CA1304368C - 1,2,2,6,6-pentamethyl-4-piperidylaminotriazine derivatives and their use as stabilizers - Google Patents
1,2,2,6,6-pentamethyl-4-piperidylaminotriazine derivatives and their use as stabilizersInfo
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- CA1304368C CA1304368C CA000545067A CA545067A CA1304368C CA 1304368 C CA1304368 C CA 1304368C CA 000545067 A CA000545067 A CA 000545067A CA 545067 A CA545067 A CA 545067A CA 1304368 C CA1304368 C CA 1304368C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
Abstract
3-16119/+/CHM 26 1,2,2,6,6-Pentamethyl-4-piperidylaminotriazine derivatives and their use as stabilizers Abstract of the Disclosure Compounds of the formula (I) (I) wherein R1 and R5 are independently hydrogen, C1-C12-alkyl, C5-C7-cyclo-alkyl or a group of the formula (II), (II) R2, R3 and R4 are independently C2-C12-alkylene, R is a group of the formula (III) (III) wherein R6 is C2-C8-dialkylamino, C1-C4-alkoxy, pyrrolidinyl, piperidino, morpholino, hexahydroazepinyl or a group of the formula (IV), (IV) R7 and R8 are independently C1-C12-alkyl, C5-C7-cycloalkyl, benzyl or a group of the formula (II), subject to the proviso that both, R1 and R5 are different from hydrogen, if R is a group
Description
1,2,2,6,6-Pentamethyl-4-piperidylaminotriazine derivatives and their use as stabilizers The present invention relates to novel 1,2,2,6,6-penta-methyl-4-piperidylaminotriazine derivatives which can be used as light stabilizers, heat stabilizers and/or oxidation stabilizers for organic materials, especially synthetic polymers.
It is known that synthetic polymers undergo progressive changes in their physical properties, such as loss of mechanical strength and colour changes, when they are exposed to sunlight or other sources of ultraviolet light.
To retard the deleterious effect of ultraviolet radiation on synthetic polymers, it has been proposed to use various additives having light-stabilizing properties, such as certain benzophenone and benzotriazole derivatives, nickel complexes, alkylidenemalonates, cyanoacrylates and sterically hindered amines.
Japanese Patent Publication Sho 57-38589, published in August 1982, describes polyalkylpiperidylaminotriazine derivatives and their use as light stabilizers, heat stabilizers and oxidation stabilizers for polymeric materials. In Example 13 of this publication the preparation of NI,NII,NIII,NIV-tetrakis-[2,4-bis[N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl]-4,7-diazadecane-1,10-diamine is disclosed.
EP 112 690, published in April 1987, describes compounds containing three 2,4-bis[pentamethylpiperidylamino]-1,3,5-triazin-6-ylamino radicals and their use as polymer stabilizers.
130436~
In Research Disclosure 25, 330 (1985) the compound N ,N ,N ,N -tetrakis[2,4-bis[N-(2,2,6,6-tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl]-4,7-diazadecane-l,10-diamine and its use as stabilizer for polyethylene films is disclosed.
The present invention pertains to novel compounds of the formula (I) R R R R
1 R2 N 3 N R4 N R5 (I) wherein Rl and R5 are independently hydrogen, Cl-C12-alkyl, C5-C7-cycloalkyl or a group of the formula (II) 3 \ ~ 3 H3C-N ~ - (II) ,_.
H C / \ CH
R2, R3 and R4 are independently C2-C12-alkylene, R is a group of the formula (III) ~N ~
I ll 6 N~ ~N
,!~ (III) H3C \ ¦ ¦ / CH3 H3C / I \ CH3 ~"..-2a -wherein R6 is C2~Ca-dialkylamino, C1-C4-alkoxy, pyrrolidinyl, piperidino, morpholino, hexahydroa~epinyl or a group of the formula (IV), ~-~
--~--R8 H3C\t i~CH3 (IV) H3C ~ CH3 R7 and R8 are independently Cl-Cl2-alkyl, Cs-C7-cycloalkyl, benzyl or a group of the formula (II), subject to the proviso that both, R
and R5 are different from hydrogen, if R i8 a group ~,C\ / N3 HsC4-~
H C ~ \ CH
H C~ \ ~ \CH
R1, Rs~ R7 and Rg as C1-Cl2-alkyl are for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl. C1-C6-alkyl which may be straight chain or branched is preferred. Rl and Rs are preferably methyl and R7 and Rg are preferably methyl, ethyl or butyl, in particular n-butyl.
R1, Rs, R7 and Rg as Cs-C7-cycloalkyl are for example cyclopentyl, cyclohexyl or cycloheptyl, preferably cyclohexyl.
Rz, R3 and R4 as C2-C12-alkylene are for example ethylene, tri-methylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, decamethylene or dodeca-methylene. C2-C6-alkylene i9 preferred. R2 and R4 as trimethylene and R3 as ethylene are particularly preferred.
R6 as C2-C8-~ialkylam~no is for example dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino or diisobutylamino.
~304368 R6 as Cl-C4-alkoxy is for example methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.
R6 is in particular morpholino.
Those compounds of formula (I) are preferred, wherein R6 is CZ-ca-di alkylamino, morpholino or a group of the formula (IV).
Those compounds of formula (I) are particularly preferred, wherein R6 is a group of the formula (IV) and R7 and R8 are independently C1~Clz-alkyl or a group of the formula (II).
R1 and R5 are preferably Cl-Clz-alkyl~ Gs-c7-cycloalkyl or a group of the formula (II), in particular Cl-C6-alkyl or a group of the formula (II).
Compounds of formula (I) wherein R1 and R5 are methyl, RZ, R3 and R4 are independently ethylene or trimethylene, R6 is a group of the formula (IV) and R7 and RB are independently Cl-C4-alkyl or a group of the formula (II), are also preferred.
Those compounds of formula (I) are of interest, wherein R1 and R5 are methyl, R2 and R4 are trimethylene, R3 is ethylene, R6 is a group of the formula (IV), R7 and R8 which are identical are Cl-Clz-alkyl.
R7 and Ra are preferably Cl-C6-alkyl, in particular methyl, ethyl or butyl, and especially preferred n-butyl.
The compounds of the formula (I) can be prepared by various methods known per se, for example by N-methylation of compounds of the formula (Ia) B~
~304368 R' R' Rl-~-R2-~-R3-~-R4-~-Rs (Ia) wherein R, and Rs are independently hydrogen, C1-C12-alkyl, Cs-C7-cyclo-alkyl or a group of the formula (II'), H3C\ /CH3 H-N\ /-- (II') R2~ R3 and R4 have the meanings given above, R' is a group of the formula (III'), ~N\
- -Rs ~.~
~-R7 (III') H3C\i i/CH3 H3C ~ CH3 R6 is C2-C3-dialkylamino, C1-C4-alkoxy, pyrrolidinyl, piperidino, morpholino, hexahydroazepinyl or a group of the formula (IV'), -~-R8 H C / \ CH (IV~) H3C ~ CH3 R7 and R,3 are independently C1-C12-alkyl, Cs-C7-cycloalkyl, benzyl or a group of the formula (II').
The N-methylation can be carried out by various methods known per se, for example by reacting the compound of the formula (Ia) with an excess of formaldehyde and formic acid (Eschweiler-Clarke reaction) or with formaldehyde and hydrogen in the presence of an hydrogenation catalyst such as e.g. platinum or palladium.
~,' 1304~68 If Rl and Rs are hydrogen, it is possible that none or only one of these hydrogens is exchanged by a methyl group during the N-methylation of the compounds of formula (Ia). This depends on the reaction conditions, for example the reaction time and the molar amount of formaldehyde and formic acid used.
Accordingly the reaction mixture may still contain amounts of compounds of the formulae (Ib) and (Ic) H-~-R2-~-R3-~-R4-~-H (Ib) H-~-R2-~-R3-~-R4-~-CH3 (Ic) wherein R, R2, R3 and R4 are as defined above. Such reaction mixtures can be used in the same way as the pure final product as long as the content of the incompletely methylated compounds of the formulae (Ib) and (Ic) does not exceed 30 %.
If desired, the compounds of the reaction mixture can be separated in a conventlonal manner, for example by chromatographic methods.
A further preferred embodiment of the invention is a composition comprising 70 % to 99 % by weight of a compound of the formula (I) wherein Rl and Rs are methyl, R, R2, R3 and R4 have the meaning~
given above and O to 30 % by weight of a compound of the formula (Ib) H-~-R2-~-R3-~-R4-~-H (Ib) and O to 30 % by weight of a compound of the formula (Ic), H-~-Rz-~-R3-~-R4-~-CH3 ~Ic) wherein R, R2, R3 and R4 are as defined above.
A composition comprising 70 % to 99 % by weight of a compound of formula (I) wherein Rl and Rs are methyl, Rz and R4 are tri-methylene, R3 is ethylene, R is a group of the formula (III) wherein R6 is a group of the formula (IV) and R7 and Rg which are identical are C1-C12-alkyl and 0 to 30 % by weight of a compound of the formula (Ib) and 0 to 30 % by weight of a compound of the formula (Ic) wherein R, R2, R3 and R4 are as defined above, is especially preferred.
The compounds of the formula (Ia) can be prepared by analogy to known processes, for example as described in US 4,108,829. Prefer-ably, they are prepared by reacting a polyamine of the formula with a triazine of the formula Cl~ -R6 ~-R7 H3C~t I~CH3 H3C ~ CH3 R1, R2, R3, R4, Rs~ R6 and R7 are as defined above.
The reaction can be carried out in an inert solvent in the presence of a base, preferably an inorganic base, in a quantity at least equivalent to the hydrochloric acid liberated in the reaction.
The starting materials are known or can be prepared by analogy to known methods.
The compounds of formula (I) are very effective in improving the light stability, heat stability and/or oxidation stability of organic materials, in particular synthetic polymers, especially polyolefins.
In general polymers which can be stabilized include:
` 1304368 1. Polymers of monoolefins and diolefins, for example poly-propylene, polyisobutylene, polybutene-l, polymethylpentene-l, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optioanlly csn be crosslinked), for example high density poly-ethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).
It is known that synthetic polymers undergo progressive changes in their physical properties, such as loss of mechanical strength and colour changes, when they are exposed to sunlight or other sources of ultraviolet light.
To retard the deleterious effect of ultraviolet radiation on synthetic polymers, it has been proposed to use various additives having light-stabilizing properties, such as certain benzophenone and benzotriazole derivatives, nickel complexes, alkylidenemalonates, cyanoacrylates and sterically hindered amines.
Japanese Patent Publication Sho 57-38589, published in August 1982, describes polyalkylpiperidylaminotriazine derivatives and their use as light stabilizers, heat stabilizers and oxidation stabilizers for polymeric materials. In Example 13 of this publication the preparation of NI,NII,NIII,NIV-tetrakis-[2,4-bis[N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl]-4,7-diazadecane-1,10-diamine is disclosed.
EP 112 690, published in April 1987, describes compounds containing three 2,4-bis[pentamethylpiperidylamino]-1,3,5-triazin-6-ylamino radicals and their use as polymer stabilizers.
130436~
In Research Disclosure 25, 330 (1985) the compound N ,N ,N ,N -tetrakis[2,4-bis[N-(2,2,6,6-tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl]-4,7-diazadecane-l,10-diamine and its use as stabilizer for polyethylene films is disclosed.
The present invention pertains to novel compounds of the formula (I) R R R R
1 R2 N 3 N R4 N R5 (I) wherein Rl and R5 are independently hydrogen, Cl-C12-alkyl, C5-C7-cycloalkyl or a group of the formula (II) 3 \ ~ 3 H3C-N ~ - (II) ,_.
H C / \ CH
R2, R3 and R4 are independently C2-C12-alkylene, R is a group of the formula (III) ~N ~
I ll 6 N~ ~N
,!~ (III) H3C \ ¦ ¦ / CH3 H3C / I \ CH3 ~"..-2a -wherein R6 is C2~Ca-dialkylamino, C1-C4-alkoxy, pyrrolidinyl, piperidino, morpholino, hexahydroa~epinyl or a group of the formula (IV), ~-~
--~--R8 H3C\t i~CH3 (IV) H3C ~ CH3 R7 and R8 are independently Cl-Cl2-alkyl, Cs-C7-cycloalkyl, benzyl or a group of the formula (II), subject to the proviso that both, R
and R5 are different from hydrogen, if R i8 a group ~,C\ / N3 HsC4-~
H C ~ \ CH
H C~ \ ~ \CH
R1, Rs~ R7 and Rg as C1-Cl2-alkyl are for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl. C1-C6-alkyl which may be straight chain or branched is preferred. Rl and Rs are preferably methyl and R7 and Rg are preferably methyl, ethyl or butyl, in particular n-butyl.
R1, Rs, R7 and Rg as Cs-C7-cycloalkyl are for example cyclopentyl, cyclohexyl or cycloheptyl, preferably cyclohexyl.
Rz, R3 and R4 as C2-C12-alkylene are for example ethylene, tri-methylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, decamethylene or dodeca-methylene. C2-C6-alkylene i9 preferred. R2 and R4 as trimethylene and R3 as ethylene are particularly preferred.
R6 as C2-C8-~ialkylam~no is for example dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino or diisobutylamino.
~304368 R6 as Cl-C4-alkoxy is for example methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.
R6 is in particular morpholino.
Those compounds of formula (I) are preferred, wherein R6 is CZ-ca-di alkylamino, morpholino or a group of the formula (IV).
Those compounds of formula (I) are particularly preferred, wherein R6 is a group of the formula (IV) and R7 and R8 are independently C1~Clz-alkyl or a group of the formula (II).
R1 and R5 are preferably Cl-Clz-alkyl~ Gs-c7-cycloalkyl or a group of the formula (II), in particular Cl-C6-alkyl or a group of the formula (II).
Compounds of formula (I) wherein R1 and R5 are methyl, RZ, R3 and R4 are independently ethylene or trimethylene, R6 is a group of the formula (IV) and R7 and RB are independently Cl-C4-alkyl or a group of the formula (II), are also preferred.
Those compounds of formula (I) are of interest, wherein R1 and R5 are methyl, R2 and R4 are trimethylene, R3 is ethylene, R6 is a group of the formula (IV), R7 and R8 which are identical are Cl-Clz-alkyl.
R7 and Ra are preferably Cl-C6-alkyl, in particular methyl, ethyl or butyl, and especially preferred n-butyl.
The compounds of the formula (I) can be prepared by various methods known per se, for example by N-methylation of compounds of the formula (Ia) B~
~304368 R' R' Rl-~-R2-~-R3-~-R4-~-Rs (Ia) wherein R, and Rs are independently hydrogen, C1-C12-alkyl, Cs-C7-cyclo-alkyl or a group of the formula (II'), H3C\ /CH3 H-N\ /-- (II') R2~ R3 and R4 have the meanings given above, R' is a group of the formula (III'), ~N\
- -Rs ~.~
~-R7 (III') H3C\i i/CH3 H3C ~ CH3 R6 is C2-C3-dialkylamino, C1-C4-alkoxy, pyrrolidinyl, piperidino, morpholino, hexahydroazepinyl or a group of the formula (IV'), -~-R8 H C / \ CH (IV~) H3C ~ CH3 R7 and R,3 are independently C1-C12-alkyl, Cs-C7-cycloalkyl, benzyl or a group of the formula (II').
The N-methylation can be carried out by various methods known per se, for example by reacting the compound of the formula (Ia) with an excess of formaldehyde and formic acid (Eschweiler-Clarke reaction) or with formaldehyde and hydrogen in the presence of an hydrogenation catalyst such as e.g. platinum or palladium.
~,' 1304~68 If Rl and Rs are hydrogen, it is possible that none or only one of these hydrogens is exchanged by a methyl group during the N-methylation of the compounds of formula (Ia). This depends on the reaction conditions, for example the reaction time and the molar amount of formaldehyde and formic acid used.
Accordingly the reaction mixture may still contain amounts of compounds of the formulae (Ib) and (Ic) H-~-R2-~-R3-~-R4-~-H (Ib) H-~-R2-~-R3-~-R4-~-CH3 (Ic) wherein R, R2, R3 and R4 are as defined above. Such reaction mixtures can be used in the same way as the pure final product as long as the content of the incompletely methylated compounds of the formulae (Ib) and (Ic) does not exceed 30 %.
If desired, the compounds of the reaction mixture can be separated in a conventlonal manner, for example by chromatographic methods.
A further preferred embodiment of the invention is a composition comprising 70 % to 99 % by weight of a compound of the formula (I) wherein Rl and Rs are methyl, R, R2, R3 and R4 have the meaning~
given above and O to 30 % by weight of a compound of the formula (Ib) H-~-R2-~-R3-~-R4-~-H (Ib) and O to 30 % by weight of a compound of the formula (Ic), H-~-Rz-~-R3-~-R4-~-CH3 ~Ic) wherein R, R2, R3 and R4 are as defined above.
A composition comprising 70 % to 99 % by weight of a compound of formula (I) wherein Rl and Rs are methyl, Rz and R4 are tri-methylene, R3 is ethylene, R is a group of the formula (III) wherein R6 is a group of the formula (IV) and R7 and Rg which are identical are C1-C12-alkyl and 0 to 30 % by weight of a compound of the formula (Ib) and 0 to 30 % by weight of a compound of the formula (Ic) wherein R, R2, R3 and R4 are as defined above, is especially preferred.
The compounds of the formula (Ia) can be prepared by analogy to known processes, for example as described in US 4,108,829. Prefer-ably, they are prepared by reacting a polyamine of the formula with a triazine of the formula Cl~ -R6 ~-R7 H3C~t I~CH3 H3C ~ CH3 R1, R2, R3, R4, Rs~ R6 and R7 are as defined above.
The reaction can be carried out in an inert solvent in the presence of a base, preferably an inorganic base, in a quantity at least equivalent to the hydrochloric acid liberated in the reaction.
The starting materials are known or can be prepared by analogy to known methods.
The compounds of formula (I) are very effective in improving the light stability, heat stability and/or oxidation stability of organic materials, in particular synthetic polymers, especially polyolefins.
In general polymers which can be stabilized include:
` 1304368 1. Polymers of monoolefins and diolefins, for example poly-propylene, polyisobutylene, polybutene-l, polymethylpentene-l, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optioanlly csn be crosslinked), for example high density poly-ethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefines and diolefines with each other or with other vinyl monomers, such as, for example, ethylene/propylene, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE), propylene~butene-l, ethylene/hexene, ethylene/ethylpentene, ethylene/heptene, ethylene/octene, propylene/isobutylene, ethylene/butene-1, propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates, ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/ acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene; as well as mixtures of such copolymers and their mixtures with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene-copolymers, LDPE/EVA, LDPE/EAA, LLDPE/EVA and LLDPE/EAA.
;
3a. Hydrocarbon resins (for example Cs-Cg) and hydrogenated modifi-cations thereof (for example tackyfiers).
;
3a. Hydrocarbon resins (for example Cs-Cg) and hydrogenated modifi-cations thereof (for example tackyfiers).
4. Polystyrene, poly-(p-methylstyrene), poly-(a-methylstyrene).
5. Copolymer3 of styrene or ~-methylstyrene with dienes or acrylic derivatives, such as, for example, styrenefoutadiene, styrene/
acrylonitrile, styrene/alkyl methacrylate, styrene/maleic anhydride, styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/nethyl acrylate; mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene, such as, for example, styrene/butadiene/
styrene, styrene/ isoprene/styrene, styrene/ethylene/butylene/
styrene or styrene/ ethylene/propylene/styrene.
acrylonitrile, styrene/alkyl methacrylate, styrene/maleic anhydride, styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/nethyl acrylate; mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene, such as, for example, styrene/butadiene/
styrene, styrene/ isoprene/styrene, styrene/ethylene/butylene/
styrene or styrene/ ethylene/propylene/styrene.
6. Graft copolymers of styrene or ~-methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 5), for instance the copolymer mixtures known a~ ABS-, MBS-, ASA- or AES-polymers.
7. Halogen-containing polymers, such as polychloroprene, chlori-nated rubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrine homo- and copolymers, polymers from halogen-containing vinyl compounds,as for example, polyvinylchloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, as for example, vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
`"` 1304368 8. Polymers which are derived from ~,~-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylate3, polyacrylamide and polyacrylonitrile.
`"` 1304368 8. Polymers which are derived from ~,~-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylate3, polyacrylamide and polyacrylonitrile.
9. Copolymers from the monomers mentioned under 8) with each other or with other unsaturated monomers, such as, for instance, acrylo-nitrile/butadien, acrylonitrile/alkyl acrylate, acrylonitrile/
alkoxyalkyl acrylate or acrylonitrile/vinyl halogenide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
alkoxyalkyl acrylate or acrylonitrile/vinyl halogenide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
10. Polymers which are derived from unsaturated alcohols and amines, or acyl derivatives thereof or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine; as well as their copolymers with olefins mentioned in 1) above.
11. Homopolymers and copolymers of cyclic ethers, such as poly-alkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ether3.
12. Polyacetals, such as polyoxymethylene and those polyoxy-methylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
13. Polyphenylene oxides and sulfides, and mixtures of poly-phenylene oxides with polystyrene or polyamides.
14. Polyurethanes which are derived from polyethers, polyesters or polybutadiens with terminal hydroxyl groups on the one side and aliphatic or aromatic polyisocyanates on the other side, as well as precursors thereof (polyisocyanates, polyols or prepolymers).
15. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corre-sponding lactams, such as polyamide 4, polyamide 6, polya~ide 6/6, ` 1304368 6/10, 6l9, 6/12 and 4l6, polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m-xylenediamine and adipic acid; polyamides prepared from hexamethylene diamine and isophthalic or/and terephthalic acid and optionally an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide. Further copolymers of the aforemen-tioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as for instance, with polyethylene glycol, polypropylene glycol or polytetramethylene glycols. Polyamides or copolyamides modified with EPDM or ABS. Polyamides condensed during processing (RIM-polyamide systems).
16. Polyureas, polyimides and polyamide-imides.
17. Polyesters which are derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate, poly-[2,2,-(4-hydroxyphenyl)-propane~ terephthalate and polyhydroxybenzoates as well as block-copolyether-esters derived from polyethers having hydroxyl end groups.
18. Polycarbonates and polyester-carbonates.
19. Polysulfones, polyethersulfones and polyetherketones.
20. Crosslinked polymers whlch are derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/
formaldehyde resins.
-21. Drying and non-drying alkyd resins.
i30~368 22. ~nsaturated polyester resins which are derived from copoly-esters of saturated and unsaturated dicarboxylic acids with poly-hydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low inflammability.
formaldehyde resins.
-21. Drying and non-drying alkyd resins.
i30~368 22. ~nsaturated polyester resins which are derived from copoly-esters of saturated and unsaturated dicarboxylic acids with poly-hydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low inflammability.
23. Thermosetting acrylic resins, derived from substituted acrylic esters, such as epoxy-acrylates, urethane-acrylates or polyester-acrylates.
24. Alkyd resins, polyester resins or acrylate resins in admixture with melamine resins, urea resins, polyisocyanates or epoxide resins as crosslinking agents.
25. Crosslinked epoxide resins which are derived from polyepoxides, for example from bis-glycidyl ethers or from cycloaliphatic di-epoxides.
26. Natural polymers, such as cellulose, rubber, gelatine and derivatives thereof which are chemically modified in a polymer-homologous manner, such as cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, such as methyl-cellulose; rosins and their derivatives.
27. Mixtures of polymers as msntioned above, for example PP/EPDM, Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC~MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic P~R, POM/acrylate, POM/MBS, PPE/HIPS, PPEIPA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPE.
28. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellithates) and also mixtures of synthetic esters ~ ~304~68 with mineral oils in any weight ratios, which materials may be used as plasticizer for polymers or as textile spinnlng oils, a~ well as aqueous emulsions of such materials.
29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
The compounds of formula (I) are especially useful as stabilizers for non-crosslinked homo- or copolymers of ~-olefins containing at least 80 % of polymerized ~-olefinl in particular homopolymers of ethylene, propylene, l-butene, 2-methylpropene, 3-methyl-1-butene or 4-methyl-1-pentene and their copolymers with each other or with other unsaturated compounds such as styrene, butadiene, vinyl acetate, acrylic acid, methyl or ethyl acrylate or methyl or ethyl methacrylate. Of particular technical interest are polyethylene and polypropylene.
The compounds of formula (I) can be mixed with the organic material in various proportions depending on the nature of the material to be stabilized, on the end use and on the presence of other additives.
In general it is advantageous to employ from 0.01 to 5 % by weight of the compounds of formula (I), relative to the weight of the material to be stabilized, preferably from 0.1 to 2 %.
The compounds of formula (I) can be incorporated into the organic material via various processes known per se, such as e.g. dry blending in the form of powders, or wet mixing in the form of solutions or suspensions, or mixing in the form of a master-batch which contains the compounds of formula (I) in a concentration of e.g. 5 to 25 % by weight; in these operation~, the organic material can be employed in the form of powder, granules, a solution, a suspension or in the form of a latex.
~304368 The compounds of formula (I) and, if desired, further additlves can also be mixed into a melt of the material to be stabilized, before or during shaping.
The resulting stabilized materials can be applied in various forms, e.g. sheets, fibres, tapes, bottles, tubes or other profiles. The compounds of formula (I) are especially useful as stabilizers for polypropylene fibres, tapes and films.
If desired, other additives, such as e.g. antioxidants, phosphites, W absorbers, nickel stabilizers, pigments, fillers, plasticizers, antistatic agents, blowing agents, flameproofing agents, lubricants, anti-corrosion agents and metal deactivators, can be added to the mixture of the compounds of the invention with the organic mate-rials. Examples of additives which can be mixed with the compounds of formula (I) are in particular:
1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methyl-phenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl-phenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(~-methylcyclo-hexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol.
1.2. Alkylated hydroquinones,for example 2,6-di-tert-butyl-4-me-thoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydro-quinone, 2,6-diphenyl-4-octadecyloxyphenol.
1.3. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thio-bls(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol).
1.4. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethyl-phenol), 2,2'-methylenebis[4-methyl-6-(~-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebi 8-(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butyl-phenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethyli-denebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(~-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(~,~-dimethyl-benzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bi 8( 5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-msthyl-2-hydroxybenzyl)-4-m~thylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis-[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4methylphenyl]
terephthalate.
1.5. Benzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimsthylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiolterephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphospho-nate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, I,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso-cyanurate.
1.6. Acylaminophenols, for example 4-hydroxyanilide of lauric acid, 4-hydroxyanilide of stearic acid, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
~ 1304368 1.7. Esters of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, diethylene glycol, octadecanol, triethylene glycol, I,6-hexanediol, penta-erythrltol, neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.8. Esters of R-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, di-ethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.9. Esters of ~-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, penta-erythritol, neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid dlamide.
1.10. Amides of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexa-r methylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)trimethylene-diamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
2. W absorbers and light stabilisers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example the 5'-methyl, 3',5'-di-tert-butyl, 5'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis(~,~-dimethylbenzyl) derivatives.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4~4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids 7 for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octyl-phenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-dl-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxy-benzoate.
2.4. Acrylates, for example ethyl ~-cyano-B,~-diphenylacrylate, isooctyl ~-cyano-~,~-diphenylacrylate, methyl ~-carbomethoxycinn-amate, methyl ~-cyano-B-methyl-p-methoxycinnamate, butyl ~-cyano-B-methyl-p-methoxycinnamate, methyl ~-carbomethoxy-p-methoxy-cinnamate and N-(~-carbomethoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis~4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldi-thiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl-phosphonic acid monoalkyl esters, e.g. of the methyl or ethyl ester, nicksl complexes of ketoximes, e.g. of 2-hydroxy-4-methyl-phenyl undecyl ketoneoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetra-methylpiperidyl) sebacate, b~s(1,2,2,6,6-pentamethylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotri-acetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethyl-piperazinone).
" 130436~3 2.7. Oxalic acid diamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-sthoxy-5-tert-butyl-2'-ethylox-anilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butylox-anilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
3. Metal deactivators, for example N,N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bistsalicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalic acid dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonyl-phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol tri-phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetra-oxa-3,9-diphosphaspiro[5.5]undecane.
5. Peroxide scavengers, for example esters of B-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(B-dodecylmercapto)propionate.
6. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
`` 1304368 7. Basic co-stabilisers, for example, melamine, polyvinylpyrroli-done, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of hlgher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
8. Nucleating agents, for example, 4-tert.butyl-benzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxydes, carbon black, graphite.
10. Other additives, for example, plasticisers, lubricants, emulsi-fiers, pigments, optical brighteners, flameproofing agents, anti-static agents and blowing agents.
The compounds of formula (I) are particularly effective in combina-tion with phenolic antioxidants, preferably those mentioned above under items 1.1 to 1.10. The antioxidant may be added in an amount of e.g. 0.01 to 0.5 % by weight, relative to the weight of the organic material.
The following examples illustrate the lnvention.
Example 1: Preparation of NI,NII~NIII~NIV-tetrakis[2~4_bis[N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl]-NI,NI -dimethyl-4,7-diazadecane-1,10-diamine To a solution of 43.4 g (0.02 moles) of NI,NII,NIII,NIV-tetrakis-[2,4-bis[N-(2,2,6,6-tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl]-4,7-diazadecane-1,10-diamine in 100 ml of water containing 18.4 g (0.4 moles) of formic acid there are added 30 ml (0.4 moles) of a 40 % aqueous formaldehyde solution during about 30 minutes.
The solution is heated under reflux for 8 hours. After cooling to room temperature an additional amount of 15 ml of 40 % formaldehyde i9 added and the solution refluxed for additional 5 hours.
After cooling a solution of 20 g (0.5 moles) of NaOH in 100 ml water is added. The precipitated solid is filtered off, washed with water, dryed under vacuum and recrystallized from isopropanol. The obtained title compound melts at 154-160C.
Analysis for C134H2s4N32(Molecular weight: 2313.7 g/mol):
calculated C = 69.56 %; H = 11.06 %; N = 19.37 %
found C = 69.36 %; H = 10.98 %; N = 19.25 %
Examples 2 to 6:
In analogy to the procedure described in Example 1 the following compounds are prepared:
H3c-~-(cH2)3-~-(cH2)2-~-(cH2)3-~-cH3 R s H3C\ /CH3 ,~ r~ CH3 .~--R8 H3C~~ i/CH3 H3C \~/ CH3 ~ . --Example No. R7 /R8 Melting point (C) 3 -C2Hs 197 - 201 4 -C3H7-i 211 - 216 -8H-czHs 186 - 190 H3C\ /CH3 6 --\ /N-&H3247 - 252 H3C/ \CH3 Example 7: Preparation of NI~NII~NIII~NIV-tetrakis[2~4-bis[N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl]-NI,NIV-dimethyl-3,6-diazaoctane-1,8-diamine This compound i8 prepared by analogy to the procedure described in Example 1.
The melting point of the product i9 151-155C.
Example 8: Light stability of polypropylene tapes 100 Parts of polypropylene powder (melt flow index: ~ 1.5 g/10 min;
measured at 230C and 2.16 kg) are blended in a barrel mixer with 0.05 parts of pentaerythrityl-tetrakis(~-3,5-di-tert-butyl-4-hydroxyphenyl)propiona~e, 0.05 parts of tris(2,4-di-tert-butyl-phenyl)phosphite 9 O. 1 part of Ca-stearate and 0.1 part of the product of Example 1 (- LS 1). Then the blend is compounded in an extruder at temperatures of 180-220C. The granules obtained on extrusion and granulation are transformed into films at 220-260C
in a second extruder equipped with a flat sheet die. The films are cut into ribbons which are drawn to achieve a stretch ratio of 1:6.
The tapes obtained with this procedure are finally 50 ~m thick and 2.5 mm wide.
The tapes are mounted without tension OTI sample holders and exposed in a Xenotest 1200. Periodically, the tensile strength of the exposed tapes i8 measured. The expo~ure time corresponding to a loss of 50 % of the initial tensile strength (Tsn) is a measure for the light-stabilizing efficiency. In the case of the stabilized sample Tso i3 3400 hours. A comparative sample without LS 1 shows a Tsn of 680 hours.
Example 9: Oven aging of polypropylene In the mixing chamber of a Brabender plastograph 38 g of unstabi-lized polypropylene powder (melt flow index: ~ 3 g/10 min; measured at 230C and 2.16 kg) are plasticized and homogeniæed with 38 mg of Ca-stearate and the stabilizers indicated in table 1 at 200C and 30 rpm for 10 minutes. The homogenized mixture is then taken out of the kneader and compression molded at 260C for 6 minutes into a 1 mm thick sheet which is cut into test specimens of 1 x 13 cm2.
The test specimens are placed in draft air ovens at 135C and checked periodically for brittleness on bending.
The test results are summarized in table 1.
Table 1:
Stabilizer Days at 135C until brittleness on bending ~% by weight) none <1 0.2 % LS 1 0.2 % AO 1 54 0.1 % LS 1 + 0.1 % AO 1 84 ~ . . _ LS 1 - Product of Example 1 AO 1 = Octadecyl R-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate Example 10:
1 g of each of the compounds indicated in table 2 and 1 g of calcium stearate are mixed in a powder mixer with 1000 g of polypropylene powder (melt index: 2 g/10 min; measured at 230C and 2.16 kg). The mixtures are extruded twice at 200 to 220C to give polymer granules which are then converted into 1 mm thick sheets (mould in accordance with DIN 53 451) by compression-in~ection for 3 minutes at 220C. The sheets obtained are exposed in a draft air oven at 135C and checked periodically for brittleness on bending at 180.
The results are shown in table 2:
Table 2:
Stabilizer Hours at 135C until brittleness on bending at 180 without 330 Compound of Example 1 1320 Compound of Example 2 1800 Compound of Example 3 1580
The compounds of formula (I) are especially useful as stabilizers for non-crosslinked homo- or copolymers of ~-olefins containing at least 80 % of polymerized ~-olefinl in particular homopolymers of ethylene, propylene, l-butene, 2-methylpropene, 3-methyl-1-butene or 4-methyl-1-pentene and their copolymers with each other or with other unsaturated compounds such as styrene, butadiene, vinyl acetate, acrylic acid, methyl or ethyl acrylate or methyl or ethyl methacrylate. Of particular technical interest are polyethylene and polypropylene.
The compounds of formula (I) can be mixed with the organic material in various proportions depending on the nature of the material to be stabilized, on the end use and on the presence of other additives.
In general it is advantageous to employ from 0.01 to 5 % by weight of the compounds of formula (I), relative to the weight of the material to be stabilized, preferably from 0.1 to 2 %.
The compounds of formula (I) can be incorporated into the organic material via various processes known per se, such as e.g. dry blending in the form of powders, or wet mixing in the form of solutions or suspensions, or mixing in the form of a master-batch which contains the compounds of formula (I) in a concentration of e.g. 5 to 25 % by weight; in these operation~, the organic material can be employed in the form of powder, granules, a solution, a suspension or in the form of a latex.
~304368 The compounds of formula (I) and, if desired, further additlves can also be mixed into a melt of the material to be stabilized, before or during shaping.
The resulting stabilized materials can be applied in various forms, e.g. sheets, fibres, tapes, bottles, tubes or other profiles. The compounds of formula (I) are especially useful as stabilizers for polypropylene fibres, tapes and films.
If desired, other additives, such as e.g. antioxidants, phosphites, W absorbers, nickel stabilizers, pigments, fillers, plasticizers, antistatic agents, blowing agents, flameproofing agents, lubricants, anti-corrosion agents and metal deactivators, can be added to the mixture of the compounds of the invention with the organic mate-rials. Examples of additives which can be mixed with the compounds of formula (I) are in particular:
1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methyl-phenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl-phenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(~-methylcyclo-hexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol.
1.2. Alkylated hydroquinones,for example 2,6-di-tert-butyl-4-me-thoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydro-quinone, 2,6-diphenyl-4-octadecyloxyphenol.
1.3. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thio-bls(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol).
1.4. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethyl-phenol), 2,2'-methylenebis[4-methyl-6-(~-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebi 8-(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butyl-phenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethyli-denebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(~-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(~,~-dimethyl-benzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bi 8( 5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-msthyl-2-hydroxybenzyl)-4-m~thylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis-[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4methylphenyl]
terephthalate.
1.5. Benzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimsthylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiolterephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphospho-nate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, I,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso-cyanurate.
1.6. Acylaminophenols, for example 4-hydroxyanilide of lauric acid, 4-hydroxyanilide of stearic acid, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
~ 1304368 1.7. Esters of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, diethylene glycol, octadecanol, triethylene glycol, I,6-hexanediol, penta-erythrltol, neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.8. Esters of R-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, di-ethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.
1.9. Esters of ~-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, penta-erythritol, neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid dlamide.
1.10. Amides of ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexa-r methylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)trimethylene-diamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
2. W absorbers and light stabilisers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example the 5'-methyl, 3',5'-di-tert-butyl, 5'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis(~,~-dimethylbenzyl) derivatives.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4~4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids 7 for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octyl-phenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-dl-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxy-benzoate.
2.4. Acrylates, for example ethyl ~-cyano-B,~-diphenylacrylate, isooctyl ~-cyano-~,~-diphenylacrylate, methyl ~-carbomethoxycinn-amate, methyl ~-cyano-B-methyl-p-methoxycinnamate, butyl ~-cyano-B-methyl-p-methoxycinnamate, methyl ~-carbomethoxy-p-methoxy-cinnamate and N-(~-carbomethoxy-~-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis~4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldi-thiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl-phosphonic acid monoalkyl esters, e.g. of the methyl or ethyl ester, nicksl complexes of ketoximes, e.g. of 2-hydroxy-4-methyl-phenyl undecyl ketoneoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetra-methylpiperidyl) sebacate, b~s(1,2,2,6,6-pentamethylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotri-acetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethyl-piperazinone).
" 130436~3 2.7. Oxalic acid diamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-sthoxy-5-tert-butyl-2'-ethylox-anilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butylox-anilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
3. Metal deactivators, for example N,N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bistsalicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalic acid dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonyl-phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol tri-phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetra-oxa-3,9-diphosphaspiro[5.5]undecane.
5. Peroxide scavengers, for example esters of B-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(B-dodecylmercapto)propionate.
6. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
`` 1304368 7. Basic co-stabilisers, for example, melamine, polyvinylpyrroli-done, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of hlgher fatty acids for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
8. Nucleating agents, for example, 4-tert.butyl-benzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxydes, carbon black, graphite.
10. Other additives, for example, plasticisers, lubricants, emulsi-fiers, pigments, optical brighteners, flameproofing agents, anti-static agents and blowing agents.
The compounds of formula (I) are particularly effective in combina-tion with phenolic antioxidants, preferably those mentioned above under items 1.1 to 1.10. The antioxidant may be added in an amount of e.g. 0.01 to 0.5 % by weight, relative to the weight of the organic material.
The following examples illustrate the lnvention.
Example 1: Preparation of NI,NII~NIII~NIV-tetrakis[2~4_bis[N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl]-NI,NI -dimethyl-4,7-diazadecane-1,10-diamine To a solution of 43.4 g (0.02 moles) of NI,NII,NIII,NIV-tetrakis-[2,4-bis[N-(2,2,6,6-tetramethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl]-4,7-diazadecane-1,10-diamine in 100 ml of water containing 18.4 g (0.4 moles) of formic acid there are added 30 ml (0.4 moles) of a 40 % aqueous formaldehyde solution during about 30 minutes.
The solution is heated under reflux for 8 hours. After cooling to room temperature an additional amount of 15 ml of 40 % formaldehyde i9 added and the solution refluxed for additional 5 hours.
After cooling a solution of 20 g (0.5 moles) of NaOH in 100 ml water is added. The precipitated solid is filtered off, washed with water, dryed under vacuum and recrystallized from isopropanol. The obtained title compound melts at 154-160C.
Analysis for C134H2s4N32(Molecular weight: 2313.7 g/mol):
calculated C = 69.56 %; H = 11.06 %; N = 19.37 %
found C = 69.36 %; H = 10.98 %; N = 19.25 %
Examples 2 to 6:
In analogy to the procedure described in Example 1 the following compounds are prepared:
H3c-~-(cH2)3-~-(cH2)2-~-(cH2)3-~-cH3 R s H3C\ /CH3 ,~ r~ CH3 .~--R8 H3C~~ i/CH3 H3C \~/ CH3 ~ . --Example No. R7 /R8 Melting point (C) 3 -C2Hs 197 - 201 4 -C3H7-i 211 - 216 -8H-czHs 186 - 190 H3C\ /CH3 6 --\ /N-&H3247 - 252 H3C/ \CH3 Example 7: Preparation of NI~NII~NIII~NIV-tetrakis[2~4-bis[N-1,2,2,6,6-pentamethyl-4-piperidyl)-n-butylamino]-1,3,5-triazin-6-yl]-NI,NIV-dimethyl-3,6-diazaoctane-1,8-diamine This compound i8 prepared by analogy to the procedure described in Example 1.
The melting point of the product i9 151-155C.
Example 8: Light stability of polypropylene tapes 100 Parts of polypropylene powder (melt flow index: ~ 1.5 g/10 min;
measured at 230C and 2.16 kg) are blended in a barrel mixer with 0.05 parts of pentaerythrityl-tetrakis(~-3,5-di-tert-butyl-4-hydroxyphenyl)propiona~e, 0.05 parts of tris(2,4-di-tert-butyl-phenyl)phosphite 9 O. 1 part of Ca-stearate and 0.1 part of the product of Example 1 (- LS 1). Then the blend is compounded in an extruder at temperatures of 180-220C. The granules obtained on extrusion and granulation are transformed into films at 220-260C
in a second extruder equipped with a flat sheet die. The films are cut into ribbons which are drawn to achieve a stretch ratio of 1:6.
The tapes obtained with this procedure are finally 50 ~m thick and 2.5 mm wide.
The tapes are mounted without tension OTI sample holders and exposed in a Xenotest 1200. Periodically, the tensile strength of the exposed tapes i8 measured. The expo~ure time corresponding to a loss of 50 % of the initial tensile strength (Tsn) is a measure for the light-stabilizing efficiency. In the case of the stabilized sample Tso i3 3400 hours. A comparative sample without LS 1 shows a Tsn of 680 hours.
Example 9: Oven aging of polypropylene In the mixing chamber of a Brabender plastograph 38 g of unstabi-lized polypropylene powder (melt flow index: ~ 3 g/10 min; measured at 230C and 2.16 kg) are plasticized and homogeniæed with 38 mg of Ca-stearate and the stabilizers indicated in table 1 at 200C and 30 rpm for 10 minutes. The homogenized mixture is then taken out of the kneader and compression molded at 260C for 6 minutes into a 1 mm thick sheet which is cut into test specimens of 1 x 13 cm2.
The test specimens are placed in draft air ovens at 135C and checked periodically for brittleness on bending.
The test results are summarized in table 1.
Table 1:
Stabilizer Days at 135C until brittleness on bending ~% by weight) none <1 0.2 % LS 1 0.2 % AO 1 54 0.1 % LS 1 + 0.1 % AO 1 84 ~ . . _ LS 1 - Product of Example 1 AO 1 = Octadecyl R-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate Example 10:
1 g of each of the compounds indicated in table 2 and 1 g of calcium stearate are mixed in a powder mixer with 1000 g of polypropylene powder (melt index: 2 g/10 min; measured at 230C and 2.16 kg). The mixtures are extruded twice at 200 to 220C to give polymer granules which are then converted into 1 mm thick sheets (mould in accordance with DIN 53 451) by compression-in~ection for 3 minutes at 220C. The sheets obtained are exposed in a draft air oven at 135C and checked periodically for brittleness on bending at 180.
The results are shown in table 2:
Table 2:
Stabilizer Hours at 135C until brittleness on bending at 180 without 330 Compound of Example 1 1320 Compound of Example 2 1800 Compound of Example 3 1580
Claims (16)
1. A compound of the formula (I) (I) wherein R1 and R5 are independently hydrogen, C1-C12-alkyl, C5-C7-cyclo-alkyl or a group of the formula (II), (II) R2, R3 and R4 are independently C1-C12-alkylene, R is a group of the formula (III) (III) wherein R6 is C2-C8-dialkylamino, C1-C4-alkoxy, pyrrolidinyl, piperidino, morpholino, hexahydroazepinyl or a group of the formula (IV), (IV) R7 and R8 are independently C1-C12-alkyl, C5-C7-cycloalkyl, benzyl or agroup of the formula (II), subject to the proviso that both, R1 and R5 are different from hydrogen, if R is a group .
2. The compound according to claim 1, wherein R6 is C2-C8-dialkyl-amino, morpholino or a group of the formula (IV).
3. The compound according to claim 1, wherein R6 is a group of the formula (IV) and R7 and R8 are independently C1-C12-alkyl or a group of the formula (II).
4. The compound according to claim 1, wherein R1 and R5 are independ-ently C1-C12-alkyl, C5-C7-cycloalkyl or a group of the formula (II).
5. The compound according to claim 1, wherein R1 and R5 are inde-pendently C1-C6-alkyl or a group of the formula (II).
6. The compound according to claim 1, wherein R1 and R5 are methyl, R2, R3 and R4 are independently ethylene or trimethylene, R6 is a group of the formula (IV) and R7 and R8 are independently C1-C4-alkyl or a group of the formula (II).
7. The compound according to claim 1, wherein R1 and R5 are methyl, R2 and R4 are trimethylene, R3 is ethylene, R6 is a group of the formula (IV), R7 and R8 which are identical are C1-C12-alkyl.
8. The compound according to claim 1, wherein R7 and R8 are inde-pendently C1-C6-alkyl.
9. The compound according to claim 1, wherein R7 and R8 are inde-pendently methyl, ethyl or butyl.
10. The compound according to claim 1, wherein R7 and R8 are n-butyl.
11. A composition comprising an organic material subject to oxida-tive, thermal and/or light induced degradation and at least one compound according to claim 1.
12. A composition according to claim 11, wherein the organic material is a synthetic polymer.
13. A composition according to claim 11, wherein the organic material is polyethylene or polypropylene.
14. A composition according to claim 11, which additionally contains a phenolic antioxidant.
15. A composition comprising 70 % to 99 % by weight of a compound according to claim 1, wherein R1 and R5 are methyl, and 0 to 30 % by weight of a compound of the formula (Ib) (Ib) and O to 30 % by weight of a compound of the formula (Ic) (Ic) wherein R, R2, R3 and R4 are as defined in claim 1.
16. A method for stabilizing an organic material against oxidative, thermal and/or light induced degradation which comprises incorporat-ing into said organic material at least one compound according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21518A/86 | 1986-08-25 | ||
| IT21518/86A IT1197466B (en) | 1986-08-25 | 1986-08-25 | METHOD FOR THE STABILIZATION OF OLEOPHINIC POLYMERS BY TRIAZINIC COMPOUNDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1304368C true CA1304368C (en) | 1992-06-30 |
Family
ID=11183001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000545067A Expired - Lifetime CA1304368C (en) | 1986-08-25 | 1987-08-21 | 1,2,2,6,6-pentamethyl-4-piperidylaminotriazine derivatives and their use as stabilizers |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US4816507A (en) |
| JP (1) | JP2522959B2 (en) |
| BE (1) | BE1002211A4 (en) |
| CA (1) | CA1304368C (en) |
| DE (1) | DE3727977C2 (en) |
| FR (1) | FR2603037B1 (en) |
| GB (1) | GB2194237B (en) |
| IT (1) | IT1197466B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1197466B (en) * | 1986-08-25 | 1988-11-30 | Ciba Geigy Spa | METHOD FOR THE STABILIZATION OF OLEOPHINIC POLYMERS BY TRIAZINIC COMPOUNDS |
| US4816585A (en) * | 1987-03-05 | 1989-03-28 | Olin Corporation | Tetraalkylpiperidinyl substituted uracil derivatives and their use as ultraviolet light stabilizers |
| IT1222049B (en) * | 1987-07-16 | 1990-08-31 | Ciba Geygi Spa | TRIAZIN PIPERIDIN COMPOUNDS USABLE AS STABILIZERS FOR SYNTHETIC POLYMERS |
| US4812500A (en) * | 1987-09-30 | 1989-03-14 | Shell Oil Company | Polyolefin compositions for water pipes and for wire and cable coatings |
| US4904714A (en) * | 1987-10-02 | 1990-02-27 | Olin Corporation | Synthetic resin composition and its method of use |
| IT1223405B (en) * | 1987-12-04 | 1990-09-19 | Ciba Geigy Spa | PROCEDURE FOR THE METHYLATION OF TRIAZINIC COMPOUNDS CONTAINING GROUPS 2,2,6,6 TETRAMETHYLPIPERIDINIC |
| AU621082B2 (en) * | 1988-02-08 | 1992-03-05 | Ciba-Geigy Ag | Tetramethylpiperidino-s-triazines |
| IT1217742B (en) * | 1988-05-31 | 1990-03-30 | Ciba Geigy Spa | POLYAMINES PARTIALLY REPLACED WITH PIPERIDIN TRIAZINE |
| IT1219701B (en) * | 1988-05-31 | 1990-05-24 | Ciba Geigy Spa | POLYAMINES PARTIALLY REPLACED WITH 4,6 BIS (N, N BIS (2,2,6,6 TETRAMETHY 4 PIPERDIL) AMINO) 1,3,5-TRIAZIN-2-IL |
| US5244948A (en) * | 1988-06-30 | 1993-09-14 | Ciba-Geigy Corporation | Process for the stabilization of polyolefins |
| DE58909397D1 (en) * | 1988-12-20 | 1995-09-28 | Ciba Geigy Ag | Process for the preparation of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine. |
| IT1227953B (en) * | 1988-12-23 | 1991-05-14 | Ciba Geigy Spa | PIPERIDIN TRIAZIN COMPOUNDS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS |
| US5019613A (en) * | 1989-03-21 | 1991-05-28 | Ciba-Geigy Corporation | N-hydrocarbyloxy derivatives of hindered amine-substituted S-triazines |
| EP0389428A3 (en) * | 1989-03-21 | 1991-10-09 | Ciba-Geigy Ag | N,n-bis(l-hydroxycarbyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) amino triazines and stabilized compositions |
| US5118736A (en) * | 1989-03-21 | 1992-06-02 | Ciba-Geigy Corporation | N,N-bis(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino triazines and stabilized compositions |
| IT1230086B (en) * | 1989-05-25 | 1991-10-05 | Ciba Geigy Spa | PIPERIDIN TRIAZIN COMPOUNDS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS. |
| US5013836A (en) * | 1989-11-21 | 1991-05-07 | The B. F. Goodrich Company | Process for methylating a hindered nitrogen atom in a polysubstituted diazacycloalkan-2-one |
| US5239071A (en) * | 1989-11-21 | 1993-08-24 | The B. F. Goodrich Company | Process for methylating a hindered nitrogen atom in an inert non-aqueous solvent |
| US5049600A (en) * | 1990-01-23 | 1991-09-17 | The B. F. Goodrich Company | Multi-component stabilizer system for polyolefins pigmented with phthalocyanine pigments |
| US5071981A (en) * | 1990-03-19 | 1991-12-10 | The B. F. Goodrich Company | Alkylated oxo-piperanzinyl-triazine |
| US5059644A (en) * | 1990-03-19 | 1991-10-22 | E. I. Du Pont De Nemours And Company | Polyacetal compositions containing at least one oxo-piperazinyltriazine hindered amine light stabilizer |
| JPH04222852A (en) * | 1990-03-19 | 1992-08-12 | E I Du Pont De Nemours & Co | Polyacetal composition containing amine photostabilizer blocked out with triazine |
| US5098944A (en) * | 1990-09-11 | 1992-03-24 | The B. F. Goodrich Company | Thermooxidative stabilization of polymers with a n4-alkylated oxo-piperazinyl-triazine |
| US5190710A (en) * | 1991-02-22 | 1993-03-02 | The B. F. Goodrich Company | Method for imparting improved discoloration resistance to articles |
| IT1271711B (en) * | 1994-11-09 | 1997-06-04 | Ciba Geigy Spa | DERIVATIVES OF 2,2,6,6-TETRAMETYLPIPERIDINE USEFUL AS LIGHT, HEAT AND OXIDATION STABILIZERS FOR ORGANIC MATERIALS |
| ES2128978B1 (en) * | 1996-04-01 | 2000-03-01 | Ciba Sc Holding Ag | POLYTHRIAZINE DERIVATIVES CONTAINING GROUPS OF POLYALKYLPIPERIDINYLOXYL OR POLYALKYLPIPERIDINYLAMINE. |
| ES2239348T3 (en) * | 1996-07-17 | 2005-09-16 | Ciba Specialty Chemicals Holding Inc. | LONG-TERM STABILIZERS, OZONE RESISTANT. |
| EP0835873A1 (en) * | 1996-10-14 | 1998-04-15 | Ciba Speciality Chemicals Holding Inc. | Mixtures of trisubstituted and tetrasubstituted polyalkylpiperidinylaminotriazine tetraamine compounds |
| US20040001826A1 (en) * | 1999-06-30 | 2004-01-01 | Millennium Pharmaceuticals, Inc. | Glycoprotein VI and uses thereof |
| ITMI20012598A1 (en) * | 2001-12-11 | 2003-06-11 | 3V Sigma Spa | DEFINED MOLECULAR WEIGHT MACROMOLECULAR HALS |
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|---|---|---|---|---|
| IT1060458B (en) * | 1975-12-18 | 1982-08-20 | Chimosa Chimica Organica Spa | TRIAZIN PIPERIDYL COMPOUNDS SUITABLE FOR THE STABILIZATION OF SYNTHETIC POLYMERS AND PROCEDURE FOR THEIR PREPARATION |
| EP0013682B1 (en) * | 1979-01-29 | 1981-10-14 | Ciba-Geigy Ag | Piperidyl-triazine derivatives, process for their production, their use as stabilizers for polymers and the polymers stabilized therewith |
| DE2944729A1 (en) * | 1979-11-06 | 1981-05-14 | Hoechst Ag, 6000 Frankfurt | NEW TRIAZINE STABILIZERS |
| IT7928324A0 (en) * | 1979-12-21 | 1979-12-21 | Chimosa Chimica Organica Spa | PIPERIDINE DERIVATIVES, STABILIZERS FOR SYNTHETIC POLYMERS. |
| DE3022896A1 (en) * | 1980-06-19 | 1981-12-24 | Hoechst Ag, 6000 Frankfurt | POLYTRIAZINYLAMINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS STABILIZERS FOR SYNTHETIC POLYMERS |
| JPS5738589A (en) * | 1980-08-19 | 1982-03-03 | Matsushita Electric Ind Co Ltd | High frequency heater |
| DE3131684A1 (en) * | 1981-08-11 | 1983-02-24 | Hoechst Ag, 6000 Frankfurt | POLYTRIAZINYL ALCOHOLS, -ESTERS AND -URETHANES, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS STABILIZERS |
| IT1152192B (en) * | 1982-05-19 | 1986-12-31 | Apital Prod Ind | COMPOUNDS FOR STABILIZING POLYMERS |
| JPS59122487A (en) * | 1982-12-28 | 1984-07-14 | Sankyo Co Ltd | Piperidyl-triazine-triamine derivative and stabilizer for polymeric materials |
| IT1163814B (en) * | 1983-07-19 | 1987-04-08 | Chimosa Chimica Organica Spa | POLYMERIC COMPOUNDS CONTAINING PIPERIDINIC AND TRIAZINIC RADICALS, PROCESS FOR THEIR PREPARATION AND USE AS STABILIZERS FOR SYNTHETIC POLYMERS |
| IT1197466B (en) * | 1986-08-25 | 1988-11-30 | Ciba Geigy Spa | METHOD FOR THE STABILIZATION OF OLEOPHINIC POLYMERS BY TRIAZINIC COMPOUNDS |
-
1986
- 1986-08-25 IT IT21518/86A patent/IT1197466B/en active
-
1987
- 1987-08-14 US US07/085,581 patent/US4816507A/en not_active Expired - Fee Related
- 1987-08-14 GB GB8719310A patent/GB2194237B/en not_active Expired - Lifetime
- 1987-08-21 DE DE3727977A patent/DE3727977C2/en not_active Expired - Fee Related
- 1987-08-21 CA CA000545067A patent/CA1304368C/en not_active Expired - Lifetime
- 1987-08-24 FR FR8711847A patent/FR2603037B1/en not_active Expired - Fee Related
- 1987-08-24 BE BE8700933A patent/BE1002211A4/en not_active IP Right Cessation
- 1987-08-25 JP JP62211209A patent/JP2522959B2/en not_active Expired - Lifetime
-
1988
- 1988-10-31 US US07/264,560 patent/US4906678A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB8719310D0 (en) | 1987-09-23 |
| BE1002211A4 (en) | 1990-10-16 |
| GB2194237B (en) | 1990-05-23 |
| DE3727977A1 (en) | 1988-03-03 |
| JPS6379886A (en) | 1988-04-09 |
| US4816507A (en) | 1989-03-28 |
| IT8621518A0 (en) | 1986-08-25 |
| DE3727977C2 (en) | 1998-03-26 |
| GB2194237A (en) | 1988-03-02 |
| IT1197466B (en) | 1988-11-30 |
| FR2603037A1 (en) | 1988-02-26 |
| US4906678A (en) | 1990-03-06 |
| JP2522959B2 (en) | 1996-08-07 |
| FR2603037B1 (en) | 1993-10-22 |
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| MKLA | Lapsed |