4,4'-Bipiperidylidene derivatives and their use as stabilizers

Claim 2

A 4,4'-bipiperidylidene compound having the formula (I): ##STR5## wherein each of the symbols Z represents a hydrogen atom, or an alkyl group having from 1 to 3 carbon atoms; and X and Y are the same or different and each represents a hydrogen atom, an oxyl group, a hydroxy group, an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 3 to 6 carbon atoms, an alkoxyalkyl group having from 1 to 3 carbon atoms in its alkyl moiety and from 1 to 18 carbon atoms in its alkoxy moiety, a cyanoalkyl group having 2 or 3 carbon atoms, an alkanoyl group having from 1 to 12 carbon atoms, an alkenoyl group having 3 or 4 carbon atoms, an 2,3-epoxypropyl group, an unsubstituted aralkyl group having 7 or 8 carbon atoms, an aralkyl group having 7 or 8 carbon atoms and having in its aryl moiety up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups and C 1-8 alkoxy groups, a group of the formula --CH 2 CH(R 1 )OR 2 wherein R 1 represents a hydrogen atom, a methyl group, or a phenyl group, and R 2 represents a hydrogen atom, or an acyl group having the formula --COR 5 wherein R 5 represents an alkyl group having from 1 to 17 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms, an unsubstituted phenyl group, a phenyl group having up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups, C 1-8 alkoxy groups and hydroxy groups, an unsubstituted aralkyl group having 7 or 8 carbon atoms, an aralkyl group having 7 or 8 carbon atoms and having in its aryl moiety up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups, C 1-8 alkoxy groups, and hydroxy groups, a styryl group, or a cyclohexyl group, a group of the formula --CH 2 COOR 3 wherein R 3 represents an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 3 to 6 carbon atoms, a phenyl group, an aralkyl group having 7 or 8 carbon atoms, or a cyclohexyl group, or a group of the formula --COOR 4 wherein R 4 represents an alkyl group having from 1 to 8 carbon atoms, a benzyl group, a phenyl group, or a cyclohexyl group and an acid addition salt thereof.

Claim 3

A compound as claimed in claim 1 wherein: each of the symbols Z represents a hydrogen atom or a lower alkyl group having from 1 to 3 carbon atoms; and X and Y are the same or different and each represents a hydrogen atom; an oxyl group; a hydroxy group; an alkyl group having from 1 to 18 carbon atoms; an alkenyl group having from 3 to 6 carbon atoms; an alkoxyalkyl group having from 1 to 3 carbon atoms in its alkyl moiety and from 1 to 18 carbon atoms in its alkoxy moiety; a cyanoalkyl group having 2 or 3 carbon atoms; an alkanoyl group having from 2 to 4 carbon atoms; an alkenoyl group having 3 or 4 carbon atoms; an unsubstituted aralkyl group having 7 or 8 carbon atoms; an aralkyl group having 7 or 8 carbon atoms and up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups and C 1-8 alkoxy groups; a group of the formula --CH 2 CH 2 OR 6 , wherein R 6 represents a hydrogen atom or an acyl group having the formula --COR 7 in which R 7 is an alkyl group having from 1 to 17 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms, a phenyl group, a p-t-butylphenyl group, a 4-hydroxy-3,5-di-t-butylphenyl group or a 4-hydroxy-3,5-di-t-butylphenethyl group; a group of the formula --CH 2 COOR 3 , wherein R 3 represents an alkyl group having from 1 to 18 carbon atoms; or a group of the formula -COOR 4 , wherein R 4 represents an alkyl group having from 1 to 4 carbon atoms.

Claim 4

A compound as claimed in claim 1, wherein: each of the symbols Z represents a hydrogen atom or a methyl group; and X and y are identical and each represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, an alkenyl group having 3 or 4 carbon atoms, a 2-alkoxyethyl group having from 1 to 18 carbon atoms in its alkoxy moiety, an alkanoyl group having from 2 to 4 carbon atoms, an alkenoyl group having 3 or 4 carbon atoms, a 2,3-epoxypropyl group, a benzyl group, or a group of the formula -CH 2 CH 2 -OR 8 , wherein R 8 represents a hydrogen atom or an acyl group of the formula -COR 9 in which R 9 represents an alkyl group having from 1 to 17 carbon atoms or a phenyl group.

Claim 5

An acid addition salt of the compounds as claimed in claim 1 with carboxylic acids.

Claim 6

A compound as claimed in claim 1, wherein selected from the group consisting of: 2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1,',2,2,2',2', 6,6, 6', 6'-decamethyl-4,4'-bipiperidylidene;

Claim 7

1'-dibutyl-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-bis(2-hydroxyethyl)-2,2,2',2', 6,6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-bis(2-acetoxyethyl)-2,2,2',2',6,6,6' ,6'-octamethyl-4,4'-bipiperidylidene; 1,1'-bis(2,3-epoxypropyl)-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-diacetyl-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-diacryloyl-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-dibenzyl-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1-butyl-2,2,2',2', 6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 2,2',6,6'-tetraethyl-2,2',3,3',6,6'-hexamethyl-4,4'-bipiperidylidene; and 2,2,',6,6'-tetraethyl-1,1',2,2',3,3',6,6'-octamethyl-4,4'-bipiperidylidene.

Claim 8

1'-dibutyl-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-bis(2-hydroxyethyl)-2,2,2',2', 6,6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-bis(2-acetoxyethyl)-2,2,2',2',6,6,6' ,6'-octamethyl-4,4'-bipiperidylidene; 1,1'-bis(2,3-epoxypropyl)-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-diacetyl-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-diacryloyl-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-dibenzyl-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1-butyl-2,2,2',2', 6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 2,2',6,6'-tetraethyl-2,2',3,3',6,6'-hexamethyl-4,4'-bipiperidylidene; and 2,2,',6,6'-tetraethyl-1,1',2,2',3,3',6,6'-octamethyl-4,4'-bipiperidylidene.

Claim 9

A compound as claimed in claim 1 selected from the group consisting of: 1,1'-diethyl-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 1,1'-diallyl-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene; 2,2,2',2',6,6,6',6'-octamethyl-1,1'-bis(2-stearoyloxyethyl)-4,4'-bipiperidylidene; 1'-hydroxy-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene-1-oxyl; and

Claim 10

1'-bis(2-benzoyloxyethyl)-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene.

Claim 11

1'-bis(2-benzoyloxyethyl)-2,2,2',2',6,6,6',6'-octamethyl-4,4'-bipiperidylidene.

Claim 12

An organic polymer composition stabilized against photo- and thermal deterioration by the incorporation of a stabilizing amount of a 4,4'-bipiperidylidene derivative having the formula (I) ##STR6##wherein each of the symbols Z represents a hydrogen atom, or an alkyl group having from 1 to 3 carbon atoms, and X and y are the same or different and each repesents a hydrogen atom, an oxyl group, a hydroxy group, an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 3 to 6 carbon atoms, an alkoxyalkyl group having from 1 to 3 carbon atoms in its alkyl moiety and from 1 to 18 carbon atoms in its alkoxy moiety; a cyanoalkyl group having 2 or 3 carbon atoms, an alkanoyl group having from 1 to 23 carbon atoms, an alkenoyl group having 3 or 4 carbon atoms, an 2,3-epoxypropyl group, an unsubstituted aralkyl group having 7 or 8 carbon atoms, an aralkyl group having 7 or 8 carbon atoms and having in its aryl moiety up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups and C -8 alkoxy groups, a group of the formula -CH 2 CH(R 1 )OR 2 wherein R 1 represents a hydrogen atom, a methyl group, or a phenyl group, and R 2 represents a hydrogen atom, or an acyl group having the formula -COR 5 wherein R 5 represents an alkyl group having from 1 to 17 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms, an unsubstituted phenyl group, a phenyl group having up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups, C 1-8 alkoxy groups and hydroxy groups, an unsubstituted aralkyl group having 7 or 8 carbon atoms, an aralkyl group having 7 or 8 carbon atoms and having in its aryl moiety up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups, C 1-8 alkoxy groups and hydroxy groups, a styryl group, or a cyclohexyl group, a group of the formula -CH 2 COOR 3 wherein R 3 represents an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 3 to 6 carbon atoms, a phenyl group, an aralkyl group having 7 or 8 carbon atoms, and a cyclohexyl group, or a group of the formula -COOR 4 wherein R 4 represents an alkyl group having from 1 to 8 carbon atoms, a benzyl group, a phenyl group, or a cyclohexyl group, and an acid addition salt thereof.

Claim 13

An organic polymer composition stabilized against photo- and thermal deterioration by the incorporation of a stabilizing amount of a 4,4'-bipiperidylidene derivative having the formula (I) ##STR6##wherein each of the symbols Z represents a hydrogen atom, or an alkyl group having from 1 to 3 carbon atoms, and X and y are the same or different and each repesents a hydrogen atom, an oxyl group, a hydroxy group, an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 3 to 6 carbon atoms, an alkoxyalkyl group having from 1 to 3 carbon atoms in its alkyl moiety and from 1 to 18 carbon atoms in its alkoxy moiety; a cyanoalkyl group having 2 or 3 carbon atoms, an alkanoyl group having from 1 to 23 carbon atoms, an alkenoyl group having 3 or 4 carbon atoms, an 2,3-epoxypropyl group, an unsubstituted aralkyl group having 7 or 8 carbon atoms, an aralkyl group having 7 or 8 carbon atoms and having in its aryl moiety up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups and C -8 alkoxy groups, a group of the formula -CH 2 CH(R 1 )OR 2 wherein R 1 represents a hydrogen atom, a methyl group, or a phenyl group, and R 2 represents a hydrogen atom, or an acyl group having the formula -COR 5 wherein R 5 represents an alkyl group having from 1 to 17 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms, an unsubstituted phenyl group, a phenyl group having up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups, C 1-8 alkoxy groups and hydroxy groups, an unsubstituted aralkyl group having 7 or 8 carbon atoms, an aralkyl group having 7 or 8 carbon atoms and having in its aryl moiety up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups, C 1-8 alkoxy groups and hydroxy groups, a styryl group, or a cyclohexyl group, a group of the formula -CH 2 COOR 3 wherein R 3 represents an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 3 to 6 carbon atoms, a phenyl group, an aralkyl group having 7 or 8 carbon atoms, and a cyclohexyl group, or a group of the formula -COOR 4 wherein R 4 represents an alkyl group having from 1 to 8 carbon atoms, a benzyl group, a phenyl group, or a cyclohexyl group, and an acid addition salt thereof.

Claim 14

A stabilized polymer composition as claimed in claim 7, wherein: each of the symbols Z represents a hydrogen atom or a lower alkyl group having from 1 to 3 carbon atoms; and X and y are the same or different and each represents a hydrogen atom; an oxyl group; a hydroxy group; an alkyl group having from 1 to 18 carbon atoms; an alkenyl group having from 3 to 6 carbon atoms; an alkoxyalkyl group having from 1 to 3 carbon atoms in its alkyl moiety and from 1 to 18 carbon atoms in its alkoxy moiety; a cyanoalkyl group having 2 or 3 carbon atoms; an alkanoyl group having from 2 to 4 carbon atoms; an alkenoyl group having 3 or 4 carbon atoms; an unsubstituted aralkyl group having 7 or 8 carbon atoms; an aralkyl group having 7 or 8 carbon atoms and up to 3 substituents selected from the group consisting of chlorine atoms, C 1-4 alkyl groups and C 1-8 alkoxy groups; a group of the formula -CH 2 CH 2 OR 6 , wherein R 6 represents a hydrogen atom or an acyl group having the formula -COR 7 in which R 7 is an alkyl group having from 1 to 17 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms, a phenyl group, a p-t-butylphenyl group, a 4-hydroxy-3,5-di-t-butylphenyl group or a 4-hydroxy-3,5-di-t-butylphenethyl group; a group of the formula -CH 2 COOR 3 wherein R 3 represents an alkyl group having from 1 to 18 carbon atoms; or a group of the formula -COOR 4 , wherein R 4 represents an alkyl group having from 1 to 4 carbon atoms.

Claim 15

A stabilized polymer composition as claimed in claim 7, wherein: each of the symbols Z represents a hydrogen atom or a methyl group; and X and Y are identical and each represents a hydrogen atom, an alkyl group haaving from 1 to 4 carbon atoms, an alkenyl group having 3 or 4 carbon atoms, a 2-alkoxyethyl group having from 1 to 18 carbon atoms in its alkoxy moiety, an alkanoyl group having from 2 to 4 carbon atoms, an alkenoyl group having 3 or 4 carbon atoms, a 2,3-epoxypropyl group, a benzyl group, or a group of the formula -CH 2 CH 2 -OR 8 , wherein R 8 represents a hydrogen atom or an acyl group of the formula -COR 9 in which R 9 represents an alkyl group having from 1 to 17 carbon atoms or a phenyl group.

Claim 16

A stabilized polymer composition as claimed in claim 7, wherein said acid addition salts are salts with carboxylic acids.

Claim 17

A stabilized polymer composition as claimed in claim 7, wherein said polymer is an olefin polymer.

Claim 18

A stabilized polymer composition as claimed in claim 7, wherein said polymer is selected from the group consisting of styrene polymers, halogenated vinyl and vinylidene polymers, polyurethanes and polyamides.

Claim 19

A stabilized polymer composition as claimed in claim 7, comprising from 0.01% to 5% by weight of said 4,4'-bipiperidylidene derivative.