JPH07285979A - Monomeric and oligomeric bisphenyl-hals phosphites as stabilizers - Google Patents

Abstract

PURPOSE: To provide a novel compd. which protects an org. material against oxidation, heat, and light-induced degradation, particularly has high stability against hydrolysis, and can prevent fading of the org. material.

CONSTITUTION: This monomeric bisphenyl-HALS phosphite is represented by formula I [wherein R₁ and R₂ represent each H, a 1-25C alkyl, a 2-24C alkenyl, a (substd.) 5-8C cycloalkyl, a 7-9C phenyl alkyl or the like; R₃ represents H or methyl; R₄ represents H, a 1-8C alkyl, OH, NO or the like; X represents O, >N-R₇ (wherein R₇ represents H, a 1-8C alkyl or the like); and A represents O, S or the like], and the oligomeric bisphenyl-HALS phosphite is represented by formula II (wherein n is 2 to 25). Examples thereof include a compd. represented by formula III. The compd. represented by formula II is obtd. by reacting a bisphenol represented by formula IV with phosphorus trichloride and reacting the product with an HALS compd. represented by formula V.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

This invention relates to novel monomer and oligomer bisphenyl-HALS phosphites, organic materials, preferably compositions comprising polymers and novel monomer and oligomer bisphenyl-HALS phosphites, and organic materials. The present invention relates to a method of using the above composition for stabilizing oxidative, thermal or light induced decay.

[0002]

Organic phosphites are known in the industry as costabilizers, secondary antioxidants and processing stabilizers, especially for polyolefins. Examples of such known phosphite stabilizers are L.L. Gechter / Har. Edited by Muller, Plastic Additives Handbook, 3rd edition, page 47,
Hansar, Munich, 1990 and EP-A-3
No. 56688.

Hindered amines, especially 2,2,6,6-
A compound containing a tetramethylpiperidyl group is preferably used as a light stabilizer (hindered amine light stabilizer, HALS).

Phosphites containing HALS structural units have been described, for example, in the. Kenich et al., J. prakt. Chem. 334, 3
33-349 (1992), US-A-5239076, GB-
A-2247241, DE-A-4306747 and FR-A-2380290.

There remains a need for effective stabilizers for organic materials that are susceptible to oxidative, thermal and / or photoinduced degradation.

[0006]

In order to meet such a demand, the present invention is directed to a composition comprising a novel monomer and oligomer bisphenyl-HALS phosphite, an organic material and a novel monomer and oligomer bisphenyl-HALS phosphite. It is an object of the present invention to provide a method for using the above composition for stabilizing an organic material and an organic material from oxidative, thermal or photoinduced degradation.

[0007]

It has now been found that selected groups of the above HALS phosphites are particularly suitable as stabilizers for organic materials susceptible to oxidative, thermal or photoinduced degradation. It should be emphasized that the above compounds are suitable as processing stabilizers for synthetic polymers.

The present invention therefore relates to monomeric compounds of formula I below and oligomeric compounds of formula II below:

[Chemical 19] (In the formula, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an unsubstituted or an alkyl group having 1 to 4 carbon atoms. A substituted cycloalkyl group having 5 to 8 carbon atoms; unsubstituted or 1 to 4 carbon atoms
Represents a phenyl group substituted with an alkyl group of 5; a cycloalkenyl group having 5 to 8 carbon atoms, which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms; or a phenylalkyl group having 7 to 9 carbon atoms. , R ₃ represents a hydrogen atom or a methyl group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,

[Chemical 20] OH, NO, —CH ₂ CN, an alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group having 5 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, 1 to 8 carbon atoms
Or an phenylalkyl group having 7 to 9 carbon atoms, which is unsubstituted or substituted on the phenyl ring by an alkyl group having 1 to 4 carbon atoms,
R ₅ and R ₆ independently of one another represent a hydrogen atom, CF ₃ , an alkyl group having 1 to 12 carbon atoms or a phenyl group, or R ₅ and R ₆ together with the carbon atom to which they are bonded 5 to 1 carbon atoms which are unsubstituted or substituted by alkyl groups having 1 to 4 carbon atoms
Two cycloalkylidene rings are formed, provided that R ₅ and R ₆ simultaneously represent a hydrogen atom, R ₄ does not represent a hydrogen atom, and R ₁ , R ₂ and R ₃ represent simultaneously a hydrogen atom. , And R ₅ and R ₆ simultaneously represent a methyl group, R ₄ does not represent a hydrogen atom, R ₇ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or
I:

[Chemical 21] R ₈ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, A represents an oxygen atom, a sulfur atom, or a compound represented by the following formula:

[Chemical formula 22] Represents an oxygen atom or the following formula:

[Chemical formula 23] Wherein Y and Z are independently of each other an alkylene group having 2 to 18 carbon atoms, an oxygen atom, a sulfur atom or the following formula:

[Chemical formula 24] 4 to 18 carbon atoms interrupted by a group represented by
Represents an alkenylene group having 4 to 8 carbon atoms or a phenylethylene group, m represents an integer of 2 to 8 and n represents a number of 2 to 25).

The alkyl group having up to 25 carbon atoms may be a branched group or an unbranched group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a secondary group. Dibutyl group, isobutyl group, tert-butyl group, 2-ethylbutyl group, n-pentyl group, isopentyl group, 1-methylpentyl group, 1,3-
Dimethylbutyl group, n-hexyl group, 1-methylhexyl group, n-heptyl group, isoheptyl group, 1,1,3
3-tetramethylbutyl group, 1-methylheptyl group, 3
-Methylheptyl group, n-octyl group, 2-ethylhexyl group, 1,1,3-trimethylhexyl group, 1,1,
3,3-Tetramethylpentyl group, nonyl group, decyl group, undecyl group, 1-methylundecyl group, dodecyl group, 1,1,3,3,5,5-hexamethylhexyl group, tridecyl group, tetradecyl group , Pentadecyl group,
Hexadecyl group, heptadecyl group, octadecyl group, eicosyl group or docosyl group. One of the preferred meanings of R ₁ and R ₂ is, for example, 1 to 18 carbon atoms.
Is an alkyl group having 1 to 12 carbon atoms, for example, an alkyl group having 1 to 8 carbon atoms.
A particularly preferred meaning of R ₂ is an alkyl group having 1 to 4 carbon atoms.

The alkenyl group having 2 to 24 carbon atoms may be a branched group or an unbranched group, for example, vinyl group, propenyl group, 2-butenyl group, 3-butenyl group, isobutenyl group. Group, n-2,4
-Pentadienyl group, 3-methyl-2-butenyl group, n
A 2-octenyl group, an n-2-dodecenyl group, an isododecenyl group, an oleyl group, an n-2-octadecenyl group or an n-4-octadecenyl group. Alkenyl groups having 3 to 18, especially 3 to 12 carbon atoms are preferred.

A cycloalkyl group having 5 to 12 carbon atoms, which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, especially 1 to 3 cycloalkyl groups having 5 to 8 carbon atoms, especially 1 Or preferably containing two branched or unbranched alkyl groups such as cyclopentyl group, methylcyclopentyl group, dimethylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group, tert-butylcyclohexyl group, cycloheptyl group. Base,
It is a cyclooctyl group or a cyclododecyl group. Preferred is a cycloalkyl group having 5 to 8 carbon atoms, especially cyclohexyl.

A phenyl group substituted by an alkyl group having 1 to 4 carbon atoms preferably contains 1 to 3, especially 1 or 2 alkyl groups, for example o-, m- or p-methylphenyl groups, 2,3-dimethylphenyl group,
2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2-methyl-6-ethylphenyl group, 4-tert-butylphenyl group,
It is a 2-ethylphenyl group or a 2,6-diethylphenyl group.

The cycloalkenyl group having 5 to 8 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms is preferably 1 to 3, especially 1 or 2 branched or unbranched alkyl groups. Including, for example, cyclopentenyl group, methylcyclopentenyl group, dimethylcyclopentenyl group, cyclohexenyl group, methylcyclohexenyl group, dimethylcyclohexenyl group, trimethylcyclohexenyl group, tert-butylcyclohexenyl group,
It is a cycloheptenyl group or a cyclooctenyl group.
A cyclohexenyl group is preferred.

1 carbon atom, unsubstituted or on the phenyl group
A phenylalkyl group having 7 to 9 carbon atoms, which is substituted by an alkyl group having 4 to 4 and preferably contains 1 to 3, especially 1 or 2, branched or unbranched alkyl group is, for example, benzyl group or α-methylbenzyl group. Group, α, α
-Dimethylbenzyl group, 2-phenylethyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2,4-dimethylbenzyl group, 2,6-dimethylbenzyl group or 4-tertiary-butyl group. It is a benzyl group. A benzyl group is preferred.

The alkoxy group having up to 18 carbon atoms may be a branched group or an unbranched group. Examples thereof include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, Isobutoxy group, pentoxy group, isopentoxy group, hexoxy group,
It is a heptoxy group, an octoxy group, a decyloxy group, a tetradecyloxy group, a hexadecyloxy group or an octadecyloxy group. An alkoxy group having 6 to 12 carbon atoms is preferable.

The cycloalkoxy group having 5 to 12 carbon atoms is, for example, a cyclopentoxy group, a cyclohexoxy group, a cycloheptoxy group, a cyclooctoxy group, a cyclodecyloxy group or a cyclododecyloxy group.
One of the preferred meanings of R ₄ is cycloalkoxy group having 5 to 8 carbon atoms. A cyclopentoxy group or a cyclohexoxy group is particularly preferable.

The alkynyl group having 3 to 6 carbon atoms may be a branched group or an unbranched group, for example, a propynyl group (propargyl group, --C).
H ₂ -C≡CH), 2-butynyl or 3-butynyl group.

The acyl group having 1 to 8 carbon atoms is, for example, a formyl group, acetyl group, propionyl group, butyryl group, pentanonyl group, hexanonyl group, heptanonyl group, octanonyl group, benzoyl group, acryloyl group or crotonyl group. An alkanoyl group having 1 to 8 carbon atoms, an alkenoyl group having 3 to 8 carbon atoms or a benzoyl group, particularly an acetyl group is preferable.

The cycloalkylidene group having 5 to 8 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms is preferably 1 to 3, especially 1 or 2 branched or unbranched alkyl group. Including, for example, cyclopentylidene group, methylcyclopentylidene group, dimethylcyclopentylidene group, cyclohexylidene group, methylcyclohexylidene group, dimethylcyclohexylidene group, trimethylcyclohexylidene group, tert-butylcyclohexylidene group , A cycloheptylidene group or a cyclooctylidene group. Cyclohexylidene group and tert-butylcyclohexylidene group are preferred.

The alkylene group having 2 to 18 carbon atoms may be a branched group or an unbranched group, for example, methylene group, ethylene group, propylene group, tetramethylene group, pentamethylene group, It is a hexamethylene group, a heptamethylene group, an octamethylene group, a decamethylene group, a dodecamethylene group or an octadecamethylene group. An alkylene group having 2 to 12 carbon atoms,
Particularly, an alkylene group having 2 to 8 carbon atoms is preferable.

Oxygen atom, sulfur atom or the following formula:

[Chemical 25] 4 to 18 carbon atoms interrupted by a group represented by
The alkylene group may be interrupted once or more than once, for example _{-CH 2 CH 2 -O-CH 2} CH 2 -,
_{-CH 2 CH 2 -S-CH 2} CH 2 -, - CH 2 CH 2
_{-NH-CH 2 CH 2 -,} - CH 2 CH 2 -N (C
_{H 3) -CH 2 CH 2 -} , - CH 2 CH 2 -O-CH 2
_{CH 2 -O-CH 2 CH 2} -, - CH 2 CH 2 - (O-
_{CH 2 CH 2 -) 2 O} -CH 2 CH 2 -, - CH 2 CH
_{2 - (O-CH 2 CH} 2 -) 3 O-CH 2 CH 2 -, -
_{CH 2 CH 2 - (O-} CH 2 CH 2 -) 4 O-CH 2 C
H ₂ — or —CH ₂ CH ₂ —S—CH ₂ CH ₂ —.

Alkenylene group Y having 4 to 8 carbon atoms
Alternatively, Z is, for example, a 2-butenyl-1,4-ylene group. Phenylethylene group _{-CH (C 6 H 5) CH} 2 -
Is.

Of the monomer compounds represented by the above formula I and the oligomer compounds represented by the formula II, preferred ones are those in which R ₁ and R ₂ are each independently a hydrogen atom or a C 1-18 atom. Alkyl group, C2-C18 alkenyl group, C5-C8 cycloalkyl group, unsubstituted or C1-C4
Represents a phenyl group substituted with an alkyl group, a cycloalkenyl group having 5 to 8 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms, R ₄ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -OH, -CH ₂ C
N, an alkoxy group having 4 to 18 carbon atoms, a cycloalkoxy group having 5 to 12 carbon atoms, an allyl group, a propargyl group, an acetyl group or a phenylalkyl group having 7 to 9 carbon atoms, and R ₅ and R ₆ Each independently represent a hydrogen atom, CF ₃ , an alkyl group having 1 to 8 carbon atoms or a phenyl group, or R ₅ and R
₆ together with the carbon atom to which they are attached form a cycloalkylidene ring having 5 to 8 carbon atoms,
R ₇ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₈ is a hydrogen atom or 1 to 4 carbon atoms.
Of the following formula:

[Chemical formula 26] Represents a group represented by X is an oxygen atom or the following formula:

[Chemical 27] Wherein Y and Z are independently of each other, an alkylene group having 2 to 12 carbon atoms, an oxygen atom or the following formula:

[Chemical 28] 4 to 12 carbon atoms interrupted by a group represented by
An alkylene group of: an alkenylene group having 4 to 8 carbon atoms or a phenylethylene group, m is an integer of 2 to 6, and n is a number of 2 to 15.

A monomer compound of the formula I and an oligomer compound of the formula II in which R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group or a phenyl group. Is also preferred.

Similarly, R ₄ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 4 to 16 carbon atoms, a cycloalkoxy group having 5 to 8 carbon atoms,
Monomeric compounds of formula I and oligomeric compounds of formula II representing allyl, propargyl, acetyl or benzyl groups are also preferred.

Particularly preferably, in the above formula, R ₁ and R ₂ are independently of each other a hydrogen atom and a carbon atom number of 1 to 1.
2 represents an alkyl group having 2 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group or a benzyl group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, 4 to 16 carbon atoms
Represents an alkoxy group of 5 to 8 carbon atoms, a cycloalkoxy group having 5 to 8 carbon atoms, an allyl group, a propargyl group, an acetyl group or a benzyl group, and R ₅ and R ₆ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Represents a group or a phenyl group, or R ₅ and R ₆ together with the carbon atom to which they are bonded form a cycloalkylidene ring having 5 to 8 carbon atoms, and R ₇ is a hydrogen atom or a carbon atom. Represents an alkyl group of the formulas 1 to 4, A is the following formula:

[Chemical 29] Represents a group represented by X is an oxygen atom or the following formula:

[Chemical 30] Wherein Y and Z each independently represent an alkylene group having 2 to 8 carbon atoms, an alkylene group having 4 to 12 carbon atoms interrupted by an oxygen atom, or an alkylene group having 4 to 8 carbon atoms. Represents an alkenylene group, m is 2
A monomer compound represented by the formula I and an oligomer compound represented by the formula II, each of which represents an integer of 1 to 6 and n represents a number of 2 to 10.

In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a phenyl group or a benzyl group, and R 1
₄ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 6 to 12 carbon atoms, an acetyl group or a benzyl group, and R ₅ and R ₆ each independently represent a hydrogen atom or 1 carbon atom. Or R ₅ and R ₆ together with the carbon atom to which they are attached form a cycloalkylidene ring having 5 to 8 carbon atoms, and A is of the formula:

[Chemical 31] Wherein X represents an oxygen atom, Y represents an alkylene group having 2 to 8 carbon atoms or an alkylene group having 4 to 12 carbon atoms interrupted by an oxygen atom, and n is 2 to Of particular interest are monomeric compounds of formula I representing the number of 10 and oligomeric compounds of formula II.

Of particular interest, in the above formula, R ₁ represents a hydrogen atom, R ₂ represents a hydrogen atom, and has 1 to 4 carbon atoms.
Represents an alkyl group or a cyclohexyl group, R ₃ represents a hydrogen atom, R ₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ and R ₆ are each independently a hydrogen atom or a carbon atom. Represents an alkyl group of the numbers 1 to 4, or R ₅ or R ₆ together with the carbon atom to which they are attached forms a cyclohexylidene ring, and A is of the formula:

[Chemical 32] A monomer compound represented by the formula I and an oligomer compound represented by the formula II, in which X represents an oxygen atom, and n represents a number of 2 to 10.

In the above formula I, if R ₄ is a hydrogen atom, then R ₅
A monomer compound in which R ₆ and R ₆ are not hydrogen atoms is particularly preferable.

The novel monomer compounds of the formula I can be prepared in a manner known per se, which is analogous to the procedure described in the documents mentioned above. For example, and this is preferred,
When the bisphosphorodichloridite of formula IV is reacted with the HALS compound of formula V:

[Chemical 33] (Wherein R ₁ , R ₂ , R ₃ , R ₄ , A and X have the same meaning as defined above), new monomer compounds of the formula I are obtained. The HALS compound of formula V is used in stoichiometric amounts, preferably in slight excess relative to the bisphosphorodichloridite of formula IV.

The reaction is carried out in the melt or in the presence of a suitable organic polar or apolar, aprotic solvent. The reaction is preferably carried out in the presence of a base, at a temperature between -20 ° C and the boiling point of the solvent, in particular between 10 ° C and 150 ° C. A base, eg an amine, may be used simultaneously as a solvent. The base can be used in several molar excesses with respect to the compound of formula IV or V used in various amounts, from catalytic to stoichiometric amounts. The hydrogen chloride formed during the reaction is converted to chloride, if appropriate through a base, and can be removed by filtration and / or washing with a suitable aqueous or solid phase. Secondary water-miscible solvents may also be used here. The product is conveniently isolated by evaporating the organic phase and drying the residue. The product is conveniently purified by chromatography on silica gel or recrystallization.

Suitable solvents for carrying out the reaction are hydrocarbons such as mesitylene, toluene, xylene, hexane,
Pentane or other petroleum ether fractions), halogenated hydrocarbons (eg di- or trichloromethane, 1,
2-dichloroethane, 1,1,1-trichloroethane or chlorobenzene), ethers (eg diethyl ether, dibutyl ether or tetrahydrofuran),
Ketones (eg acetone, ethylmethylketone, diethylketone, methylpropylketone or cyclohexanone) as well as acetonitrile, butylacetate, dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone are included.

Suitable bases are primary, secondary and especially tertiary amines (eg trimethylamine, triethylamine, tributylamine, N, N-dimethylamine, N, N-diethylamine or pyridine), hydrides (eg lithium hydride, hydrogen). Sodium or potassium hydride)
Or alkoxide (eg sodium methoxide).

Hydrides (eg sodium hydride, sodium borohydride or lithium aluminum hydride), alkali metals, alkali metal hydroxides or sodium methoxide are used as bases and correspond to the HALS compounds of the formula V. The alkoxide may first be formed and any reaction product formed (eg water or methanol) may be distilled (eg as an azeotrope with toluene as an azeotrope before reaction with the bisphosphorodichloridite of formula IV). ) Removed.

The compounds of formula IV are known or
Or for example DE-A-3928291 or Earl. A. Bartlett et al., J. Amer. Chem. Soc. 109
(19), 5699 (1987) can be produced by a method known per se. The compounds of formula IV, which are required for the preparation of the novel compounds of formula I, can be prepared in situ in analogy to the procedure described in the literature and are represented by the formula V without further isolation. And a monomer compound of formula I is obtained. Formula V
The HALS compound represented by the formula (1) is known, or can be produced by a method known per se, for example, as described in US-A-42333412. The novel oligomeric compounds of formula II can be prepared similarly to the above monomeric compounds of formula I.

The present invention further includes the following formula VI:

[Chemical 34] A bisphenol represented by the formula: wherein R ₁ , R ₂ , R ₃ and A have the same meaning as defined above or a mixture of bisphenols represented by the formula VI, first reacted with phosphorus trichloride. Then, the following formula VII:

[Chemical 35] Where R ₁ , R ₂ , R ₃ , n and A have the same meaning as defined above, and then the compound of formula VII is V:

[Chemical 36] Of the formula II consisting of reacting with a HALS compound of the formula where R ₄ and X have the same meaning as defined above or a mixture of HALS compounds of the formula V. It relates to a preferred method for producing oligomeric compounds.

Preferred reaction conditions for the second reaction step (reaction with a HALS compound of formula V), such as temperature, solvent, base or catalyst are those described above for the novel monomer compounds of formula I. Matches

The reaction of the bisphenol of formula VI with phosphorus trichloride to obtain the oligomeric compound of formula VII is carried out in the melt or preferably in the presence of a suitable organic polar or non-polar solvent. . This reaction is preferably a base or phase-transfer reagent.
In the presence of a temperature between 20 ° C and the boiling point of the solvent, especially 20
Temperature between ℃ and 150 ℃, eg 40 ℃ to 120 ℃
Is preferably carried out.

Suitable solvents for carrying out the reaction are hydrocarbons (eg mesitylene, toluene, xylene, hexane,
Pentane or other petroleum ether fractions), halogenated hydrocarbons (eg di- or trichloromethane, 1,
2-dichloroethane, 1,1,1-trichloroethane or chlorobenzene), ethers (eg diethyl ether, dibutyl ether or tetrahydrofuran),
Ketones (eg acetone, ethylmethylketone, diethylketone, methylpropylketone or cyclohexanone) as well as acetonitrile, butylacetate, dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone are included. Preferred solvents are hydrocarbons,
In particular toluene and xylene.

The base or phase transfer reagent is preferably used in catalytic amounts with respect to the bisphenol of formula VI. The catalyst is preferably used in an amount of 1 to 10 mol%, especially 2 to 8 mol%, based on the bisphenol of the formula VI.

Suitable bases are tertiary amines such as trimethylamine, triethylamine, tributylamine, N,
Includes N-dimethylaniline, N, N-diethylaniline, pyridine and 4-dimethylaminopyridine.
Particularly preferred is 4-dimethylaminopyridine.

Examples of suitable phase transfer reagents are quaternary ammonium salts such as tetrabutylammonium chloride and tetrabutylammonium bromide. Tetrabutylammonium bromide is particularly preferred.

The structural composition of the oligomeric compound of formula VII is determined by the reaction conditions, such as the solvent or reaction temperature, and the molar mixing ratio and concentration of the bisphenol of formula VI and phosphorus trichloride. The preferred molar mixing ratio of the bisphenol of the formula VI and phosphorus trichloride is 1: 1 to 1: 5, particularly preferably 1: 1 to 1 :.
It is 3.

The oligomeric compound of formula VII is preferably not isolated. When the reaction with phosphorus trichloride is complete, the excess phosphorus trichloride is conveniently removed by distillation together with an amount of solvent. The resulting solution of the oligomeric compound of formula VII is further reacted directly with the HALS compound of formula V to give the novel compound of formula II.

The bisphenol of formula VI and the formula V for the preparation of the novel oligomeric compounds of formula II
The preferred molar mixing ratio with the HALS compound represented by is 1: 1 to 1: 6, in particular 1: 1.2 to 1: 5, for example 1: 1.4 to 1: 4.4.

The novel monomeric and oligomeric compounds of the formulas I and II are conveniently isolated by filtration of the precipitated salts of the base used and evaporation of the filtrate under reduced pressure. An example of a preferable filter medium is Celite.
e), silica gel, porous diatomaceous earth and aluminum silicate.

Due to the complete precipitation of the ammonium salt, the evaporated filter residue is taken up again in a nonpolar solvent, for example toluene / hexane and refiltered. Excess HALS compound of formula V is preferably removed by distillation under reduced pressure.

Bisphenols of the formula VI are known or Hovenvale, Methods of Organic Chemistry, 6th.
/ Vol. 1c, 1030.
As mentioned above, the HALS compounds of formula V are known or can be prepared by methods known per se, for example as described in US Pat. No. 4,233,412.

The above two-step method preferably provides a mixture of oligomeric compounds of formula II. Therefore, the present invention provides a bisphenol of formula VI or a mixture of bisphenols of formula VI with phosphorus trichloride and a HALS compound of formula V or HA of formula V.
It relates to oligomeric products obtained by reacting with a mixture of LS compounds.

The novel oligomeric compounds of formula II have the formula VIII:

[Chemical 37] [In the formula, the terminal group E ₁ is, for example, —PCl ₂ , the following formula IX or X:

[Chemical 38] And a terminal group E ₂ is, for example, a chlorine atom or the following formula XI:

[Chemical Formula 39] Or a terminal group E ₁ and E ₂ together form a direct bond (cyclic compound), R 1
₄ and X have the same meaning as defined above], and may be linear or cyclic.

In formula VIII above, oligomeric compounds in which E ₁ represents a group of the formula IX and E ₂ represents a group of the formula XI are preferred.

The novel monomeric and oligomeric compounds of the formulas I and II are suitable for stabilizing organic materials against oxidative, thermal or photoinduced degradation. Examples of such materials are: 1. Polymers of mono- and di-olefins such as polypropylene, polyisobutylene, polybutene-
1, poly-4-methylpentene-1, polyisoprene or polybutadiene, and polymers of cycloolefins such as cyclopentene or norbornene, polyethylene (uncrosslinked or crosslinked), such as high density polyethylene (HDPE), low density polyethylene. (L
DPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, ie the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different processes, in particular the following processes: a) Radical polymerization (usually under high temperature and high pressure). b) Catalytic polymerization using a catalyst which usually contains one or more metals from group IVb, Vb, VIb or VIII of the Periodic Table. These metals are usually one or more ligands, typically π (pi)-or σ (sigma) -coordinated oxides, halides, alcoholates, esters, ethers, amines, alkyls, It has alkenyl and / or aryl. Even if these metal complexes are free bodies,
Alternatively, it may be fixed to a substrate, typically activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst may be used by itself in the polymerization, and other activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxane. Is I in the periodic table
a, IIa and / or IIIa elements).
The activators may be modified in a conventional manner with other ester, ether, amine or silyl ether groups.
The catalyst system is usually Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalyst.
e catalyst, SSC).

2. Item 1. Mixtures of the polymers mentioned under 1, such as polypropylene and polyisobutylene, polypropylene and polyethylene (eg PP / HDPE, PP / LDPE) and different types of polyethylene (eg LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and low density polyethylene (LD) thereof.
PE), propylene / butene-1 copolymer, propylene / isobutylene copolymer, ethylene /
Butene-1 copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene /
Heptene copolymers, ethylene / octene copolymers,
Propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers), And ethylene, propylene and dienes such as hexadiene,
Terpolymers with dicyclopentadiene or ethylidene norbornene; and with each other of the above copolymers, and 1. Mixtures with the polymers mentioned in 1, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE.
/ EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers, and mixtures thereof with other polymers such as polyamides.

4. Hydrocarbon resins (for example having 5 to 9 carbon atoms) and hydrogenated modifications thereof (for example tackifiers) and mixtures of polyalkylenes and starch.

5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylics such as styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene. / Acrylonitrile / Methyl acrylate; high impact mixtures of styrene copolymers with another polymer such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; and block copolymers of styrene such as styrene / butadiene / styrene, styrene / isoprene / Styrene, styrene /
Ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

7. Graft copolymers of styrene or α-methylstyrene, such as polybutadiene on styrene, polybutadiene-styrene or polybutadiene-
Acrylonitrile copolymer styrene, polybutadiene styrene and acrylonitrile (or methacrylonitrile), polybutadiene styrene, acrylonitrile and methyl methacrylate, polybutadiene styrene and maleic anhydride; polybutadiene styrene, acrylonitrile and maleic anhydride, polybutadiene styrene and maleimide 6. Styrene and alkyl acrylates or methacrylates for polybutadiene; styrene and acrylonitrile for ethylene / propylene / diene terpolymers, styrene and acrylonitrile for polyalkyl acrylates or polyalkylmethacrylates, styrene and acrylonitrile for acrylate / butadiene copolymers, and Section 6. Mixtures with the copolymers listed under, for example the copolymer mixtures known as ABS-, MBS-, ASA- or AES-polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylenes, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds such as polyvinyl chloride. , Polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.

9. Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; polymethylmethacrylate, polyacrylamide and polyacrylonitrile, impact-modified with butyl acrylate.

10. Item 9. Copolymers of the monomers mentioned with one another or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylonitrile / halogenated vinyl copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers .

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyrate,
Polyallyl phthalate or polyallyl melamine; and these and 1. Copolymers with the olefins described under.

12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxides, polypropylene oxides or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxy end group-containing polyethers, polyesters or polybutadienes as one component and aliphatic or aromatic polyisocyanates as the other component, and precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams. For example, polyamide 4, polyamide 6, polyamide 6/6, 6/1
Aromatic polyamides starting from 0, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, m-xylene, diamine and adipic acid; hexamethylenediamine and isophthalic acid and / or terephthalic acid And polyamides produced with or without the addition of elastomers as modifiers, for example poly-
2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; the above polyamide and polyolefin, olefin copolymer,
Block copolymers with ionomers or chemically bonded or grafted elastomers or with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and EPDM or ABS modified polyamides or copolyamides; and during processing Condensed polyamide (RIM polyamide type).

17. Polyureas, polyimides, polyamideimides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,
4-dimethylol-cyclohexaneterephthalate and polyhydroxybenzoates and block copolyetheresters derived from hydroxy-terminated polyethers; and polycarbonate or MBS modified polyesters.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers 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.

22. Dry and non-dry alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinkers,
And halogen-containing modifications thereof having low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylic esters such as epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.

26. Cross-linked epoxy resins derived from polyepoxides such as bisglycidyl ether or cycloaliphatic diepoxides.

27. Natural polymers such as cellulose,
Gum, gelatin and chemically modified polymeric homologues derivatives thereof, such as cellulose acetate, cellulose propionate and cellulose butyrate or cellulose ethers such as methyl cellulose; and rosins and their derivatives.

28. Mixtures of the aforementioned polymers (polyblends), eg PP / EPDM, polyamide / EPD
M or ABS, PVC / EVA, PVC / ABS, P
VC / MBS, PC / ABS, PBTP / ABS, PC
/ ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PP
O / HIPS, PPO / PA 6.6 and copolymers,
PA / HDPE, PA / PP, PA / PPO.

29. Natural and synthetic organic materials, which are pure monomeric compounds or mixtures of such compounds, such as mineral oils, animal and vegetable fats, oils and waxes or the above oils, fats based on synthetic esters (eg phthalates, adipates, phosphates or trimellitates) And waxes, and mixtures of synthetic esters and mineral oils mixed in all weight ratios, the materials typically being used as fiber spinning oils and as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubbers, eg natural latex of carboxylated styrene / butadiene copolymers.

The present invention therefore comprises (a) an organic material which is susceptible to oxidative, thermally or photoinduced degradation, and (b) at least one monomer or oligomeric compound of formula I or II or of formula VI A bisphenol represented by formula VI or a mixture of bisphenol represented by formula VI with phosphorus trichloride and a HALS compound represented by formula V or formula V
And a composition comprising at least one oligomeric product obtained by reacting with a mixture of HALS compounds represented by

The organic material to be protected is preferably a natural, semi-synthetic or preferably synthetic organic material. Particularly preferred are thermoplastic polymers, especially PVC or polyolefins, especially polyethylene and polypropylene.

It should be emphasized about the action of the novel compounds on thermal and oxidative degradation, as occurs during the processing of thermoplastics, in particular on heating. The new compounds are therefore very suitable for use as processing stabilizers.

The monomeric and oligomeric compounds of the formulas I and II are 0.01 to 10%, for example 0.01 to 5%, based on the weight of the organic material to be stabilized,
It is preferably added to the material to be stabilized in an amount of 0.025 to 3%, in particular 0.025 to 1%.

In addition to the monomeric and oligomeric compounds of the formulas I and II, the novel compositions can also contain other costabilizers, such as: Antioxidant 1.1. Examples of alkylated monophenols 2,6-di-tert-butyl-4-methylphenol, 2-
Tert-Butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tertiary Butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,
6-dioctadecyl-4-methylphenol, 2,4
6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-
(1'-methylundeci-1'-yl) phenol,
2,4-Dimethyl-6- (1'-methylheptadecyl-
1'-yl) phenol, 2,4-dimethyl-6-
(1'-Methyltridec-1'-yl) phenol and mixtures thereof.

1.2. Examples of alkylthiomethylphenol 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-diphenol Dodecylthiomethyl-4-nonylphenol.

1.3. Examples of hydroquinones and alkylated hydroquinones 2,6-di-tert-butyl-4-methoxyphenol, 2,
5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4 -Hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) Adipate.

1.4. Examples of tocopherols α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Examples of hydroxylated thiodiphenyl ether 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-) 3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,3)
6-di-secondary amylphenol), 4,4'-bis (2,2
6-Dimethyl-4-hydroxyphenyl) disulfide.

1.6. Examples of alkylidene bisphenol 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4 -Methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-
Cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol),
2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (6-tert-butyl-4-isobutylphenol), 4,4'-methylenebis (2,6- Di-tert-butylphenol), 4,4 '
-Methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-) 5-methyl-2-hydroxybenzyl) -4
-Methylphenol, 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-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-ditert-butyl-4- Hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl-4-n-dodecylmercaptobutane, 1,1,5
5-Tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7. Examples of O-, N- and S-benzyl compounds 3,5,3 ', 5'-Tetra-tert-butyl-4,4'-
Dihydroxydibenzyl ether, octadecyl-4-
Hydroxy-3,5-dimethylbenzyl mercaptocetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithio Terephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Examples of hydroxybenzylated malonates Dioctadecyl-2,2-bis (3,5-ditert-butyl-2-hydroxybenzyl) malonate, Dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methyl) Benzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-ditertiarybutyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3
-Tetramethylbutyl) phenyl] -2,2-bis (3,5-ditert-butyl-4-hydroxybenzyl) malonate.

1.9. Examples of aromatic hydroxybenzyl compounds 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene,
1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene,
2,4,6-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.10. Examples of triazine compounds 2,4-bis (octylmercapto) -6- (3,5-
Di-tert-butyl-4-hydroxyanilino) -1,3,5
-Triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino)-
1,3,5-triazine, 2-octyl mercapto-
4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-
Tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 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, 2,4,6-Tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) ) -1,3,5-Triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,
5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11. Examples of benzylphosphonates Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-
4-Hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di-tert-butyl- Calcium salt of 4-hydroxybenzyl-phosphonic acid monoethyl ester.

1.12. Examples of acylaminophenols 4-hydroxylauric acid-anilide, 4-hydroxystearic acid-anilide, octyl N- (3,5-di-
Tertiary butyl-4-hydroxyphenyl) -carbamate.

1.13. β- (3,5-di-tert-butyl-
Ester of 4-hydroxyphenyl) propionic acid with the following monohydric or polyhydric alcohols Examples of alcohols: methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thia Pentadecanol, trimethylhexanediol, trimethylpropane, 4-hydroxymethyl-
1-phospha-2,6,7-trioxabicyclo [2.
2.2] Octane.

1.14. Ester of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with the following monohydric or polyhydric alcohols Examples of alcohols: methanol, ethanol, octanol, octadecanol, 1,6- Hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thia Pentadecanol, trimethylhexanediol, trimethylpropane, 4-hydroxymethyl-
1-phospha-2,6,7-trioxabicyclo [2.
2.2] Octane.

1.15. Ester of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with the following monohydric or polyhydric alcohols Examples of alcohols: methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thia Pentadecanol, trimethylhexanediol, trimethylpropane, 4-hydroxymethyl-
1-phospha-2,6,7-trioxabicyclo [2.
2.2] Octane.

1.16.3 Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and the following monohydric or polyhydric alcohols Examples of alcohols: methanol, ethanol, octanol, octadecanol, 1,6 -Hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thia Pentadecanol, trimethylhexanediol, trimethylpropane, 4-hydroxymethyl-
1-phospha-2,6,7-trioxabicyclo [2.
2.2] Octane.

1.17. β- (3,5-di-tert-butyl-
Examples of amides of 4-hydroxyphenyl) propionic acid N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine,
N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine,
N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

2. UV absorbers and light stabilizers 2.1.2 Examples of 2- (2'-hydroxyphenyl) benzotriazole 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 (3 ', 5'-di Tert-butyl-2 '
-Hydroxyphenyl) benzotriazole, 2-
(5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-
(1,1,3,3-Tetramethylbutyl) phenyl) benzotriazole, 2- (3 ′, 5′-ditert-butyl-
2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-
5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-tert-butyl-2 '
-Hydroxyphenyl) benzotriazole, 2-
(2'-hydroxy-4'-octyloxyphenyl)
Benzotriazole, 2- (3 ', 5'-ditertiary amyl-2'-hydroxyphenyl) benzotriazole, 2
-(3 ', 5'-bis (α, α-dimethylbenzyl)-
2'-hydroxyphenyl) benzotriazole; 2-
(3'-tert-butyl-2'-hydroxy-5 '-(2-
Octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3′-tert-butyl-
5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2- Methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 '
-Tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole,
2- (3'-tert-butyl-2'-hydroxy-5'-
(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'-
[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-
Methylphenyl) benzotriazole and 2- (3 '
-Tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenylbenzotriazole mixture, 2,2'-methylene-bis [4-
(1,1,3,3-Tetramethylbutyl) -6-benzotriazol-2-ylphenol]; 2- [3′-tert-butyl-5 ′-(2-methoxycarbonylethyl)-
Transesterification of the 2'-hydroxyphenyl] -2H- benzotriazole with polyethylene glycol 300; _{[R-CH 2 CH 2 -COO (} CH 2) 3 - ] ₂ -
(In the formula, R = 3′-tert-butyl-4′-hydroxy-
5'-2H-benzotriazol-2-ylphenyl).

2.2 Examples of 2-hydroxybenzophenones 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4
-Benzyloxy-, 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Examples of esters of substituted and unsubstituted benzoic acids 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tertiarybutylbenzoyl) resorcinol, benzoylresorcinol, 2 , 4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl- 4-hydroxybenzoate,
2-Methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Examples of acrylates ethyl α-cyano-β, β-diphenyl acrylate,
Isooctyl α-cyano-β, β-diphenyl-acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate , Methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

2.5. Examples of Nickel Compounds A nickel complex of 2,2′-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as a 1: 1 or 1: 2 complex, optionally n-. Butylamine, with other ligands such as triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, monoalkyl esters such as methyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid Alternatively, a nickel salt of ethyl ester, a ketoxime such as 2-hydroxy-
Nickel complex of 4-methyl-phenyl undecyl ketoxime, nickel complex of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with other ligands.

2.6. Examples of sterically hindered amines Bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-tetramethylpiperidyl) succinate, bis (1,2,2,6) 6-pentamethylpiperidyl) sebacate, bis (1,2,2)
2,6,6-Pentamethylpiperidyl) n-butyl-
3,5-Ditert-butyl-4-hydroxybenzylmalonate, 1- (2-hydroxyethyl) -2,2,6,6
-A condensation product of tetramethyl-4-hydroxypiperidine and succinic acid, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tertiary octylamino- 2,6-dichloro-1,
Condensation product with 3,5-triazine, tris (2,2,2
6,6-Tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1'- (1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2 6,6-
Tetramethylpiperidine, bis (1,2,2,6,6-
Pentamethylpiperidyl) -2-n-butyl-2- (2
-Hydroxy-3,5-ditertiarybutylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-
2,4-dione, bis (1-octyl-2,2,6,6
-Tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis (2,2,6,6-
Tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-
Condensation product with triazine, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis Condensation product with (3-aminopropylamino) ethane, 2-chloro-4,6-di (4-n-butylamino-
1,2,2,6,6-pentamethylpiperidyl) -1,
Condensation product of 3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-
Dodecyl-7,7,9,9-tetramethyl-1,3,8
-Triazaspiro [4.5] decane-2,4-dione,
3-dodecyl-1- (2,2,6,6-tetramethyl-
4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4
-Piperidyl) pyrrolidine-2,5-dione.

2.7. Examples of oxamide 4,4'-dioctyloxyoxanilide, 2,2'-
Diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-ditertiary butoxyanilide, 2,2'-didodecyloxy-5,5'-ditertiary butoxyanilide, 2
-Ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxyanilide and the compound and 2-ethoxy-2 '-Ethyl-5,4'-
Mixtures with di-tert-butyl-oxanilide, mixtures of ortho- and para-methoxy-disubstituted oxanilides, and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8.2- (2-hydroxyphenyl)
Examples of -1,3,5-triazine 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-
Hydroxy-4-octyloxyphenyl) -4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,
6-bis (2,4-dimethylphenyl) -1,3,5-
Triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) ) -4,6-bis (4-
Methylphenyl) -1,3,5-triazine, 2- (2
-Hydroxy-4-dodecyloxyphenyl) -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6
-Bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3)
-Octyloxypropyloxy) phenyl] -4,6
-Bis (2,4-dimethyl) -1,3,5-triazine.

3. Examples of metal deactivators N, N'-diphenyloxamide, N-salicyral-
N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-ditert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino- 1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-diacetyladipoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide , N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

4. Examples of phosphites and phosphonites Triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritol diphosphite, tris (2 , 4-Ditert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-) Methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-ditert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis ( 2,4,6-Tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-ditert-butylphenyl)
4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-1
2H-dibenz [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenz [d, g] -1,3 Two
-Dioxaphosphocin, bis (2,4-di-tert-butyl-
6-methylphenyl) methylphosphite, bis (2,2
4-ditert-butyl-6-methylphenyl) ethylphosphite.

5. Examples of peroxide scavengers Esters of β-thiodipropionic acid, such as lauryl,
Stearyl, myristyl or tridecyl ester, zinc salt of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.

6. Examples of polyamide stabilizers Copper salts and salts of divalent manganese in combination with iodides and / or phosphorus compounds.

7. Examples of basic costabilizers melamine, polyvinylpyrrolidone, dicyandiamide,
Triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinate. Nolate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.

8. Examples of nucleating agents 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

9. Examples of fillers and reinforcing agents: calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica,
Barium sulphate, metal oxides and hydroxides, carbon black and graphite.

10. Examples of other additives Plasticizers, lubricants, emulsifiers, pigments, brighteners, flame retardants, antistatic agents and foaming agents.

11. Benzofuranones and indolinones such as US-A-4325863, US-A-43.
38244, US-A-5175312, US-A-5.
216052, US-A-5252643, DE-A-
4316611, DE-A-4316622, DE-A
-4316876, EP-A-05983939 or EP-A-0591102, or 3-
[4- (2-acetoxyethoxy) phenyl] -5,7
-Di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7 -Di-tert-butyl-3- (4- [2-hydroxyethoxy] phenylbenzofuran-2-one], 5,
7-Ditert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-
Dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one.

The costabilizers other than benzofuranone listed in item 11 are added at a concentration of, for example, 0.01 to 10% based on the total weight of the material to be stabilized.

Other preferred compositions are, in addition to component (a) and the monomeric and oligomeric compounds of the formulas I and II, other additives, in particular phenolic antioxidants, light stabilizers and / or processing agents. Contains a stabilizer.

Particularly preferred additives are phenolic antioxidants (item 1 in the list above), sterically hindered amines (item 2.6 in the list above), phosphites and phosphonites (item 4 in the list above) and peroxides. Scavenger (item 5 in the list above).

Other additives (stabilizers) which are likewise particularly preferred are also benzofuran-2-ones, for example US-A-43.
25863, US-A-4338244, US-A-5.
175312, US-A-5216052, US-A-
5252643, DE-A-4316611, DE-A
-4316622, DE-A-4316876, EP-
A-05899839 and EP-A-0591102.

Examples of such benzofuran-2-ones are of the formula:

[Chemical 40] [Wherein R ′ ₁₁ represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system, and R ′ ₁₂ represents a hydrogen atom,
R _'14 represents a hydrogen atom, an alkyl group, a cyclopentyl group having 1 to 12 carbon atoms, cyclohexyl group or a chlorine atom, R' ₁₃ is either the same meanings as R _'12 or R' _14, or the following formula:

[Chemical 41] {In the formula, R ′ ₁₆ has a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by an oxygen atom or a sulfur atom, and has 3 to 16 carbon atoms in total. Dialkylaminoalkyl group, cyclopentyl group, cyclohexyl group, phenyl group or 1 to 3 having a total of up to 18 carbon atoms
Represents a phenyl group substituted with 4 alkyl groups, s
Represents 0, 1 or 2, and the substituents R ′ ₁₇ are independently of each other a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a total of 1 to 16 carbon atoms. or two phenyl group substituted by an alkyl group, the formula: -C ₂ H ₄ OH, -
_{C 2 H 4 -O-C t} H 2t + 1 or

[Chemical 42] Or represents together with the nitrogen atom to which they are bound to form a piperidine group or a morpholine group, t represents 1 to 18, and R ′ ₂₀ represents a hydrogen atom or the number of carbon atoms. Represents an alkyl group having 1 to 22 or a cycloalkyl group having 5 to 12 carbon atoms, A represents an alkylene group having 2 to 22 carbon atoms which may be interrupted by a nitrogen atom, an oxygen atom or a sulfur atom, and R ′
₁₈ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
A cyclopentyl group, a cyclohexyl group, a phenyl group, a phenyl group substituted by 1 or 2 alkyl groups having up to 16 carbon atoms or a benzyl group, and R ′ ₁₉ represents an alkyl group having 1 to 18 carbon atoms; represents, D is -O -, - S -, - SO -, - SO 2 - or -C (R _{'21) 2} - represents a substituent R' ₂₁ are each independently hydrogen, carbon atoms 1 represents a to 16 alkyl group, to two R _'21 1 no carbon atoms combined in 1
6 ', _R'21 is further a phenyl group or the following formula:

[Chemical 43] (In the formula, s, R ′ ₁₆ and R ′ ₁₇ have the same meanings as described above), and E is the following formula:

[Chemical 44] (Wherein, R _'11, R' ₁₂ and R _'14 are as defined above) represents a group represented by a group represented by}, and R' ₁₅ represents a hydrogen atom, the number of carbon atoms 1 to 20 alkyl groups, cyclopentyl groups, cyclohexyl groups, chlorine atoms or the following formulas:

[Chemical formula 45] (In the formula, R ′ ₁₆ and R ′ ₁₇ have the same meanings as above)
In or represents a group represented by or R _'15 is R' is a compound represented by forming a tetramethyl group is with _14].

[0126] Preferred among the above benzofuran-2-one, in the above formula, R _'13 is hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a chlorine atom or the following formula:

[Chemical formula 46] Or -D-E (wherein, s, although _{R '16, R' 17,} D and E are as defined above, R _'16 is especially hydrogen,
It represents an alkyl group having 1 to 18 carbon atoms, a cyclopentyl group or a cyclohexyl group).

[0127] The benzofuran-2-one other preferred among the above formula, R _'11 is substituted by one or two alkyl groups having up to 12 carbon atoms phenyl or together phenyl It represents a group, R _'12
Represents a hydrogen atom, R ′ ₁₄ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ′ ₁₃ represents a hydrogen atom,
An alkyl group having 1 to 12 carbon atoms, represented by the following formula:

[Chemical 47] Or a group represented by -D-E, R _'15 is not hydrogen or C 1 -C to 20 alkyl group, the formula:

[Chemical 48] In or represents a group represented by or R _'15 is R' form a tetramethylene group is combined with the _14, s, R _'16, R' _17,
D and E are compounds having the same meanings as defined above.

[0128] The benzofuran-2-ones, especially interesting in the above formula, R _'13 represents a hydrogen atom, an alkyl group, or -D-E of 1 to 12 carbon atoms,
It R _'12 and R' ₁₄ is not hydrogen or C 1 -C independently of one another represent 4 alkyl, and R _'15
Is a compound having 1 to 20 carbon atoms, and D and E have the same meanings as defined above.

[0129] Finally Further, in the above formula, R _'13 is hydrogen, C 1 -C 4 alkyl or -D-E
The stands, R _'12 and R' ₁₄ represents a hydrogen atom, and R _'15 represents an alkyl group, a cyclopentyl group or cyclohexyl group having 1 to 4 carbon atoms, D is a group -C
(R ′ ₂₁ ) ₂ −, and E is the following formula:

[Chemical 49] Wherein the substituents R ′ ₂₁ are the same or different from each other, each represents an alkyl group having 1 to 4 carbon atoms, and R ′ ₁₁ , R ′ ₁₂ , R ′ ₁₄ and R ′ ₁₅ are Benzofuran-2-one, which has the same meaning as above, is also of particular interest.

The amount of benzofuran-2-one additionally used can vary within wide limits. For example, 0.000
It can be present in the novel composition according to the invention in an amount of 1 to 5% by weight, preferably 0.001 to 2% by weight, in particular 0.01 to 2% by weight.

The monomeric and oligomeric compounds of the formulas I and II according to the invention and any other additives may be used in known manner in polymeric organic materials, for example by dissolving or dispersing the dissolved or dispersed compounds. It is incorporated by applying it to a polymeric organic material and then evaporating the solvent if necessary. The novel compounds of the formulas I and II can also be added to the materials to be stabilized in the form of masterbatches containing the compounds in a concentration of 2.5 to 25% by weight.

The novel monomer and oligomer compounds of the formulas I and II according to the invention may be added before or during the polymerization or before the crosslinking. The monomeric and oligomeric compounds of the formulas I and II according to the invention may be incorporated into the material to be stabilized in the raw form or encapsulated in waxes, oils or polymers.

The monomeric and oligomeric compounds of the formulas I and II according to the invention may be sprayed onto the polymer to be stabilized. They can dilute other additives (for example the conventional additives mentioned above) or their melts, so that they can be sprayed together with said additives onto the polymer to be stabilized. A particularly advantageous method is the addition by spraying during the deactivation of the polymerization catalyst, in which case the steam used for the deactivation may be used for the spraying.

In the case of polyolefins which are polymerized in the form of beads, it is advantageous, for example, to apply the novel compounds of the formulas I and II according to the invention by spraying, if desired with other additives. May be.

The materials thus stabilized can be used in a very wide range of moldings, such as films, fibers, tapes, molding compositions, binders for profiles or paints, adhesives or adhesive cements.

As mentioned above, the organic material to be protected is preferably an organic polymer, especially a synthetic polymer. Thermoplastic materials, especially polyolefins, are advantageously protected among others. Above all, the excellent activity of the compounds of formula I as processing stabilizers (heat stabilizers) should be emphasized. For this purpose, they are advantageously added to the polymer before or during processing. However, other polymers (eg elastomers) or lubricants or hydraulic fluids (working fluids) can also be stabilized against degradation (degradation), eg light-induced degradation or thermo-oxidative degradation. Elastomers are listed above in the list of possible organic materials.

Suitable lubricants and hydraulic fluids are based, for example, on mineral or synthetic oils or mixtures thereof. Lubricants are known to the person skilled in the art and are relevant to the technical literature, for example Dieter Klamann, "Schmierstoffe und verwandte Pro.
dukte "(Verlag Chemie, Weinheim 1982), Schewe-Kob
ek, "Das Schmiermittel-Taschenbuch" (Dr. AlfredHut
hig-Verlag, Heidelberg, 1974) and "Ullmanns Enzyk.
lopadie der technischen Chemie "vol. 13, pages 85-
94 (Verlag Chemie, Weinheim 1977).

Therefore, a preferred embodiment of the present invention is the formula I
And the monomeric and oligomeric compounds of formula II and the bisphenols of formula VI or of formula V
To a product obtained by reacting a mixture of bisphenols of formula I with phosphorus trichloride and a HALS compound of formula V or a mixture of HALS compounds of formula V against oxidative, thermal or photoinduced decay It is to be used for stabilizing organic materials.

The novel monomeric and oligomeric compounds of the formulas I and II are distinguished by extremely high hydrolytic stability and advantageous coloring properties, ie low fading of the organic material during processing. Organic materials stabilized by the compounds of the invention are particularly well protected against photoinduced degradation.

The present invention therefore comprises a monomer or oligomeric compound of the formula I or II or a bisphenol of the formula VI or a mixture of bisphenols of the formula VI with phosphorus trichloride and the formula V. HA
Oxidation, heat or light consisting of mixing or applying at least one of the products obtained by reacting with an LS compound or a mixture of HALS compounds of formula V, into or into an organic material. The present invention relates to a method for stabilizing an organic material against induced decay.

[0141]

The present invention will be described in more detail by the following examples. Parts and percentages are by weight. Example 1: Preparation of compound (101) (Table 1) a) Phosphorus trichloride 9.10 ml (14.28 g, 104 mmol, 2.6 eq) was added to 4,4'-cyclohexylidene bis (2- Tributylphenol) 15.22 g (4
0.0 mmol, 1.0 eq) and 0.20 g (1.60 mmol) of 4-dimethylaminopyridine are added dropwise to a stirred suspension in 46 ml of toluene at room temperature under a nitrogen atmosphere. The mixture is then warmed to 100 ° C. over 1 hour and stirred at this temperature for 1.5 hours. When the evolution of hydrogen chloride gas has subsided, the mixture is stirred at 100 ° C. for a further 30 minutes with a slow flow of nitrogen. The resulting solution is diluted with 20 ml of toluene and excess phosphorus trichloride is removed by distillation with about 20 ml of toluene. The solution contains 4,4'-cyclohexylidene bis (2-tert-butylphenyldichlorophosphite).

B) 2,2 of the above solution (Example 1a)
6,6, -Tetramethylpiperidin-4-ol 27.
4 g (175 mmol, 4.4 eq) and 22.2 g (220 mmol, 5.5 eq) of triethylamine are added dropwise to a stirred suspension in 250 ml of toluene under nitrogen atmosphere at room temperature over 10 minutes. The reaction mixture is then warmed to 105 ° C. and stirred at this temperature for a further 5 hours. The white suspension is cooled to room temperature and filtered through Celite and the filtrate is evaporated on a vacuum rotary evaporator. The residue is hexane / toluene 1:
Take up in one solvent mixture and filter through Celite again. The filtrate is evaporated on a vacuum rotary evaporator and the residue is dried in high vacuum, mp 48
17.84 g of compound (101) (Table 1) at -52 ° C
(42%) is obtained.

Example 2: Preparation of compound (102) (Table 1) In the same manner as in Example 1, 4,4 'in 50 ml of toluene.
23.2 g (40.0 mmol, cyclohexylidene bis (2-tert-butylphenyldichlorophosphite))
1.0 equivalent) of 2,2,2,6,6-pentamethylpiperidin-4-ol 27.4 g (160 mmol, 4.
Reaction with 0 equivalents gives 23.74 g (53%) of compound (102) (Table 1), mp 51-57 ° C.

Example 3: Oligomer compound (103)
Preparation of (Table 2) a) Phosphorus trichloride (4.55 ml, 7.10 g, 52 mmol, 2.6 eq) was added to 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 7.85 g (2).
0.0 mmol, 1.0 equiv.) And 0.20 g (1.60 mmol) 4-dimethylaminopyridine are added dropwise at 50 ° C. to a stirred suspension in 15 ml of toluene under a nitrogen atmosphere. After about 30 minutes, the mixture is warmed to 75 ° C and stirred at this temperature for 1.5 hours. The reaction mixture is then evaporated on a vacuum rotary evaporator and the residue (9.14 g) dissolved in 50 ml toluene.

B) 1,2,2,6,6-pentamethylpiperidin-4-ol 10.55 g (61.6 mmol, 3.1 eq) and triethylamine 8.57 g
(84.7 mmol, 4.2 eq) of toluene 100 m
bisdichlorophosphite (see Example 3 above)
(a)) to a stirred solution of 50 ml of toluene in a nitrogen atmosphere over a period of 15 minutes. The reaction mixture is then warmed to 105 ° C. and at this temperature a further 5
Stir for hours. The white suspension is cooled to room temperature and filtered through Celite and the filtrate is evaporated on a vacuum rotary evaporator. Distillation of excess 1,2,2,6,6-pentamethylpiperidin-4-ol at 160 ° C./0.08 mbar in a valve tube oven gave compound (103) (2nd melting point 73-76 ° C.).
Table) 7.52 g (43%) is obtained.

2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane in Example 3 was replaced with 2,
2-bis (3-tert-butyl-4-hydroxyphenyl)
Propane or 2,2-bis (3-isopropyl-4-
Compound (104) or (105) is obtained by substituting hydroxyphenyl) propane (Table 2).

Example 4: Oligomer compound (106)
Preparation of (Table 2) a) Phosphorus trichloride (2.60 ml, 4.12 g, 30.0 mmol, 1.5 equivalents) was added with 4,4'-cyclohexylidenebis (2-tert-butylphenol) (7.61 g). (20.
0 mmol, 1.0 eq) and 4-dimethylaminopyridine 0.10 g (0.80 mmol) toluene 40
Add dropwise to a stirred suspension in ml at 50 ° C. under nitrogen atmosphere. The reaction mixture is then warmed to 105 ° C. over 1 hour and stirred at this temperature for 1.5 hours. When the evolution of hydrogen chloride gas has subsided, the mixture is stirred for a further 30 minutes at 105 ° C. with a slow flow of nitrogen. The resulting solution is diluted with 20 ml of toluene and excess phosphorus trichloride is removed by distillation with about 20 ml of toluene.

B) 2,2 of the above solution (Example 4a)
6,6-Tetramethylpiperidin-4-ol 9.42
g (60.0 mmol, 3.0 eq) and 10.12 g (100 mmol, 5.0 eq) of triethylamine were added dropwise to a stirred suspension in 100 ml of toluene under nitrogen atmosphere at room temperature over 10 minutes. To do. The thick suspension is then warmed to 105 ° C. and a further 5 minutes at this temperature.
Stir for hours. The reaction mixture is cooled to room temperature and filtered through Celite, and the filtrate is evaporated on a vacuum rotary evaporator. The residue was dried in high vacuum to give an oligomeric compound (106), mp 69-78 ° C.
(Table 2) 12.26 g (70%) are obtained.

Example 5: Oligomer compound (107)
Preparation of (Table 2) 1,2,2,6,6-pentamethylpiperidin-4-ol 10.28 g of 2,2,6,6-tetramethylpiperidin-4-ol in Example 4 (60. 0 mmol, 3.0 equivalents) by melting point 53-58 ° C
An oligomeric compound (107) of (Table 2) is obtained.

Example 6: Oligomer compound (108)
Preparation of (Table 2) a) Phosphorus trichloride 2.10 ml (3.30 g, 24.0 mmol, 1.2 eq.) Of 4,4'-cyclohexylidenebis (2-tert-butylphenol) 7.61 g (20.
0 mmol, 1.0 equiv.) And 0.26 g (0.80 mmol) of tetrabutylammonium bromide in a stirred suspension in 40 ml of toluene are added dropwise at 50 ° C. under a nitrogen atmosphere. The reaction mixture is then warmed to 105 ° C. over 1 hour and stirred at this temperature for 1.5 hours. When the evolution of hydrogen chloride gas has subsided, the mixture is stirred at 105 ° C. for a further 30 minutes with a slow flow of nitrogen. The resulting solution is diluted with 20 ml of toluene and excess phosphorus trichloride is removed by distillation with about 20 ml of toluene.

B) 1, 2 of the above solution (Example 6a)
2,6,6-pentamethylpiperidin-4-ol 4.
80 g (28.0 mmol, 1.4 eq) and 10.12 g (100 mmol, 5.0 eq) of triethylamine were added dropwise to a stirred suspension in 100 ml of toluene under nitrogen atmosphere at room temperature over 10 minutes. To do. The thick suspension is then warmed to 105 ° C. and stirred at this temperature for a further 5 hours. The reaction mixture is cooled to room temperature and filtered through Celite, and the filtrate is evaporated on a vacuum rotary evaporator. The residue is dried in high vacuum to give 12.2 g (95%) of oligomeric compound (108) (Table 2), mp 95-115 ° C.

Table 1

[Table 1]

Table 2: Oligomer compounds

[Table 2]

[Table 3] (Footnote of the above table) Mn: number average molecular weight Mw: weight average molecular weight a) measured by GPC (gel permeation chromatography) b) measured by MALDI (matrix assisted laser deprotonation)

Example 7: Stabilization of polypropylene during multiple extrusion Irganox® 1076 (n-
Octadecyl 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate Polypropylene powder pre-stabilized with 0.025% [Profax® 6501] 1.3 kg (melt flow index 3 0.2 g / 10 min, measured at 230 ° C./2.16 kg) Irganox 1010 (pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 0.05%, steered Calcium phosphate 0.05%, dihydrotalcite [DH
T4A (registered trademark), Kyowa Chemical Industry Co., Ltd., Mg _4.5
Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O] 0.03% and the compound of Table 1 0.05%. This mixture was extruded at 100 rpm in an extruder with a cylinder diameter of 20 mm and a length of 400 mm, adjusting the three heating zones to the following temperatures: 260, 270, 280 ° C.
The extrudate is cooled by drawing it through a water bath and then granulated. This granulate is extruded repeatedly. After three extrusions, the melt flow index is measured (230
C and 2.16 kg). A large increase in the melt flow index means significant chain length degradation, ie low stabilization. The results are shown in Table 3.

[0155]

Example 8: Stabilization of polyethylene during processing Polyethylene powder [Lupolen® 5
260Z] 100 parts of Irganox 1010 (pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 0.05
Parts and 0.1 part of the stabilizer from Table 1, and the mixture was mixed on a Brabender Plastograph at 220
Mix at 0 ° C and 50 rpm. During this time, the compounding resistance is continuously recorded as torque. During the compounding time, the polymer begins to crosslink after an extended period of time, which is evident from the rapid increase in torque. Fourth
The table shows the time to a significant increase in torque as a measure of stabilizing effect. The longer this time, the better the stabilizing effect.

[0157]

Claims (17)

[Claims] 1. A monomer compound represented by the following formula I or an oligomer compound represented by the following formula II: (In the formula, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an unsubstituted or an alkyl group having 1 to 4 carbon atoms. A substituted cycloalkyl group having 5 to 8 carbon atoms; a phenyl group which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms; an unsubstituted or substituted carbon group with an alkyl group having 1 to 4 carbon atoms A cycloalkenyl group having 5 to 8 atoms; or a phenylalkyl group having 7 to 9 carbon atoms, R ₃ represents a hydrogen atom or a methyl group, R ₄ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms , OH, NO, —CH ₂ CN, an alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group having 5 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, 1 to 8 carbon atoms
Or an phenylalkyl group having 7 to 9 carbon atoms, which is unsubstituted or substituted on the phenyl ring by an alkyl group having 1 to 4 carbon atoms, R ₅ and R ₆ are independent of each other. Represents a hydrogen atom, CF ₃ , an alkyl group having 1 to 12 carbon atoms or a phenyl group, or R ₅ and R ₆ together with the carbon atom to which they are bonded are unsubstituted or have 1 carbon atom. 5 to 1 carbon atoms substituted with an alkyl group of 4 to 4
Two cycloalkylidene rings are formed, provided that R ₅ and R ₆ simultaneously represent a hydrogen atom, R ₄ does not represent a hydrogen atom, and R ₁ , R ₂ and R ₃ represent simultaneously a hydrogen atom. , And R ₅ and R ₆ simultaneously represent a methyl group, R ₄ does not represent a hydrogen atom, R ₇ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or the following formula III: R ₈ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, A represents an oxygen atom, a sulfur atom, or a compound represented by the following formula: Represents a group represented by: X is an oxygen atom or the following formula: Represents a group represented by: Y and Z are independently of each other an alkylene group having 2 to 18 carbon atoms, an oxygen atom, a sulfur atom or the following formula: 4 to 18 carbon atoms interrupted by a group represented by
Represents an alkenylene group having 4 to 8 carbon atoms or a phenylethylene group, m represents an integer of 2 to 8, and n represents 2 to 25.
Represents the number of). 2. In the above formula, R ₁ and R ₂ are independently of each other a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a cycloalkyl having 5 to 8 carbon atoms. Represents an alkyl group, an unsubstituted or substituted phenyl group having 1 to 4 carbon atoms, a cycloalkenyl group having 5 to 8 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms, and R ₄ is hydrogen An atom, an alkyl group having 1 to 4 carbon atoms,
OH, —CH ₂ CN, an alkoxy group having 4 to 18 carbon atoms, a cycloalkoxy group having 5 to 12 carbon atoms, an allyl group, a propargyl group, an acetyl group or a phenylalkyl group having 7 to 9 carbon atoms, R ₅ and R ₆ independently of one another represent a hydrogen atom, CF ₃ , an alkyl group having 1 to 8 carbon atoms or a phenyl group, or R ₅ and R ₆ together with the carbon atom to which they are bonded To form a cycloalkylidene ring having 5 to 8 carbon atoms, R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₈ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Where A is an oxygen atom and the following formula: Represents a group represented by: X is an oxygen atom or the following formula: Represents a group represented by: Y and Z are independently of each other an alkylene group having 2 to 12 carbon atoms, an oxygen atom or the following formula: 4 to 12 carbon atoms interrupted by a group represented by
Represents an alkenylene group having 4 to 8 carbon atoms or a phenylethylene group, m represents an integer of 2 to 6, and n represents 2 to 15
The compound of claim 1, which represents the number of 3. The compound according to claim 1, wherein R ₁ and R _{2 in the} above formula each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group or a phenyl group. 4. In the above formula, R ₄ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 4 to 16 carbon atoms, a cycloalkoxy group having 5 to 8 carbon atoms, an allyl group, and propargyl. The compound according to claim 1, which represents a group, an acetyl group or a benzyl group. 5. In the above formula, R ₁ and R ₂ are independently of each other a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and a cycloalkyl having 5 to 8 carbon atoms. Represents an alkyl group, a phenyl group or a benzyl group, R ₄ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Alkoxy group having 4 to 16 carbon atoms, 5 carbon atoms
Or represents a cycloalkoxy group, an allyl group, a propargyl group, an acetyl group or a benzyl group, wherein R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group; Or R ₅ and R ₆ together with the carbon atom to which they are bonded form a cycloalkylidene ring having 5 to 8 carbon atoms, and R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Where A is the following formula: Represents a group represented by: X is an oxygen atom or the following formula: Wherein Y and Z are independently of each other an alkylene group having 2 to 8 carbon atoms, an alkylene group having 4 to 12 carbon atoms interrupted by an oxygen atom, or 4 to 8 carbon atoms.
Represents an alkenylene group of, m represents an integer of 2 to 6, and n represents 2 to 10
The compound of claim 1, which represents the number of 6. In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a phenyl group or a benzyl group, and R ₄ is a hydrogen atom or a carbon atom. An alkyl group having 1 to 4 atoms,
An alkoxy group having 6 to 12 carbon atoms, an acetyl group or a benzyl group, R ₅ and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or R ₅ and R ₆ Together with the carbon atom to which they are attached form a cycloalkylidene ring having 5 to 8 carbon atoms, wherein A is of the formula: X represents an oxygen atom, Y represents an alkylene group having 2 to 8 carbon atoms or an alkylene group having 4 to 12 carbon atoms interrupted by an oxygen atom, and n is 2 to A compound according to claim 1 which represents a number of 10. 7. In the above formula, R ₁ represents a hydrogen atom, R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a cyclohexyl group, R ₃ represents a hydrogen atom, and R ₄ represents hydrogen. An atom or an alkyl group having 1 to 4 carbon atoms, R ₅ and R ₆ independently of each other represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ₅ and R ₆ are bonded to each other. Together with the carbon atom being formed to form a cyclohexylidene ring, A is of the formula: The compound according to claim 1, which represents a group represented by: X represents an oxygen atom, and n represents a number of 2 to 10. 8. The following formula VI: embedded image (Wherein the general symbols have the same meanings as defined in claim 1) or a mixture of bisphenols of the formula VI are first reacted with phosphorus trichloride to give the following formula VII: : [Chemical 15] (Wherein the general symbols in the formula have the same meanings as defined in claim 1) and then the compound of formula VII is converted to the following formula V: 2. A HALS compound of formula (wherein the general symbols have the same meaning as defined in claim 1) or a mixture of HALS compounds of formula V. A method for producing an oligomer compound represented by formula II. 9. The following formula VI: embedded image (Wherein the general symbols have the same meanings as defined in claim 1) or a mixture of bisphenols of formula VI and phosphorus trichloride and the following formula V: An oligomeric product obtained by reacting with a HALS compound of formula (wherein the general symbols have the same meaning as defined in claim 1) or a mixture of HALS compounds of formula V. 10. An organic material which is a) susceptible to oxidative, thermal or light induced decay, and b) at least one compound of formula I or II according to claim 1 or at least one claim 9. A composition comprising the oligomer product of. 11. The composition according to claim 10, which further comprises other additives in addition to the components (a) and (b). 12. The composition according to claim 11, wherein the other additive is a phenolic antioxidant, a light stabilizer and / or a processing stabilizer. 13. The other additive is benzofuran-2-.
The composition according to claim 11, which is at least one compound of on-type. 14. A composition according to claim 10, wherein component (a) is a natural, semi-synthetic or synthetic polymer. 15. The composition of claim 10 in which component (a) is a thermoplastic polymer. 16. The composition according to claim 10, wherein the component (a) is a polyolefin. 17. The composition according to claim 10, wherein component (a) is polyethylene or polypropylene.