Stabilization of synthetic polymers by penta-or-hexa-substituted 4-piperidinol derivatives

Claim 2

A polymer composition stabilized against photo- and thermal- deterioration wherein there is incorporated, in an amount sufficient to prevent said deterioration, a stabilizer comprising a 4-piperidinol derivative having the formula (I) ##STR37## or an acid addition salt thereof, wherein: R 1 and R b are the same or different and each represents a hydrogen atom, a lower alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, provided that R a and R b do not simultaneously represent hydrogen atoms; R c and R d are the same or different and each represents a lower alkyl group; R e represents an alkyl group; R f represents an alkyl group, a phenyl group, an aralkyl group or a 5- or 6-membered aromatic heterocyclic group containing an oxygen, sulphur or nitrogen atom; or R e and R f , together with the carbon atom to which they are attached, represent a cycloalkyl group or a group of the formula ##STR38## wherein R g and R h are the same or different and each represents a hydrogen atom or a lower alkyl group, provided that R h does not represent a hydrogen atom when R g represents a lower alkyl group; R i and R j are the same or different and each represents a lower alkyl group; and X is as hereafter defined: X represents a hydrogen atom, an oxyl radical, an alkyl group, an alkenyl group, an alkoxy-alkyl group, an aralkyl group, which is unsubstituted or which has one or more substituents in its aryl moiety, a 2,3-epoxypropyl group, a group of formula --CH 2 COOR 1 wherein R 1 represents an alkyl group, an alkenyl group, a phenyl group, an aralkyl group or a cyclohexyl group; a group of formula: ##STR39## wherein R 2 represents a hydrogen atom, a methyl group or a phenyl group and R 3 represents a hydrogen atom or an acyl group; an aliphatic acyl group or a group of formula --COOR 4 wherein R 4 represents an alkyl group, a benzyl group or a phenyl group; n is an integer of from 1 to 4 inclusive; when n = 1: Y represents: a hydrogen atom; an aliphatic, araliphatic, alicyclic, aromatic or heterocyclic acyl group; a group of formula --CO.R 5 .COOH wherein R 5 represents an alkylene group, whose chain may optionally be interrupted by a sulphur atom, or a phenylene group, or a metal salt or a lower alkyl ester thereof; a monovalent group obtained by removing a hydroxy group from a sulphur-containing acid; a monovalent group obtained by removing a hydroxy group from a phosphorus-containing acid; a group of formula ##STR40## wherein R 7 represents a hydrogen atom, a lower alkyl group, an aralkyl group or a phenyl group; and R 8 represents an alkyl group, a substituted or unsubstituted aryl group, an aralkyl group or a cyclohexyl group; or R 7 and R 8 , together with the nitrogen atom to which they are attached, represent a piperidino group, a 1-pyrrolidinyl group or a morpholino group; an alkyl group; an alkenyl group; an aralkyl group, which is unsubstituted or has one or more substituents in its aryl moiety; a cyclohexyl group; or a group having the formula: ##STR41## in which R 9 represents a hydrogen atom, a methyl group or a phenyl group and R 10 represents an alkyl group; when n = 2: Y represents an aliphatic, araliphatic, aromatic, alicyclic or heterocyclic diacyl group; a carbonyl group; a sulphinyl group; a sulphonyl group; a group obtained by removing two hydroxy groups from a phosphorus-containing acid; a group of formula ##STR42## a group of formula ##STR43## in which R 7 is as defined above and R 12 represents an alkylene group, an arylene group, which is unsubstituted or has one or more methyl substituents, a xylylene group, a cyclohexylene group, a group of formula ##STR44## (in which R 13 represents an oxygen atom or a methylene group); a group of formula ##STR45## (in which R 14 represents a hydrogen atom or a methyl group); a group of formula ##STR46## or a group of formula ##STR47## an alkylene group; an alkenylene group; a xylylene group or a group of the formula ##STR48## when n = 3: Y represents: a group having the formula ##STR49## a group of formula ##STR50## or a group of the formula ##STR51## when n = 4: Y represents: a group of the formula ##STR52## or a group of the formula ##STR53##

Claim 3

A polymer composition according to claim 1, wherein said 4-piperidinol derivative is incorporated in an amount of from 0.01 to 5.0% by weight, based upon the weight of the polymer.

Claim 4

A polymer composition according to claim 1, wherein said polymer is an olefin or diene polymer.

Claim 5

A polymer composition according to claim 1, wherein said polymer is a halogenated vinyl or vinylidene polymer.

Claim 6

A polymer composition according to claim 1, wherein said polymer is a polyurethane.

Claim 7

A polymer composition according to claim 1, wherein said polymer is a polyamide.

Claim 8

A polymer composition according to claim 1, wherein Y is as defined but other than hydrogen.

Claim 9

A polymer composition according to claim 1, wherein R a and R b are the same or different 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, or an alkynyl group having 3 or 4 carbon atoms, a benzyl group or a phenylethyl group, provided that R a and R b do not simultaneously represent a hydrogen atom; R c and R d are the same or different and each represents an alkyl group having from 1 to 5 carbon atoms; R e represents an alkyl group having from 1 to 9 carbon atoms; R f represents an alkyl group having from 1 to 9 carbon atoms, a phenyl group, a benzyl or phenylethyl group, a 2-, 3- or 4-pyridyl, 2-furyl or 2-thienyl group, or R e and R f , together with the carbon atom to which they are attached, represent a cycloalkyl group having from 5 to 7 carbon atoms, a 2,2,6,6-tetramethylpiperidyl group or a 2,6-diethyl-2,3,6-trimethylpiperidyl group; X represents a hydrogen atom; an oxyl group; an alkyl group having from 1 to 8 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; an aralkyl group having 7 or 8 carbon atoms, which is unsubstituted or has up to 3 chlorine, C 1-4 alkyl, C 1-8 alkoxy or hydroxy substituents, the substituents being the same or different; a 2,3-epoxypropyl group; a group of the formula --CH 2 --COOR 1 wherein R 1 is an alkyl group having from 1 to 18 carbon atoms, an alkenyl group having from 3 to 6 carbon atoms, a phenyl group, a benzyl group, a phenethyl group or a cyclohexyl group; a group of the formula ##STR54## wherein R 2 represents a hydrogen atom, a methyl group of a phenyl group, and R 3 represents a hydrogen atom or a group of the formula --COR 15 in which R 15 represents an alkyl group having from 1 to 17 carbon atoms, an alkenyl group having from 2 to 4 carbon atoms, a phenyl group which is unsubstituted or has up to 3 chlorine, C 1-4 alkyl, C 1-8 alkoxy or hydroxy substituents, the substituents being the same or different, an aralkyl group having 7 or 8 carbon atoms which is unsubstituted or has up to 3 chlorine, C 1-4 alkyl, C 1-8 alkoxy or hydroxy substituents in its aryl moiety, the substituents being the same or different, a styryl group or a cyclohexyl group; an alkanoyl or alkenoyl group having up to 4 carbon atoms; or a group of the formula --COOR 4 in which R 4 represents an alkyl group having from 1 to 8 carbon atoms, a benzyl group or a phenyl group; when n = 1: Y represents a hydrogen atom; a group of the formula --COR 16 in which R 16 represents a hydrogen atom, an alkyl group having from 1 to 17 carbon atoms, an alkenyl group having from 2 to 5 carbon atoms, an alkynyl group having 2 or 3 carbon atoms, a phenyl group which is unsubstituted or has up to 3 chlorine, C 1-4 alkyl, C 1-8 alkoxy, hydroxy or nitro substituents, the substituents being the same or different, a naphthyl group, a styryl group, an aralkyl group having 7 or 8 carbon atoms which may be unsubstituted or have up to 3 chlorine, C 1-4 alkyl, C 1-8 alkoxy or hydroxy substituents, the substituents being the same or different, a phenoxymethyl group, a cyclohexyl group, a 2-, 3- or 4-pyridyl group, a 2-furyl group or a 2-thienyl group; a group of the formula --CO--R 5 --COOH in which R 5 represents an alkylene group having from 1 to 10 carbon atoms whose chain may be interrupted by a sulfur atom; or a phenylene group; or a metal salt thereof or an alkyl ester thereof having from 1 to 4 carbon atoms in its alkyl moiety; a group of the formula --SO 2 .R 6 in which R 6 represents an alkyl group having from 1 to 3 carbon atoms, a phenyl group or a tolyl group; a group of the formula ##STR55## a group of the formula ##STR56## in which R 7 represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a benzyl group a phenylethyl group or a phenyl group, and R 8 represents an alkyl group having from 1 to 18 carbon atoms, a phenyl group which may be unsubstituted or substituted by a chlorine atom or an alkyl group having from 1 to 4 carbon atoms, a naphthyl group, a benzyl group, a phenylethyl group or a cyclohexyl group, or R 7 and R 8 together with the nitrogen atom to which they are attached, represent a piperidino group, a 1-pyrrolidinyl group or a morpholino group; an alkyl group having from 1 to 18 carbon atoms; an alkenyl group having from 3 to 6 carbon atoms; an aralkyl group having from 7 to 9 carbon atoms which is unsubstituted or substituted with up to 3 C 1-4 alkyl and/or hydroxy substituents in its aryl moiety; a cyclohexyl group; or a group of the formula ##STR57## in which R 9 represents a hydrogen atom, a methyl group or a phenyl group, and R 10 represents an alkyl group having from 1 to 8 carbon atoms; when n = 2: Y represents a group of the formula --CO--(R 17 ) m --CO-- in which m is 0 or 1; and R 17 represents an alkylene group having from 1 to 10 carbon atoms, the chain of which may be interrupted by a sulfur atom, an alkenylene group having from 2 to 4 carbon atoms, a phenylene group, a cyclohexylene group, a 2,4-pyridinediyl group, a 2,5-pyridinediyl group, or a 2,5-thiophenediyl group; a carbonyl group; a sulphinyl group; a sulfonyl group; a group of the formula ##STR58## in which R 11 represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a phenyl group, a benzyl group, or a 4-hydroxy-3,5-di-tert-butylbenzyl group; a group of the formula ##STR59## a group of the formula ##STR60## in which R 7 is as defined above; and R 12 represents an alkylene group having from 2 to 10 carbon atoms, an arylene group having from 6 to 10 carbon atoms and optionally having one or more methyl substituents, a cyclohexylene group, a group of the formula ##STR61## in which R 13 represents an oxygen atom or a methylene group, a group of the formula ##STR62## in which R 14 represents a hydrogen atom or a methyl group, a group of the formula ##STR63## an alkylene group having from 1 to 10 carbon atoms; an alkenylene group having from 4 to 10 carbon atoms; a xylylene group; or a group of the formula ##STR64## when n = 4: Y represents a group of the formula ##STR65## or a group of the formula ##STR66##

Claim 10

A polymer composition according to claim 8, wherein Y is as defined but other than hydrogen.

Claim 11

A polymer composition according to claim 1, wherein R a and R b are the same or different and each represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, or an allyl group, provided that R a and R b do not simultaneously represent a hydrogen atom; R c and R d are the same or different and each represents an alkyl group having from 1 to 5 carbon atoms; R e represents an alkyl group having from 1 to 5 carbon atoms; R f represents an alkyl group having from 1 to 9 carbon atoms, a phenyl group, a benzyl or 2-phenylethyl group, a 2-, 3- or 4-pyridyl group or a 2-furyl group, or R e and R f , together with the carbon atom to which they are attached, represent a cyclopentyl group, a cyclohexyl group or a 2,2,6,6-tetramethylpiperidyl group; X represents a hydrogen atom; an alkyl group having from 1 to 8 carbon atoms; an alkenyl group having 3 or 4 carbon atoms; an alkoxyalkyl group having in all from 3 to 6 carbon atoms; a benzyl group; a methylbenzyl group; a 2,3-epoxypropyl group; a group of the formula --CH 2 COOR 1 in which R 1 represents an alkyl group having from 1 to 4 carbon atoms; a group of the formula ##STR67## in which R 2 represents a hydrogen atom, a methyl group or a phenyl group; and R 3 represents a hydrogen atom or a group of the formula --COR 15 in which R 15 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 benzyl group or a 4-hydroxy-3,5-di-tert-butyl-phenylethyl group; or an alkanoyl or alkenoyl group having up to 4 carbon atoms; when n = 1: Y represents: a hydrogen atom; a group of the formula --COR 16 in which R 16 represents; an alkyl group having from 1 to 17 carbon atoms, an alkenyl group having from 2 to 5 carbon atoms, an alkynyl group having 2 or 3 carbon atoms, a phenyl group which is unsubstituted or is substituted by a chlorine atom, an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 8 carbon atoms, a hydroxy group or a nitro group, or a 4-hydroxy-3,5-di-tert-butylphenyl group, a benzyl or phenylethyl group, a 4-hydroxy-3,5-di-tert-butyl-phenylethyl group, a naphthyl group, a styryl group, a cyclohexyl group, or a phenoxymethyl group; a group of the formula --CO--R 5 --COO--alkyl in which R 5 represents an alkylene group having from 1 to 8 carbon atoms or a phenylene group, and the alkyl has from 1 to 4 carbon atoms; a group of the formula --SO 2 --R 6 in which R 6 represents a methyl, phenyl or tolyl group; a group of the formula ##STR68## a group of the formula ##STR69## in which R 7 represents a hydrogen atom, a methyl, phenyl or benzyl group; and R 8 represents an alkyl group having from 1 to 18 carbon atoms, a phenyl group which may be unsubstituted or substituted by a chlorine atom or a methyl group, a naphthyl group, a benzyl group, a phenylethyl group or a cyclohexyl group; or R 7 and R 8 together with the nitrogen atom to which they are attached represent a piperidino group, a 1-pyrrolidinyl group or a morpholino group; an alkyl group having from 1 to 18 carbon atoms; an allyl group; a benzyl group; a cyclohexyl group; or a group of the formula ##STR70## in which R 9 represents a hydrogen atom or a methyl group; and R 10 represents a methyl or ethyl group; when n = 2: Y represents; a group of the formula --CO--(R 17 ) m --CO-- in which m is 0 or 1; and R 17 represents an alkylene group having from 1 to 10 carbon atoms, a group of the formula --CH 2 CH 2 --S--CH 2 CH 2 -- or --CH═CH--, a phenylene group, a cyclohexylene group or a 2,5-thiophenediyl group; a carbonyl group; a sulphinyl group; a group of the formula >P-phenyl; ##STR71## a group of the formula --CO--NH--R 12 --NH--CO-- in which R 12 represents an alkylene group having from 2 to 10 carbon atoms, a phenylene group, a tolylene group, a xylylene group, a naphthylene group, a cyclohexylene group or a group of the formula ##STR72## an alkylene group having from 2 to 6 carbon atoms; a 2-butenylene group; a m-xylylene group; or a group of the formula ##STR73## when n = 3: Y represents a group of formula ##STR74## and, when n = 4: Y represents a group of the formula ##STR75##

Claim 12

A polymer composition according to claim 10, wherein Y is as defined but other than hydrogen.

Claim 13

A polymer composition according to claim 1, wherein: R a , R c and R e each represents methyl groups; R b represents a hydrogen atom; R d and R f each represents ethyl groups; X represents a hydrogen atom, a methyl group, an allyl group, a benzyl group, a 2,3-epoxypropyl group, or a group of the formula --CH 2 CH 2 OR 3 in which R 3 represents a hydrogen atom, an alkanoyl group having from 2 to 18 carbon atoms or a benzoyl group; n is 1, 2 or 3; when n is 1: Y represents a group of the formula --COR 16 in which R 16 represents an alkyl group having from 1 to 17 carbon atoms, a phenyl group which is unsubstituted or has up to three C 1-4 alkyl and/or hydroxy substituents, or a 4-hydroxy-3,5-di-tert-butylphenethyl group; or a group of the formula --CO--NHR 8 in which R 8 represents an alkyl group having from 1 to 18 carbon atoms, a phenyl group or a cyclohexyl group; and when n = 2: Y represents a group of the formula --CO--(R 17 ) m --CO-- in which m is 0 or 1; and R 17 represents an alkylene group having from 1 to 10 carbon atoms, a group of the formula --CH 2 CH 2 SCH 2 CH 2 -- or a phenylene group; a sulphinyl group; or a group of the formula --CO--NH--R 12 --NH--CO-- in which R 12 represents a hexamethylene group, a 2,4-tolylene group or a methylenedi-p-phenylene group.

Claim 14

A polymer composition according to claim 12, wherein n is 1 and Y represents a group of the formula --COR 16 , or n is 2 and Y represents a group of the formula --CO--R 17 --CO-- wherein R 16 and R 17 are as defined in claim 12.

Claim 15

A polymer composition according to claim 13, wherein X represents a hydrogen atom, a methyl group, an allyl group, a benzyl group or a 2,3-epoxypropyl group.

Claim 16

A polymer composition according to claim 14, wherein n = 1 and Y represents a group of the formula --COR 16 (R 16 represents an alkyl group having from 1 to 17 carbon atoms or a phenyl group), or n = 2 and Y represents a group of the formula --CO--R 17 --CO-- (R 17 represents an alkylene group having from 1 to 10 carbon atoms).

Claim 17

A polymer composition according to claim 1, wherein said 4-piperidinol derivative is selected from the group consisting of:

Claim 18

6-diethyl-2,3,6-trimethyl-4-piperidyl stearate, 2,6-diethyl-2,3,6-trimethyl-4-piperidyl crotonate, 2,6-diethyl-2,3,6-trimethyl-4-piperidyl benzoate, 2,6-diethyl-2,3,6-trimethyl-4-piperidyl p-t-butylbenzoate, 2,6-diethyl-2,3,6-trimethyl-4-piperidyl β-(4-hydroxy-3,5-di-t-butylphenyl)-propionate, 1-(2,3-epoxypropyl)-2,6-diethyl-2,3,6-trimethyl-4-piperidyl benzoate, 1-(2-acetoxyethyl)-2,6-diethyl-2,3,6-trimethyl-4-piperidyl benzoate, 1-(2-benzoyloxyethyl)-2,6-diethyl-2,3,6-trimethyl-4-piperidyl benzoate, 1-acetyl-2,6-diethyl-2,3,6-trimethyl-4-piperidyl benzoate, bis(2,6-diethyl-2,3,6-trimethyl-4-piperidyl)sebacate, bis(2,6-diethyl-2,3,6-trimethyl-4-piperidyl)terephthalate, tris(2,6-diethyl-2,3,6-trimethyl-4-piperidyl)phosphite, and acid addition salt thereof.

Claim 19

6-diethyl-2,3,6-trimethyl-4-piperidyl stearate, 2,6-diethyl-2,3,6-trimethyl-4-piperidyl crotonate, 2,6-diethyl-2,3,6-trimethyl-4-piperidyl benzoate, 2,6-diethyl-2,3,6-trimethyl-4-piperidyl p-t-butylbenzoate, 2,6-diethyl-2,3,6-trimethyl-4-piperidyl β-(4-hydroxy-3,5-di-t-butylphenyl)-propionate, 1-(2,3-epoxypropyl)-2,6-diethyl-2,3,6-trimethyl-4-piperidyl benzoate, 1-(2-acetoxyethyl)-2,6-diethyl-2,3,6-trimethyl-4-piperidyl benzoate, 1-(2-benzoyloxyethyl)-2,6-diethyl-2,3,6-trimethyl-4-piperidyl benzoate, 1-acetyl-2,6-diethyl-2,3,6-trimethyl-4-piperidyl benzoate, bis(2,6-diethyl-2,3,6-trimethyl-4-piperidyl)sebacate, bis(2,6-diethyl-2,3,6-trimethyl-4-piperidyl)terephthalate, tris(2,6-diethyl-2,3,6-trimethyl-4-piperidyl)phosphite, and acid addition salt thereof.