 31 R 32 where R 31 and R 32 are independently hydrogen or alkyl of 1 to 20 carbon atoms, --SR 33 where R 33 is aryl of 6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms, --OH, --OCH 3 , --CN, --CF 3 , --NO 2 , --F, --Cl, --Br and --I; T is a direct bond or --CR 34 R 35 -- where R 34 and R 35 independently have the same meaning as R 1 ; and X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are independently --O--, --S-- or --NR 36 -- where R 36 has the same meaning as R 20 .

Claim 11

A composition according to claim 8 wherein the organic polymer is a polyolefin.

Claim 12

A composition according to claim 9 wherein the polyolefin is polypropylene.

Claim 13

A composition according to claim 8 where in the compound of component (b) of formula I, II or III, Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 or Ar 6 is phenyl.

Claim 14

A composition according to claim 8 where in the compound of component (b) of formula I, II or III, R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogen or methyl.

Claim 15

A composition according to claim 8 where in the compound of component (b) of formula I, R 5 and R 6 are hydrogen and T is a direct bond; or R 5 is hydrogen and R 6 is tetradecyl, and T is a direct bond; or R 5 and R 6 are hydrogen and T is --C(CH 3 ) 2 --.

Claim 16

A composition according to claim 8 where in the compound of component (b) of formula III, R 5 and R 6 are alkyl of 6 to 12 carbon atoms.

Claim 17

A composition according to claim 8 where in the compound of component (b) of formula I, II or III, X 1 , X 2 , X 3 , X 4 , X 5 or X 6 is --O--.

Claim 18

A composition according to claim 8 wherein the compound of component (b) is 1-hydroxy-2,6-diphenyl-4-piperidone ethylene ketal; 1-hydroxy-2,6-diphenyl-4-piperidone 1,2-hexadecylene ketal; 3,15-diaza-3,15-dihydroxy-7,11,18,21-tetraoxa-2,4,14,16-tetraphenyl-trispiro[5.2.2.5.2.2]henicosane; 3,15-diaza-3,15-dihydroxy-1,13-dimethyl-7,11,18,21-tetraoxa-2,4,14,16-tetraphenyl-trispiro[5.2.2.5.2.2.]henicosane; 9-aza-9-hydroxy-3,3,7-trimethyl-1,5-dioxa-8,10-diphenylspiro[5,5]undecane; 1-hydroxy-2,6-diphenyl-4,4-dimethoxypiperidine; 1-hydroxy-2,6-diphenyl-4,4-dihexyloxypiperidine; or 1-hydroxy-2,6-diphenyl-4,4-dioctyloxypiperidine.

Claim 19

A composition according to claim 8 which additionally contains an effective stabilizing amount of a phenolic antioxidant selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

Claim 20

A composition according to claim 17 wherein the phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis(4,6-di-tert-butylphenol).

Claim 21

A compound of the formula IV, V or VI ##STR8## wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 are independently aryl of 6 to 10 carbon atoms or said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOR 15 where R 15 is hydrogen or alkyl of 1 to 20 carbon atoms, --COR 16 where R 16 is alkyl of 1 to 20 carbon atoms, --NR 17 R 18 where R 17 and R 18 are independently hydrogen or alkyl of 1 to 20 carbon atoms, --SR 19 where R 19 is aryl of 6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms --OH, --OCH 3 , --CN, --CF 3 , --NO 2 , -- F, --Cl, --Br and --I; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogens, a linear or branched alkyl of 1 to 30 carbon atoms said alkyl terminated with --OR 20 , --NR 21 R 22 , --SR 23 , --COOR 24 or --CONR 25 R 26 , where R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are independently hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 3 to 18 carbon atoms said alkyl interrupted by one or more --O--, --S--, --SO--, --SO 2 --, --CO--, --COO--, --OCO--, --CONR 27 --, --NR 27 CO-- or --NR 28 -- where R 27 and R 28 independently have the same meaning as R 20 alkenyl of 3 to 20 carbon atoms aryl of 6 to 10 carbon atoms said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOR 29 where R 29 is hydrogen or alkyl of 1 to 20 carbon atoms, --COR 30 where R 30 is alkyl of 1 to 20 carbon atoms, --NR 31 R 32 where R 31 and R 32 are independently hydrogen or alkyl of 1 to 20 carbon atoms, --SR 33 where R 33 is aryl of 6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms, --OH, --OCH 3 , --CN, --CF 3 , --NO 2 , --F, --Cl, --Br and --I; T is a direct bond or --CR 34 R 35 -- where R 34 and R 35 independently have the same meaning as R 1 ; and X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are independently --O--, --S-- or --NR 36 -- where R 36 has the same meaning as R 20 .

Claim 22

A compound of the formula IV, V or VI ##STR8## wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 are independently aryl of 6 to 10 carbon atoms or said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOR 15 where R 15 is hydrogen or alkyl of 1 to 20 carbon atoms, --COR 16 where R 16 is alkyl of 1 to 20 carbon atoms, --NR 17 R 18 where R 17 and R 18 are independently hydrogen or alkyl of 1 to 20 carbon atoms, --SR 19 where R 19 is aryl of 6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms --OH, --OCH 3 , --CN, --CF 3 , --NO 2 , -- F, --Cl, --Br and --I; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogens, a linear or branched alkyl of 1 to 30 carbon atoms said alkyl terminated with --OR 20 , --NR 21 R 22 , --SR 23 , --COOR 24 or --CONR 25 R 26 , where R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are independently hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 3 to 18 carbon atoms said alkyl interrupted by one or more --O--, --S--, --SO--, --SO 2 --, --CO--, --COO--, --OCO--, --CONR 27 --, --NR 27 CO-- or --NR 28 -- where R 27 and R 28 independently have the same meaning as R 20 alkenyl of 3 to 20 carbon atoms aryl of 6 to 10 carbon atoms said aryl substituted by one to three substituents selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, --COOR 29 where R 29 is hydrogen or alkyl of 1 to 20 carbon atoms, --COR 30 where R 30 is alkyl of 1 to 20 carbon atoms, --NR 31 R 32 where R 31 and R 32 are independently hydrogen or alkyl of 1 to 20 carbon atoms, --SR 33 where R 33 is aryl of 6 to 10 carbon atoms or alkyl of 1 to 20 carbon atoms, --OH, --OCH 3 , --CN, --CF 3 , --NO 2 , --F, --Cl, --Br and --I; T is a direct bond or --CR 34 R 35 -- where R 34 and R 35 independently have the same meaning as R 1 ; and X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are independently --O--, --S-- or --NR 36 -- where R 36 has the same meaning as R 20 .

Claim 23

The compound according to claim 19 which is 2,6-diphenyl-4-piperidone ethylene ketal; 2,6-diphenyl-4-piperidone 1,2-hexadecylene ketal; 3,15-diaza-7,11,18,21-tetraoxa-2,4,14,16-tetraphenyl-trispiro[5.2.2.5.2.2]henicosane; 3,15-diaza-1,13-dimethyl-7,11,18,21-tetraoxa-2,4,14,16-tetraphenyl-trispiro[5.2.2.5.2.2.]henicosane; or 9-aza-3,3,7-trimethyl-1,5-dioxa-8,10-diphenylspiro[5,5]undecane.