CA2146824A1 - Monomeric and oligomeric bisphenyl-hals phosphites as stabilizers - Google Patents

Monomeric and oligomeric bisphenyl-hals phosphites as stabilizers

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Publication number
CA2146824A1
CA2146824A1 CA002146824A CA2146824A CA2146824A1 CA 2146824 A1 CA2146824 A1 CA 2146824A1 CA 002146824 A CA002146824 A CA 002146824A CA 2146824 A CA2146824 A CA 2146824A CA 2146824 A1 CA2146824 A1 CA 2146824A1
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Prior art keywords
hydrogen
formula
c4alkyl
tert
compound
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CA002146824A
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French (fr)
Inventor
Rita Pitteloud
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BASF Schweiz AG
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Individual
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    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/529—Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Abstract

Monomeric and oligomeric bisphenyl-HALS phosphites as stabilizers Abstract of the disclosure The invention relates to novel monomeric compounds of the formula I and oligomeric compounds of the formula II
(I)

Description

I

Monomeric and oli~omeric bisphenYl-HALS phosphites as stabilizers The present invention relates to novel monomeric and oligomeric bisphenyl-HALS phos-phites, to compositions comprising an organic material, preferably a polymer, and the novel monomeric and oligomeric bisphenyl-HALS phosphites, and to the use thereof for the stabilization of organic materials against oxidative, thermal or light-induced degrada-tion.
.
Organic phosphites are known in industry as costabilizers, secondary antioxidants and pro-cessing stabilizers, inter alia for polyolefins; examples of such known phosphite stabilizers are given in R. Gachter/H. Miiller (Eds.), Plastics Additives Handbook,3rd Ed., p. 47, Hanser, Munich,1990, and EP-A-356 688.

Hindered amines, including, in particular, compounds containing 2,2,6,6-tetramethylpipe-ridyl groups, are preferably used as light stabilizers (hindered amine light stabilizers, HALS).

Phosphites containing HALS structural units are described, for example, by T. K~nig et al, ;
J. prakt. Chem. 334,333-349 (1992), in US-A-5 239 076, GB-A-2 247 241, DE-A-4 306 747 and FR-A-2 380 290.

There continues to be a demand for effective stabiliærs for organic materials which are -sensitive to oxidative, thermal and/or light-induced degradation. ~
. . . -: :-: ::
It has now been found that a selected group of such HALS phosphites is particularly sui-table as stabilizers for organic materials which are sensitive to oxidative, thermal or light~
induced degradation. Particular emphasis should be made of the suitability of said com~
pounds as processing stabiliærs for synthetic polymers.
.., , . ~ . .
The present invention therefore relates to monomeric compounds of the formula I and -- - -oligomeric compounds of the formula II - `~
~ ': ~ ' '``~

` 21~682~
.
L ~ ~ Rz ~A J~RZ 11 2 (I) H3C$CH3~
z t n inwhich ~ ~ .
Rl and R2, independently of one another, are hydrogen, Cl-C25aL~cyl, C2-C24aLkenyl, un- .
substituted or Cl-C4ally1-substituted Cs-C8cycloalkyl; unsubstituted or C~-C4aLlcyl-substi-tuted phenyl; unsubsdtuted or Cl-C4aL~yl-substituted Cs-C8cycloaL~enyl; or CTCgphenyl-alkyl, R3 is hydrogen or methyl, R4 is hydrogen, Cl-Cgalkyl, O, OH, NO, -CH2CN, Cl-C18aLlcoxy, C5-Cl2cycloaL~oxy,C3-C6aL~enyl, C3-C6alkynyl, Cl-C8acyl, or C7-CgphenylaLkyl which is unsubstituted or substituted on the phenyl ring by C~-C4alkyl, R5 and R6, independently of one another, are hydrogen, CF3, C~-CI2aLkyl or phenyl, or Rs - - -and R6, together with the carbon atom to which they are bonded, form an unsubstituted or Cl-C4aL~yl-substituted Cs-CI2cycloalkylidene ring; with the proviso that, if R5 and R6 are . -simultaneously hydrogen, R4 is not hydrogen; and with the proviso that, if Rl, R2 and R3 are simultaneously hydrogen and R5 and R6 are simultaneously methyl, R4 is not hydrogen, R7 is hydrogen, Cl-C8alkyl or a radical of the formula III -: -.:.:

21~682~
, --R4 (m) CH3 :
CH3 ~;
R8 is hydrogen or Cl-C8aLtcyl, A is oxygen, sulfur,--C--, -CH2CH2-C-O-Y-O-C-CH2CH2- ~r ~(cH2)m-o-c-z-c-o-(cH2) X is oxygen or /~R7, ~ . -Y and Z, independent1y of one another, are C2-Cl8alkylene, C4-Cl8alkylene which is -interrupted by oxygen, sulfur or ~N--R8; C4-C8aLkenylene or phenylethylene, m is an integer from 2 to 8, and n is a number from 2 to 25.
,.. . ~., ", Al~yl having up to 25 carbon atoms is a branched or unbranched radical, for example I ^ `
methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, l-methylpentyl, 1,3-dimethylbutyl, n-hexyl, l-methylhexyl, n-heptyl, -isoheptyl, 1,1,3,3-tetramethylbutyl, l-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, l-methylundecyl, ; -dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hepta-decyl, octadecyl, eicosyl or docosyl. One of the preferred meanings of Rl and R2 is, for example, Cl-Cl8alkyl, in particular Cl-Cl2aLkyl, for example Cl-C8alkyl. A particularly preferred meaning of R2 is Cl-C4aLkyl.

Alkenyl having 2 to 24 carbon atoms is a branched or unbranched radical, for example ~ -vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,~pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl.
Preference is given to alkenyl having 3 to 18, in particular 3 to 12, carbon atoms.

Unsubstituted or Cl-C4alkyl-substituted C5-Cl2cycloaLlcyl, in particular C5-C8cycloaLkyl, .

21~6824 which preferably contains 1 to 3, in particular 1 or 2, branched or unbranched aL~cyl radi-cals, is, for example, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cyclo-heptyl, cyclooctyl or cyclododecyl. Preference is given to Cs-C8cycloaLkyl, in particular cyclohexyl. -Cl-C4aL~yl-substituted phenyl, which preferably contains 1 to 3, in particular 1 or 2, aL~yl groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphe-nyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.

Unsubstituted or Cl-C4alkyl-substituted C5-Cgcycloalkenyl, which preferably contains 1 to 3, in particular 1 or 2, branched or unbranched aLkyl radicals, is, for example, cyclopen-tenyl, methylcyclopentenyl, dimethylcyclopentenyl, cyclohexenyl, methylcyclohexenyl, dimethylcyclohexenyl, trimethylcyclohexenyl, tert-butylcyclohexenyl, cycloheptenyl or cyclooctenyl. Preference is given to cyclohexenyl.

C7-Cgphenylalkyl which is unsubstituted or substituted on the phenyl radical by Cl-C4-aLkyl and which preferably contains 1 to 3, in particular 1 or 2, branched or unbranched alkyl radicals is, for example, benzyl, a-methylbenzyl, a,a-dimethylbenzyl, 2-phenyl-ethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-di-methylbenzyl or 4-tert-butylbenzyl. Benzyl is preferred.
. ~ . .. .
AL~coxy having up to 18 carbon atoms is a branched or unbranched radical, forexample methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy7 hexadecyloxy or octadecyloxy. Preference is given to aLtcoxy having 6 to 12 carbon atoms.

CycloaLlcoxy having S to 12 carbon atoms is, for example, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy or cyclododecyloxy. One of the preferred mea-nings of R4 is Cs-C8cycloalkoxy. Particular preference is given to cyclopentoxy and cyclo-hexoxy. ~ .

AL~cynyl having 3 to 6 carbon atoms is a branched or unbranched radical, for example pro-pynyl (propargyl, --CH2-C--CH), 2-butynyl or 3-butynyl.

_, . . . .
, ;. , .; , , . , . ,, ., .. . ~.
~, . :- . : . : ;: . . :. ..

. . . . . .

- 21~824 Acyl having 1 to 8 carbon atoms is, for example, formyl, acetyl, propionyl, butyryl, penta~
noyl, hexanoyl, heptanoyl, octanoyl, benzoyl, acryloyl or crotonyl. Preference is given to C1-C8aLkanoyl, C3-C8aL1~enoyl or benzoyl, in particular acetyl.

Unsubstituted or Cl-C4aL~cyl-substituted C5-C8cycloaLI~ylidene, which preferably contains 1 to 3, in particular 1 or 2, branched or unbranched alkyl radicals, is, for example, cyclo-pentylidene, methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene, methyl-cyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclo- ~ -hexylidene, cycloheptylidene or cyclooctylidene. Preference is given to cyclohexylidene and tert-butylcyclohexylidene.

C2-CI8alkylene is a branched or unbranched radical, for example methylene, ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethy- -lene, decamethylene, dodecamethylene or octadecarnethylene. Preference is given to ` `~ -C2-CI2aLkylene, in particular C2-C8alkylene. I ~
. . " .
C4-CI8AL~cylene which is interrupted by oxygen, sulfur or ~R8 can be interrupted ~ - -once or more than once and is, for example, -CH2CH2-O-CH2CH2-, -CH2CH2-S-CH2CH2-,-CH2CH2-NH-CH2CH2-,-CH2CH2-N(CH3)-CH2CH2-, :~.;','' -CH2CH2-O-CH2CH2-O-CH2CH2-,-CH2CH2-(O-CH2CH2-)20-CH2CH2-, :'~- u"
-CH2CH2-(O-CH2CH2-)30-CH2CH2-, -CH2CH2-(O-CH2CH2-)40-CH2CH2- or . - ~- :
C4-C8allcenylene Y or Z is, for example, 2-buten-1,4-ylene. ~ -Phenylethylene is -CH(C6H5)CH2-.

Preference is given to monomeric compounds of the formula I and oligomeric compounds of the formula II in which Rl and R2, independently of one another, are hydrogen, Cl-Cl8alkyl, C2-CI8aL~cenyl, C5-C8cycloalkyl, unsubstituted or Cl-C4alkyl-substituted phenyl, Cs-Cgcycloalkenyl or C7-CgphenylaLkyl, R4 is hydrogen, Cl-C4alkyl, OH, -CH2CN, C4-Cl8aL~oxy, C5-Cl2cycloaL~coxy, allyl, pro-pargyl, acetyl or C7-CgphenylaL~cyl;
.

, . ,.,j, .... -~.,..... --~` 214~2~
- 6 - ~
.

Rs and R6, independently of one another, are hydrogen, CF3, Cl-C8alkyl or phenyl, or Rs and R6, together with the carbon atom to which they are bonded, form a C5-C8cycloalkyli-dene ring; .: . :
R7 is hydrogen or Cl-C8alkyl, R8 is hydrogen or Cl-C4alkyl, Ais oxygen, IC , -CH2CH2-C-O-Y-O-C-CH2CH2- or -(CH2)m-O-C-Z-C-O-(CH2)m-, X is oxygen or / R7, ~ -Y and Z, independently of one another, are C2-CI2aLkylene, C4-Cl2alkylene which is interrupted by oxygen or /N~R8; C4-C8alkenylene or phenylethylene, m is an integer from 2 to 6, and n is a number from 2 to lS.

Preference is also given to the monomeric compounds of the formula I and oligomeric compounds of the formula II in which Rl and R2, independently of one another, are .
hydrogen, Cl-Cgalkyl, cyclohexyl or phenyl.

Preference is likewise given to the monomeric compounds of the formula I and oligomeric compounds of the formula II in which R4 is hydrogen, Cl-C4alkyl, C4-Cl6alkoxy, Cs-C8-cycloaIkoxy, allyl, propargyl, acetyl or benzyl.

Particular preference is given to the monomeric compounds of the formula I and oligo- -meric compounds of the formula II in which Rl and R2, independently of one another, are hydrogen, Cl-Cl2aLIcyl, CrCl2alkenyl, : ~ .
Cs-C8cycloalkyl, phenyl or benzyl, ~ .:
R4 is hydrogen, Cl-C4alkyl, C4-Cl6alkoxy, C5-C8cycloaIkoxy, allyl, propargyl, acetyl or : ::
benzyl;
R5 and R6, independently of one another, are hydrogen, Cl-C8alkyl or phenyl, or R5 and ~ ::
R6, together with the carbon atom to which they are bonded, form a C5-C8cycloalkylidene rmg;
R7 is hydrogen or Cl-C4aLkyl, A is Cl , -CH2CH2-C-O-Y-O-C-CH2CH2- or -(CH2)m-O-C-Z-C-O-(CH2)m-, R6 ..

,, : S ~ .t ! ; . ' : '~, ' `

.;',.~', ,. . '.' . , : ' . . . ' ' 21~682~

X is oxygen or / R7, Y and Z, independently of one another, are C2-C8aL~cylene, C4-CI2alkylene which is inter-rupted by oxygen; or C4-C8alkenylene, m is an integer from 2 to 6, and n is a number from 2 to 10.

Of particular interest are the monomeric compounds of the formula I and oligomeric com-pounds of the formula II in which Rl and R2, independently of one another, are hydrogen, Cl-C8aLkyl, cyclohexyl, phenyl or benzyl, : -:
R4 is hydrogen, Cl-C4alkyl, C6-CI2aLkoxy, acetyl or benzyl;
Rs and R6, independently of one another, are hydrogen or C~-C8alkyl, or R5 and R6, to-gether with the carbon atom to which they are bonded, form a Cs-C8cycloalkylidene ring; :
Rs O O
A is--Cl-- or -CH2CH2-C-O-Y-O-C-CH2CH2-R6 .~
X is oxygen, Y is C2-C8aL~cylene or C4-CI2aLlcylene which is interrupted by oxygen; and.; : .:
n is a number from 2 to 10.

Of specific interest are the monomeric compounds of the formula I and oligomeric com-pounds of the formula lI in which Rl is hydrogen, R2 is hydrogen, Cl-C4alkyl or cyclohexyl, R3 is hydrogen, ~ :
R4 is hydrogen or Cl-C4aL~cyl, R5 and R6, independently of one another, are hydrogen or Cl-C4aL~cyl, or R5 or R6, to- ~ .
gether with the carbon atom to which they are bonded, form a cyclohexylidene ring;
Rs A is--C--R6 ~ .
X is oxygen, and ~ ::
n is a number from 2 to 10. ~;

Particular preference is given to the monomeric compounds of the formula I in which, if 'i` i "' ' :` ' ' ~ ~ : : ., . ~

21~6824 R4 is hydrogen, R5 and R6 are not hydrogen.

The novel monomeric compounds of the formula I can be prepared in a manner known per se analogously to the literature procedures mentioned at the outset.

For example, and this is preferred, a bisphosphorodichloridite of the formula IV is reacted with an HALS compound of the formula V

~ R3 {~4 (V) in which Rl, R2, R3, R4, A and X are as defined above, to give the novel monomeric com~
pounds of the formula I.

The HALS compound of the forrnula V is used in stoichiometric amounts, preferably in a ~ -slight excess, with respect to the bisphosphorodichloridite of the formula IV.

The reaction is carried out in the melt or in the presence of a suitable organic, polar or ~ -apolar, aprotic solvent. This reacdon is preferably carried out in the presence of a base at temperatures between -20C and the boiling point of the solvent, in particular at tempera^
tures between 10 and 150C.

Bases such as amines can simultaneously also be used as solvent.

The base can be employed in various amounts, from catalytic via stoichiometric amounts up to an excess of several times the molar amount with respect to the compounds of the formula IV or V employed. The hydrogen chloride formed during the reaction is, if appro~
priate, converted through the base into chloride, which can be removed by filtration and/or -~ `
washing with a suitable aqueous or solid phase; a second, water-immiscible solvent can also be employed here. The products are expediently isolated by evaporating the organic :
phase and drying the residue. The products are expediently purified by chromatography on ~ -silica gel or by recrystallization.

:

21~6824 ~

Suitable solvents for carrying out the reaction include hydrocarbons (for example mesi-tylene, toluene, xylene, hexane, pentane or other petroleum ether fractions), halogenated ~ ~
hydrocarbons (for example di- or trichloromethane,1,2-dichloroethane, l,1,1-trichloro- ~ - -ethane or chlorobenzene), ethers (for exarnple diethyl ether, dibutyl ether or tetrahydro- - -furan), ketones (for example acetone, ethyl methyl ketone, diethyl ketone, methyl propyl ketone or cyclohexanone), furthermore acetonitrile, butyl acetate, dimethyl formamide, di-methyl sulfoxide or N-methylpyrrolidone.

Suitable bases include primary, secondary and in particular tertiary amines (for example trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline or pyridine), hydrides (for example lithium hydride, sodium hydride or potassium hydride) or alkoxides (for example sodium methoxide). ~ i-If hydrides (for example sodium hydride, sodium borohydride or lithium aluminiumhydride), alkali metals, alkali metal hydroxides or sodium methoxide are used as bases, the corresponding alkoxide of the HALS compound of the formula V can frst be formed;
any reaction product formed (for example water or methanol) is removed by distillation (for example as an azeotrope with toluene) before the reaction with the bisphosphorodi-chloridite of the formula IV.

The compounds of the formula IV are known or can be prepared by processes known per ~ -se, as described, for exarnple, in DE-A-3 928 291 or by R.A. Bartlett et al, J. Amer. Chem.
Soc. l09 (19),5699 (1987).

The compounds of the formula IV required for the preparation of the novel compounds of the formula I can be prepared in situ analogously to the abovementioned literature proce-dures, and reacted further, without isolation, with the HALS compounds of the formula V
to give the monomeric compounds of the formula I.

The HALS compounds of the formula V are known or can be prepared by processes known per se, as described, for example, in US-A-4 233 412.

The novel oligomeric compounds of the formula II can be prepared analogously to the above-described monomeric compounds of the formula I.

The invention furthermore relates to a preferred process for the preparation of the oligo-~.. ~ ., ,;. ~ - - , ~ . . " . . .

2 1 ~ 6 ~

meric compounds of the formula II, which comprises first reacting a bisphenol of the for- ;
mula VI or a mixture of bisphenols of the formula VI . ~ -~

R, R, R2 ~A J~ R ( I) in which Rl, R2, R3 and A are as defined above, with phosphorus trichloride to give a compound of the formula VII ~ ~ -tR~A~e L

in which Rl, R2, R3, n and A are as defined above, and subsequently reacting the com~
polmd of the formula VII with an HALS compound of the formula V or a mixture of ;~
HALS compounds of the formula V

_I CH3 HX ~--R4 (V) ~ ~;
CH3 ~:

in which R4 and X are as defined above.

The preferred reaction conditions for the second reaction step (reaction with the HALS
compound of the formula V), for example temperature, solvent, base or catalyst, corres-pond to those as described above for the novel monomeric compounds of the formula I. ~ ~ ;

The reaction of the bisphenol of the formula VI with phosphorus trichloride to give the ::~
oligomeric compound of the formula VII is carried out in the melt or preferably in the pre-21~682~

sence of a suitable organic, polar or apolar solvent. This reaction is preferably carried out in the presence of a base or phase-transfer reagent at temperatures between 20C and the boiling point of the solvent, in particular at temperatures of from 20C to 150C, for example from 40C to 120C.

Suitable solvents for carrying out the reacdon include hydrocarbons (for example mesity-lene, toluene, xylene, hexane, pentane or other petroleum ether fracdons), halogenated hydrocarbons (for example di- or trichloromethane, 1,2-dichloroethane, 1,1,1-trichloro-ethane or chlorobenzene), ethers (for example diethyl ether, dibutyl ether or tetrahydro-furan), ketones (for example acetone, ethyl methyl ketone, diethyl ketone, methyl propyl ketone or cyclohexanone), furthermore acetonitrile, butyl acetate, dimethyl formamide, di-methyl sulfoxide or N-methylpyrrolidone. Preferred solvents are hydrocarbons, in pardcu-lar toluene and xylene.

The base or phase-transfer reagent is preferably used in catalydc amounts with respect to the bisphenol of the formula VI. The catalyst is preferably employed in an amount of from l to 10 mol%, in pardcular from 2 to 8 mol%, with respect to the bisphenol of the formula VI.
: :..
Suitable bases include terdary amines, for example trimethylamine, triethylamine, tri-butylamine, N,N-dimethylaniline, N,N-diethylaniline, pyridine and 4- dimethylaminopyri-dine. Pardcular preference is given to 4-dimethylaminopyridine.
:~
Exarnples of suitable phase-transfer reagents are quaternary ammonium salts, for example tetrabutylammonium chloride and tetrabutylammonium bromide. Particular preference is given to tetrabutylammonium bromide.

The structural composidon of the oligomeric compounds of the formula VII depends on the reaction conditions, for example the solvent or reaction temperature, and on the molar -mixing rado and concentration of the bisphenol of the formula VI and phosphorus trichlo-ride.

Preferred molar mixing ratios between the bisphenols of the formula VI and phosphorus trichloride are 1:1 to 1:5, particularly preferably from 1:1 to 1:3.

The oligomeric compounds of the formula VII are preferably not isolated. When the reac-21~6,~24 tion with phosphorus trichloride is complete, the excess phosphorus trichloride is expe- ~ ;
diently removed by distillation together with some of the solvent. The resultant solution of the oligomeric compounds of the forrnula VIl is further reacted tel quel with an HALS
compound of the formula V to give the novel compounds of the formula II.

Preferred molar mixing ratios between the bisphenols of the formula VI and the HALS
compounds of the formula V for the preparation of novel oligomeric compounds of the formula II are from 1:1 to 1:6, in particular from 1:1.2 to 1:5, for example from 1:1.4 to 1:4.4.

The novel monomeric and oligomeric compounds of the formulae I and II are expediently isolated by filtradon of the precipitated salts of the bases employed and evaporation of the filtrate under reduced pressure.

Examples of preferred filtration aids are Celite, silica gel, kieselguhr and aluminium sili~
cate.
: ', .'~
For complete precipitadon of the ammonium salts, the evaporated filtration residue is pre- ~-ferably taken up again in an apolar solvent, for example toluenethexane, and re-filtered.
The excess HALS compound of the formula V is preferably removed by distillation under reduced pressure.

The bisphenols of the formula VI are known or can be prepared as described in Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Volume 6/lc, 1030.

As mentioned above, the HALS compounds of the formula V a~e known or can be pre-pared by processes known per se, as described, for example, in US-A-4 233 412.

The two-step process described above preferably gives mixtures of oligomeric compounds of the formula II.

The present invention therefore also relates to oligomeric products obtainable by reacting ~ - -a bisphenol of the formula VI or a mixture of bisphenols of the formula VI with phospho-rus trichloride and an HALS compound of the formula V or a mixture of HALS com- - - -pounds of the formula V.

:.................................................... - . : . .: . - , . .

2146~2~

The novel oligomeric compounds of the formula lI can, as shown in the formula VIII, be linear or cyclic, H3HC3C~cCHH3 1 E, ~ I~A~p3 R3 R3 n in which the terminal group El is, for example, -PCl2, a radical of the formula IX or a radi~
cal of the formula X, [ 3 ~2 and the terminal group E2 is, for example, chlorine or a radical of the formula XI; - - :~

~_~ CH3 --X~--R4 (XI) ~ ~ :

CH3 :
or furthermore the terminal groups E1 and E2 together form a direct bond (cyclic com-- ~ pounds) in which R4 and X are as defined above.

Preference is given to oligomeric compounds of the formula VIII in which E1 is a radical of the formula lX and E2 is a radical of the formula XI.

The novel monomeric and oligomeric compounds of the formulae I and II are suitable for the stabilization of organic materials against oxidative, thermal or light-induced degrada-tion.
Examples of such materials are:

l. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut- l-ene, poly-4-methylpent- l-ene, polyisoprene or polybutadiene, as well as poly-mers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which opdonaUy can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially ~ - ;
by the foUowing, methods: ~ -a) radical polymerisation (normally under high pressure and at elevated temperature).

b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or vm of the Periodic Table. These metals usuaUy have one or more than one ligand, typically oxides, ha1ides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ~- or c~-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, dtanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the ~ ~ -polymerisation or further activators may be used, typicaUy metal aUcyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said ~
metals being elements of groups Ia, lIa and/or I~a of the Periodic Table. The ~ ~-activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil -Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). . -21~6824 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 monoolefins and diolefins with each other or with other vinyl mono-mers, for example ethylene/propylene copolymers, linear low density polyethylene(LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-l-ene copolymers, propylene/isobutylene copolymers, ethylene/but-l-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, 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 mon-oxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpoly-mers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethy-lidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and altemating or random polyalkylene/carbon mon-oxide copolymers and mixtures thereof with other polymers, for example polyamides. -4. Hydrocarbon resins (for example Cs-Cg) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyaLkylenes and starch.

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

6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/buta-dienelalkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copoly-mers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/-propylene/diene terpolymer; 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 a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and aLkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyaL~yl acrylates or polyaLkyl methacrylates, styrene and acrylonitrile on acrylate/buta-diene copolymers, as well as mixtures thereof with the copolymers listed under 6), 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 polyethylene, copolymers of ethylene and chlorinated ethylene, epi- -chlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene -chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from a,~-unsaturated acids and derivatives thereof such as polyacry-lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylo-nitriles, impact-modified with butyl acrylate. ~ ~B
10. Copolymers of the monomers mentioned under 9) with each other or with other -~
unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/-aL~cyl acrylate copolymers, acrylonitrile/aL~coxyaL~yl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, poly-vinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as weU as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, poly~
ethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, ~ -',`. . ~ ; - : : ~ : : '.

21~6~2~ -acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with sty-rene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybuta-dienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursorsthereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or ;
from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, poly-amide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or graf-ted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as we11 as polyamides or copolyamides modified with EPDM
or ABS; and polyamides condensed during processing (RIM polyamide systems). - ~ -~
17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also -polyesters modified with polycarbonates or MBS.
. :~, 19. Polycarbonatesandpolyestercarbonates. ~-20. Polysulfones, polyether sulfones and polyether ke~ones.
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.

21~6~24 22. Drying and non-drying aLkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. AL~yd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.
26. Crosslinlced epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homolo~
gous derivatives thereof, for example cellulose acetates, cellulose propionates and cellu-lose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly- -amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PClthermoplastic PUR, POM/acrylate, POM/MBS, PPO/HlPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.
29. Naturally occurring and synthetic organic materials which are pure monomeric com-pounds 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, adi-pates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emul-sions of such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.

. . ~ ., .. . : . ~ . . .. - . . . ~ .

21~6~2~

The invention therefore furthermore relates to compositions comprising (a) an organic material subjected to oxidative, thermal or light-induced degradation and (b) at least one monomeric or oligomeric compound of the formula I or II or at least one oligomeric pro- ~-duct obtainable by reacting a bisphenol of the formula VI or a mixture of bisphenols of the formula VI with phosphorus trichloride and an H~LS compound of the formula V or a mixture of HALS compounds of the formula V.

The organic materials to be protected are preferably natural, semisynthetic or preferably synthetic organic materials. Particular preference is given to thermoplastic polymers, in particular PVC or polyolefins, in particular polyethylene and polypropylene.

Particular emphasis should be placed on the action of the novel compounds against ther-mal and oxidative degradation, in particular on heating, as occurs in the processing of ther-moplastics. The novel compounds are therefore highly suitable for use as processing stabi-lizers.

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

In addition to the monomeric and oligomeric compounds of the formulae I and II, the novel compositions can contain further costabilizers, for example the following:
1. Antioxidants 1.1. AL~cylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(oc-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, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-di-methyl-6-(1'-methylt~idec-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, .. :.,: , . : , , ,. ,- . : ., 21~682~

2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-do-decylthiomethyl-4-nonylphenol .

1.3. HYdroquinones and aL~Ylated hYdroguinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-di- -phenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxy-anisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate. -~: .
1.4. Tocopherols, for example o~-tocopherol"~-tocopherol, ~-tocopherol, ~tocopherol and mixtures thereof (Vitamin E). ~ ~ -1.5. Hvdroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methyl-phenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thio-bis(6-tert-butyl-2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis-(2,6-dim- -~
ethyl-4-hydroxyphenyl)disulfide.

1.6. AL~cYlidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(oc-methyl~
cyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methy-lenebis[6-(a-methylbenzyl)-4nonylphenol], 2,2'-methylenebis[6-(oc,oc-dimethylbenzyl)-4-nonylphenol], 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-methyl-phenyl)-3-n-dodecylmer-captobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)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-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-te~-t-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane.

1.7. O-. N- and S-benzvl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxy-dibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris-(3,5-di-tert-: 21~6~2~

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-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate .

1.8. Hydroxybenzvlated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malo-nate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyi-4-hydroxybenzyl)malonate, bis-[4-(1, 1 ,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris-(3,5-di-tert-butyl-4-hy-droxybenzyl)-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. Triazine Compounds, for example 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-hydroxy-anilino)-1,3,5-triazine, 2-octylmercapto-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-di-methylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-tri-azine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3 ,S-tris(3 ,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. BenzYlphosPhonates~ for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphos-phonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-S-tert-butyl-4-hydroxy3-methylbenzyl-phosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid. -1.12. AcYlaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of ,B-(3.5-di-tert-butvl-~hvdroxvphenYl)ProPionic acid with mono- or poly- ~ -hydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9- - ~ -nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, di-ethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri-:' - ~:

r~ .

21~6824 methylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo~2.2.2]octane.

1.14. Esters of ,B-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, l,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-thiapentadecanol, trimethylhexanedi-ol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. ~

l.lS. Esters of ~(3.5-dicyclohexYI-4-hydroxvphenvl)propionic acid with mono- or poly- ~ -hydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, di-ethylene glycol, triethylene glycol, pentaerythtitol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri-methylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. -1.16. Esters of 3.5-di-tert-butyl-4-hYdroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, l,9-nonane-diol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaondecanol, 3-thiapentadecanol, trimethylhexanediol, tri-methylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
, .
1.17. Amides of ,B (3,5-di-tert-butvl-4-hYdroxYphenYI)propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine.

2. UV absorbers and li~ht stabilisers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 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)benzo-triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- ~ -2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole,2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-. :..
~,' ~' "

21~6~24 di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(oc,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycar-bonylethyl)phenyl)-S-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-car-bonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyl-oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonyl-ethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzo-triazole, and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-azole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxy-phenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3~, where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2.2. 2-HvdroxYbenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-de-cyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 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-hydroxy-benzoate.

2.4. Acrvlates, for example ethyl a-cyano-~"B diphenylacrylate, isooctyl a-cyano-,~"~di- ~- ;
phenylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-~methyl-p-methoxy-cinnamate, butyl a-cyano-~methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N-(,l~carbomethoxy-,l~-cyanovinyl)-2-methylindoline. ~ ~;
2.5. Nickel comPounds, for example nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetra- ; ~ -methylbutyl)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 the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-S-. .

214682~

hydroxypyrazole, with orwithoutadditionalligands.

2.6. StericallY hindered amines, for example bis(2,2,6,6-tetramethyl-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-piperidyl)succinate, bis(1,2,2,6,6-pentamethylpiperidyl)sebacate, bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succi-nic acid, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenedi- -~
amine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperi~
dyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4- piperidyl)-1,2,3,4-butane-tetracar-boxylate, 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-penta-methylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl- 1 ,3,8-triazasprio[4.5]decan-2,4-dion, bis( 1 -octyloxy-2,2,6,6-tetra-methylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butyl-amino-2,2,6,6-tetramethylpiperidyl )-1,3,5-triazine and 1,2-bis(3-aminopropylamino)-ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentarnethylpiperi- ~; -dyl)-1,3,5-triazine and l,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)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrroli-dine-2,5-dione.

2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioc-tyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'- ~ -ethyloxanilide,N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethox-anilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disub- -stituted oxanilides.
: : . ~ -: ,~:
2.8. 2-(2-HYdroxYPhenY~ 3~s-triazines~ for example 2,4,6-tris(2-hydroxy-4-octyloxy-phenyl)-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-hy- -droxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyl- ~ -oxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2hydroxy-~: :

21~82~

3-butyloxy-propoxy)phenyll-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)- 1 ,3,5-triazine.

3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl di-hydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-di-acetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)-thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phos-phites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, triocta-decyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phos-phite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaeryt hritol diphosphite, diisode-cyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol di-phosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphsophite, tristearyl sorbitol tri-phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyl- -oxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10 tetra-tert-butyl- 1 2-methyl-dibenz[d,g] -1,3 ,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6- -methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

5. Peroxide scaven~ers, 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 disulf~de, penta-erythritol tetrakis(,l~dodecylmercapto)propionate.

6. PolYamide stabilisers, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, tri-aUyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyure~
thanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium rici-noleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.
: ::

' ';-~:' ~' : : ~ : :: . ~ . .. .
: ~ : . .

214682~

8. Nucleatin~ a~ents, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid. ;~

9. Fillers and reinforcinx a~ents, for example, calcium carbonate, silicates, glass fibres, ~ ~-asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

10. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

11. Benzofuranones and indolinones, for example those disclosed in US-A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A-5 216 052, US-A-5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102 or 3-[4-(2-acet-oxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyl-oxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]-phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-piva-loyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
"~ -: . ~ .
The costabilizers, with the exception of the benzofuranones mentioned under point 11, are added, for example, in concentrations of from 0.01 to 10 %, based on the total weight of the material to be stabilized.
:
.. ~:: .: .- , Other preferred compositions comprise, in addition to component (a) and the monomeric ~ ~ -and oligomeric compounds of the formulae I and II, other additives, in particular phenolic - - , antioxidants, light stabilizers and/or processing stabilizers. ~ ~
: . ~
Particularly preferred additives are phenolic andoxidants (point 1 in the list), sterically hindered amines (point 2.6 in the list), phosphites and phosphonites (point 4 in the list) and peroxide scavengers (point 5 in the list).

Other additives (stabilizers) which are likewise particularly preferred are benzofuran-2-ones, as described, for example, in US-A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A-5 216 052, US-A-5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A-0 589 839 and EP-A-0 591 102.

':: ~., ' .c. .- . . - : . ~

-21~6~2~ -Examples of such benzofuran-2-ones are compounds of the formula R ", ~ :

in which R'll is an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system;
R'l2 is hydrogen; ~:
R'l4 is hydrogen, aLl~yl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chlorine;
O
R' 13 iS æ defined for R' 12 or R' 14 or is a radical of the formula -(CH2~C-OR' 16' . --(CH2~-N(R'17)2, ~CH23~-O-A-O-C~CH2 s~E~
O o o o ,,~ "~
(CH2)s~C~NR 18-A-NR 18-C-(CH2)s-E ~ --(cH2)s-c-NR~l8-A-o-c-(cH2)s-E, ~CH3~C--N/ \h--C~cH2~ E, -CH2-S-R'lg, -CH(C6H5)-C-OR'~6 ........ .. :.
or-D-E, in which R'l6 is hydrogen, alkyl having 1 to 18 carbon atoms, alkyl having 2 to 18 carbon atoms which is interrupted by oxygen or sulfur, dialkylaminoalkyl having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl which is substituted by 1 to 3 alkyl radicals having a total of at most 18 carbon atoms;
sisO, 1 or2; :~ ~-the substituents R'17, independently of one another, are hydrogen, alkyl having 1 to 18 - ~ -carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is subs.~ituted by 1 or 2 aLkyl :~
radicals having a total of at most 16 carbon atoms, a radical of the formula -C2H40H, ;~
O - ~
-C2H4-a-CtH2hl or -C2H4-O-C-R'20, or, together with the nitrogen atom to which they are bonded, form a piperidine or morpholine radical;
; '~

~-.... .. . - - - . ~ . -21~682~

t is from 1 to 18;
R'20 is hydrogen, aLkyl having 1 to 22 carbon atoms or cycloalkyl having 5 to 12 carbon atoms; : ~:
A is aLkylene having 2 to 22 carbon atoms which may be interrupted by nitrogen, oxygen or sulfur;
R'l8 is hydrogen, aL~cyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 aLkyl radicals having a total of at most 16 carbon atoms, or benzyl;
R'l9 is aL~cyl having 1 to 18 carbon atoms;
D is -O-, -S-, -SO-, -SOr or -C(R 21)2-; -~
the substituents R'2~, independently of one another, are hydrogen, Cl-Cl6alkyl, where the two R'21 radicals together contain 1 to 16 carbon atoms, R'21 is furthermore phenyl or a . ~:

radical of the formula ~CH2~C-OR'l6 or ~CH23~C-N(R'17)2, in which s, R'16 and R' ,7 are as defined above;
E is a radical of the formula :

D~ :~: .`: .-:
~ 15 .
R~o R'12 H R 11 in which R'll, R'l2 and R'l4 are as defined above; and R'l5 is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a radical of the formula -CH2-C-OR~I6 or -CH2-C-N(R~I7)2, in which R'l6 and R'l7 are as defined above, or R'ls together with R'14 forms a tetramethylene radical.

Preference is given to benzofuran-2-ones in which R'l3 is hydrogen, aLkyl having 1 to 12 :
carbon atoms, cyclopentyl, cyclohexyl, chlorine or a radical of the formula ~CH2~-OR 16 ~ ~CH23~-N(R'I7)2 or -D-E, in which s, R'l6, R'l7, D and E
are as defined above, and R'l6 is, in particular, hydrogen, aL~cyl having 1 to 18 carbon ... , .. - .. .. .

..... , ~ .~ . . .

214682~

atoms, cyclopentyl or cyclohexyl.

Preference is also given to benzofuran-2-ones in which R' 1 l is phenyl or phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 12 carbon atoms; R'12 is hydrogen; R'l4 is hydrogen or aLkyl having 1 to 12 carbon atoms; R'13 is hydrogen, alkyl having 1 to 12carbon atoms, ~CH23~C-OR 16, ~CH23~-N(R 17)2 or-D-E;

R'15 is hydrogen, alkyl having 1 to 20 carbon atoms, -CH2-~-OR'16 or -CH2-~-N(R 17)2 or R 15 together with R' 14 forms a tetramethylene radical, where s, R'~6, R'17, D and E are as defined at the outset.

Likewise of particular interest are benzofuran-2-ones in which R'l3 1s hydrogen, aLkyl having 1 to 12 carbon atoms or -D-E; R'12 and R'14, independently of one another, are hydrogen or alkyl having 1 to 4 carbon atoms; and R'l5 is aLkyl having 1 to 20 carbon atoms, where D and E are as defined at the outset.

Finally, likewise of particular interest are benzofuran-2-ones in which R'l3 is aLkyl having ~ -1 to 4 carbon atoms or -D-E; R'12 and R'14 are hydrogen; and R'15 is alkyl having 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, where D is a -C(R'21)2- group and E is a radical of the forrnula ` ~ ~ -.... ~ ::
R' ~ 15 ;~ C=O, R'-2 H R "
.,.'.: ~:
where the substituents R'2l are identica1 or different and are each alkyl having 1 to 4 ;
carbon atoms, and R'11, R'12, R'14 and R'ls are as defined above.

The amount of benzofuran-2-ones additionally employed can vary within broad limits. For example, they can be present in the novel compositions in amounts of from 0.0001 to 5 %

' .

,. . , - ~ ~,. . , . ,, - -, . . . v, .

" 21~682~

by weight, preferably from 0.001 to 2 % by weight, in particular from 0.01 to 2 % by weight.

The monomeric and oligomeric compounds of the formulae I and II and any further addi~
tives are incorporated into the polymeric, organic material by known methods, for example before or during shaping or alternatively by application of the dissolved or dis-peræd compounds to the polymeric, organic material, if necessary with subsequent evapo-ration of the solvent. The novel compounds of the formulae I and II can also be added to the materials to be stabilized in the form of a masterbatch, which contains theæ in, for example, a concentration from 2.5 to 25 % by weight.
-.. .
. , ~ ,. ~
The novel monomeric and oligomeric compounds of the formulae I and II can also be added before or during polymerization or before crosslinking.
,:~:: , ,, -:
The monomeric and oligomeric compounds of the formulae 1 and II can be incorporated .
into the material to be stabilized in pure form or encapsulated in waxes, oils or polymers.

The monomeric and oligomeric compounds of the formulae I and II can also be sprayed onto the polymer to be stabilized. They are capable of diluting other additives (for -example the conventional additives mentioned above) or their melts, so that they can also ~ ~ ~
be sprayed onto the polymer to be stabilized together with these additives. A particularly - -advantageous method is the addition by spraying during deactivation of the polymeriza-tion catalysts, where, for example, the steam uæd for deactivation can be used for the spraying.

In the case of polyolefins polymerized in bead form, it may, for example, be advantageous ` ~:
to apply the novel compounds of the formulae I and II, if desired together with other addi~
tives, by spraying.

The materials stabilized in this way can be uæd in a very wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or adhesive cements.

As mentioned above, the organic materials to be protected are preferably organic poly-mers, particularly synthetic polymers. Thermoplastic materials, in particular polyolefins, ~ ;
are particularly advantageously protected. In particular, the excellent activity of the com-- 214682~
pounds of the formula I as processing stabilizers (heat stabilizers) should be emphasized.
For this purpose, they are advantageously added to the polymer before or during proces-sing thereof. However, other polymers (for example elastomers) or lubricants or hydraulic fluids can also be stabilized against degradation, for example light-induced or thermo-oxi-dative degradation. Elastomers are given in the above list of possible organic materials. -~

Suitable lubricants and hydraulic fluids are based, for example, on mineral or synthetic oils or mixtures thereof. The lubricants are known to the person skilled in the art and are described in the relevant specialist literature, for example in Dieter Klamann, "Schmier-stoffe und verwandte Produkte" [Lubricants and Related Products] (Verlag Chemie, Wein-heim, 1982), in Schewe-Kobek, "Das Schmiermittel-Taschenbuch" [The Lubricant Hand- i book] (Dr. Alfred Huthig-Verlag, Heidelberg, 1974) and in "Ullmanns Enzyklopadie der technischen Chemie" ~Ullmann's Encyclopedia of Industrial Chemistry], Vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).

A preferred embodiment of the present invention is therefore the use of monomeric and oligomeAc compounds of the formulae I and II and products obtainable by reacting a bis-phenol of the formula VI or a mixture of bisphenols of the formula VI with phosphorus tri-chloAde and an HALS compound of the formula V or a mixture of HALS compounds of the formula V, for the stabilization of organic mateAals against oxidative, thermal or light-induced degradation.

The novel monomeAc and oligomeric compounds of the formulae I and II are distin-guished by pronounced excellent hydrolysis stability and advantageous colouring be-haviour, ie low discoloration of the organic materials during processing.

Organic mateAals which have been stabilized by means of the compounds of the present invendon are particularly well protected against light-induced degradation.

The present invention therefore also relates to a process for the stabilization of an organic mateAal against oxidative, thermal or light-induced degradation, which comprises incor-porating or applying at least one monomeAc or oligomeric compound of the formula I or II
or a product obtainable by reacting a bisphenol of the formula VI or a mixture of bisphe-nols of the formula VI with phosphorus trichloride and an HALS compound of the formula V or a mixture of HALS compounds of the formula V, into or to this mateAal.

... .. . . . . .

" 21~6~2~

The examples below illustrate the invention in greater detail. Parts and percentages are by weight. -Example 1: Preparadon of compound (101) (Table 1). ;;

a) 9.10 ml (14.28 g,104 mmol, 2.6 equivalents) of phosphorus trichloride are added drop~
wise at room temperature to a stirred suspension, under a nitrogen atmosphere, of 15.22 g (40.0 mmol, 1.0 equivalent) of 4,4'-cyclohexylidenebis(2-tert-butylphenol) and 0.20 g (1.60 mmol) of 4-dimethylaminopyridine in 46 ml of toluene. The mixture is subsequently warmed to 100C over the course of one hour and stirred at this temperature for 1.5 hours. ~ ~`
When the evolution of hydrochloric acid gas has subsided, the mixture is stirred at 100C :~
for a further 30 minutes under a gentle stream of nitrogen. The resultant solution is diluted with 20 ml of toluene, and the excess phosphorus trichloride is removed by distillation to- - `
gether with about 20 ml of toluene. The solution contains 4,4'-cyclohexylidenebis(2-tert-butylphenyl dichlorophosphite). ~ -b) The solution described above (Example la) is added dropwise at room temperature over the course of 10 minutes to a stirred suspension, under a nitrogen atmosphere, of 27.4 g (175 mmol, 4.4 equivalents) of 2,2,6,6-tetramethylpiperidin-4-ol and 22.2 g (220 mmol, 5.5 equivalents) of triethylamine in 250 ml of toluene. The reaction mixture is subsequent- - ~1 ly warmed to 105C and stirred at this temperature for a further 5 hours. The white sus-pension is cooled to room temperature and filtered through Celite, and the filtrate is eva-porated on a vacuum rotary evaporator. The residue is taken up in a hexane/toluene 1:1 -solvent mixture and re-filtered through Celite. The filtrate is evaporated on a vacuum rotary evaporator, and the residue is dried in a high vacuum, giving 17.84 g (42 %) of compound (101), m.p. 48-52C (Table 1).
. .
Example 2: Preparation of compound (102) (Table 1). ;~

Analogously to Example 1, 23.2 g (40.0 mmol,1.0 equivalent) of 4,4'-cyclohexylidenebis-(2-tert-butylphenyl dichlorophosphite) in 50 ml of tol~dene (Example la) are reacted with 27.4 g (160 mmol,4.0 equivalents) of 1,2,2,6,6-pentamethylpiperidin-4-ol to give 23.7 g (53 %) of compound (102), m.p. 51-57C (Table 1).

Example 3: Preparation of the oligomeric compound (103) (Table 2).

`- 21~682~

' :' a) 4.55 ml (7.10 g,52 mmol, 2.6 equivalents) of phosphorus t~ichloride are added drop-wise at 50C to a stirred suspension, under a nitrogen atmosphere, of 7.85 g (20.0 mmol, 1.0 equivalent) of 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane and 0.20 g (1.60 mmol) of 4-dimethylaminopyridine in 15 ml of toluene. After about 30 minutes, the mixture is warmed to 75C and stirred at this temperature for 1.5 hours. The reaction mixture is sub-sequently evaporated on a vacuum rotary evaporator, and the residue (9.14 g) is dissolved in 50 ml of toluene.

b) A solution of lO.SS g (61.6 mmol, 3.1 equivalents) of 1,2,2,6,6-pentamethylpiperidin- -4-ol and 8.57 g (84.7 mmol, 4.2 equivalents) of triethylamine in 100 ml of toluene is added dropwise over the course of 15 minutes to a stirred solution, under a nitrogen atmosphere, of 9.14 g (20 mmol, 1.0 equivalent) of bisdichlorophosphite (see above, -Example 3a) in S0 ml of toluene. The reaction mixture is subsequently warmed to 105C
and stirred at this temperature for a further S 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 the excess 1,2,2,6,6-pentarnethylpiperidin-4-ol in a bulb-tube oven at 160CJ0.08 mbar gives 7.52 g (43 %) of compound (103), m.p. 73-76C(Table 2).

Replacement of 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane by 2,2-bis(3-sec-butyl-~hydroxyphenyl)propane or 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane in Example 3 gives compounds (104) or (105) (Table 2).

Example 4: Preparation of the oligomeric compound (106) (Table 2).

a) 2.60 ml (4.12 g,30.0 mmol, 1.5 equivalent) of phosphorus trichloride are added drop-wise at 50C to a stirred suspension, under a nitrogen atmosphere, of 7.61 g (20.0 mmol, 1.0 equivalent) of 4,4'-cyclohexylidenebis(2-tert-butylphenol) and 0.10 g (0.80 mmol) of 4-dimethylaminopyridine in 40 ml of toluene. The reaction mixture is subsequently ~ -warmed to 105C over the course of one hour and stirred at this temperature for 1.5 hours.
When the evolution of hydrochloric acid gas has subsided, the mixture is stirred at 105C
for a further 30 minutes under a gentle stream of nitrogen. The resultant solution is diluted with 20 ml of toluene, and the excess phosphorus trichloride is removed by distillation .
together with about 20 ml of toluene.

b) The solution described above (Example 4a) is added dropwise at room temperature over ;

21~6~2~ ~
~, the course of 10 minutes to a stirred suspension, under a nitrogen atmosphere, of 9.42 g -(60.0 mmol, 3.0 equivalents) of 2,2,6,6-tetramethylpiperidin-4-ol and 10.12 g (100 mmol, S.0 equivalents) of triethylamine in 100 ml of toluene. The thick suspension is subsequent-ly warmed to 105C and stirred at this temperature for a further S hours. The reaction mix-ture is cooled to room temperature and filtered through Celite, and the filtrate is evapo-rated on a vacuum rotary evaporator. Drying of the residue in a high vacuum gives 12.26 g (70 %) of the oligomeric compound (106), m.p. 69-78C (Table 2).
. ~ .
Example S: Preparation of the oligomeric compound (107) (Table 2).

Replacement of 2,2,6,6-tetramethylpiperidin-4-ol by 10.28 g (60.0 mmol, 3.0 equivalents) of 1,2,2,6,6-pentamethylpiperidin-4-ol in Example 4 gives 16.92 g (89 %) of the oligome-ric compound (107), m.p. 53-58C (Table 2).
:: ~
Example 6: Preparation of the oligomeric compound (108) (Table 1).

a) 2.10 ml (3.30 g, 24.0 mmol, 1.2 equivalents) of phosphorus trichloride are added drop-wise at 50C to a stirred suspension, under a nitrogen atmosphere, of 7.61 g (20.0 mmol, 1.0 equivalent) of 4,4'-cyclohexylidenebis(2-tert-butylphenol) and 0.26 g (0.80 mmol) of tetrabutylammonium bromide in 40 ml of toluene. The reaction mixture is subsequently warmed to 105C over the course of one hour and stirred at this temperature for l.S hours.
When the evolution of hydrochloric acid gas has subsided, the mixture is stirred at 105C
for a further 30 minutes under a gentle stream of nitrogen. The resultant solution is diluted with 20 ml of toluene and the excess phosphorus trichloride is removed by distillation to- ;
gether with about 20 ml of toluene.

b) The solution described above (Example 6a) is added dropwise at room temperature over the course of 10 minutes to a stirred suspension, under a nitrogen atmosphere, of 4.80 g (28.0 mmol, 1.4 equivalents) of 1,2,2,6,6-pentamethylpiperidin-4-ol and 10.12 g (100 mmol, 5.0 equivalents) of triethylamine in 100 ml of toluene. The thick suspension is sub-sequently warmed to 105C and stirred at this temperature for a further S hours. The reac-tion mixture is cooled to room temperature and filtered through Celite, and the filtrate is evaporated on a vacuum rotary evaporator. Drying of the residue in a high vacuum gives 12.2 g (95 %) of the oligomeric compound (108), m.p. 95- 115C (Table 2).

21~682~

- 35 - :

Zo ~

Z ~ ~ ~ o ~ ~ "
o, o, ~ o ~ ~ o~ oo. ~ ~.
_ ~ ~ ~ r~ r~
V ~ ~

~ F

E 1~ o~

I
~ I ~ I 7 I I I I I
_~ :' .`
~ Z ~ _ O ~ ~

; ':

21~68~4 Table 2: Oligomeric compounds No. Compound Mn Mw/Mnm(c~c) H3~0H3 03 _ ~ T logo~) 1.9()a) 1 73 76 1 n ; .

104 _ ~CH ) CHCHO~3~ J~OH--P _ 1285a) 1.96a) 45 H Cf\CH n __ ~ : ~ :

105 _ o~ ~o--P_ _ 774a) 2.50a)Oil H Cf~CH 2 n ~ ~:

826b~ 1~30b)69-78 2~6~2~
, Table 2: Oligomeric compounds (continuation) ~ Compolmd Mn Mw/Mn (~C ;

H3C ~CH3 107 O 1752b) 1.30b) 53-58 _o~ ~0_P _ - '~
,C~ ~CH3 H3C \CH ~ H3C~ CH3 n CH~

108 O 2065b) 1 30b) 95-115 ~
~~0~`9~~0~~ I' I

Mn = number average molecular weight Mw= weightaveragemolecularweight a) determination by GPC (gel permeation chromatography) b) determination by MALDI (matrix assisted laser desorption ionization).

Example 7: Stabilization of polypropylene during multiple extlusion. -1.3 kg of polypropylene powder (~)Profax 6501) which has been prestabilized by means of 0.025 % of Irganox~3 1076 (n-octadecyl 3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate) (having a melt flow index of 3.2, measured at 230C and 2.16 kg) are mixed with 0.05 %
of Irganox~) 1010 (pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propio-nate]), 0.05 % of calcium stearate,0.03 % of dihydrotalcite [DHT 4A(~), Kyowa Chemical Industry Co., Ltd., Mg45Ak(OH)13CO3.3.5 H2O] and 0.05 % of the compound from Table 1. This mixture is extruded in an extruder having a barrel diameter of 20 mm and a length .~

;: ,. .:

21g682~

of 400 mm at 100 revolutions per minute, the three heating zones being set at the fol-lowing temperatures: 260, 270, 280C. The extrudate is cooled by drawing through a water bath and subsequently granulated. These granules are re-extruded. After 3 extru-sions, the melt flow index is measured (at 230C and 2.16 kg). A large increase in the melt flow index means considerable chain degradation, ie poor stabilization. The results are shown in Table 3.

Table 3:
Compound fromMelt tlow index Table 2after 3 extrusions _ 20.0 103 5.2 -104 5.3 ~ ;
105 5.2 . ' `

Example 8: Stabilization of polyethylene during processing.

100 parts of polyethylene powder (Lupolen~5260 Z) are mixed with 0.05 part of Irga- ;
nox~) 1010 (pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and -0.1 part of stabilizer from Table 1, and the mixture is compounded in a Brabender Plasto-graph at 220C and 50 revolutions per minute. During this time, the compounding resis-tance is recorded continuously as torque. During the compound time, the polymer, after an extended constant time, begins to crosslink, which is evident from the rapid increase in ; -torque. Table 4 shows the time before significant increase in the torque as a measure of the stabilizer action. The longer this time, the better the stabilizer action.

i.'~ . '. ' . ' . , ~ ' " ., ' ' ~ ' ~': : .: .

.j. ;.' ' . ' .' ' ' ' , :.

"` "i' ~ ' ' - 214682~

Table 4:
Compound from Time before torque ~ -Tables 1 and 2 increase (min.) 101 155s 102 16.0 106 15.0 107 _17.0 ~' ;'''~
- '';~ ' ':'"' '- ;-'' ,. .,~ ' ',.' ,.,',,." ,,',";',..........
.- ': ..: ~,':

'~: '',~'"

;-` ' 'i :: : , ,` -, : ' ' : ' .

Claims (18)

1. A monomeric compound of the formula I or an oligomeric compound of the formula II
(I) (II) in which R1 and R2, independently of one another, are hydrogen, C1-C25alkyl, C2-C24alkenyl, un-substituted or C1-C4alkyl-substituted C5-C8cycloalkyl; unsubstituted or C1-C4alkyl-substi-tuted phenyl; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkenyl; or C7-C9phenyl-alkyl, R3 is hydrogen or methyl, R4 is hydrogen, C1-C8alkyl, O°, OH, NO, -CH2CN, C1-C118alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C3-C6alkynyl, C1-C8acyl, or C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl ring by C1-C4alkyl, R5 and R6, independently of one another, are hydrogen, CF3, C1-C12alkyl or phenyl, or R5 and R6, together with the carbon atom to which they are bonded, form an unsubstituted or C1-C4alkyl-substituted C5-C12cycloalkylidene ring; with the proviso that, if R5 and R6 are simultaneously hydrogen, R4 is not hydrogen; and with the proviso that, if R1, R2 and R3 are simultaneously hydrogen and R5 and R6 are simultaneously methyl, R4 is not hydrogen, R7 is hydrogen, C1-C8alkyl or a radical of the formula III
(III) R8 is hydrogen or C1-C8alkyl, A is oxygen, sulfur, , -CH2CH2-?-O-Y-O-?-CH2CH2- or -(CH2)m-O-?-Z-?-O-(CH2)m-, X is oxygen or ?-R7, Y and Z, independently of one another, are C2-C18alkylene, C4-C18alkylene which is inter-rupted by oxygen, sulfur or ?-R8; C4-C8alkenylene or phenylethylene, m is an integer from 2 to 8, and n is a number from 2 to 25.
2. A compound according to claim 1, in which R1 and R2, independently of one another, are hydrogen, C1-C18alkyl, C2-C18alkenyl, C5-C8cycloalkyl, unsubstituted or C1-C4alkyl-substituted phenyl, C5-C8cycloalkenyl or C7-C9phenylalkyl, R4 is hydrogen, C1-C4alkyl, OH, -CH2CN, C4-C18alkoxy, C5-C12cycloalkoxy, allyl, pro-pargyl, acetyl or C7-C9phenylalkyl;
R5 and R6, independently of one another, are hydrogen, CF3, C1-C8alkyl or phenyl, or R5 and R6, together with the carbon atom to which they are bonded, form a C5-C8cyclo-alkylidene ring;
R7 is hydrogen or C1-C4alkyl, R8 is hydrogen or C1-C4alkyl, A is oxygen,. -CH2CH2-?-O-Y-O-?-CH2CH2- or -(CH2)m-O-?-Z-?-O-(CH2)m-, X is oxygen or ?-R7, Y and Z, independently of one another, are C2-C12aLkylene, C4-C12alkylene which is inter-rupted by oxygen or ?-R8; C4-C8alkenylene or phenylethylene, m is an integer from 2 to 6, and n is a number from 2 to 15.
3. A compound according to claim 1, in which R1 and R2, independently of one another, are hydrogen, C1-C8alkyl, cyclohexyl or phenyl.
4. A compound according to claim 1, in which R4 is hydrogen, C1-C4alkyl, C4-C16alkoxy, C5-C8cycloalkoxy, allyl, propargyl, acetyl or benzyl.
5. A compound according to claim 1, in which R1 and R2, independently of one another, are hydrogen, C1-C12alkyl, C2-C12alkenyl, C5-C8cycloalkyl, phenyl or benzyl, R4 is hydrogen, C1-C4alkyl, C4-C16alkoxy, C5-C8cycloalkoxy, allyl, propargyl, acetyl or benzyl;
R5 and R6, independently of one another, are hydrogen, C1-C8alkyl or phenyl, or R5 and R6, together with the carbon atom to which they are bonded, form a C5-C8cycloalkylidene ring;
R7 is hydrogen or C1-C4alkyl, A is , -CH2CH2-?-O-Y-O-?-CH2CH2- or -(CH2)m-O-?-Z-?-O-(CH2)m- , X is oxygen or ?-R7 , Y and Z, independently of one another, are C2-C8alkylene, C4-C12alkylene which is inter-rupted by oxygen; or C4-C8alkenylene, m is an integer from 2 to 6, and n is a number from 2 to 10.
6. A compound according to claim 1, in which R1 and R2, independently of one another, are hydrogen, C1-C8alkyl, cyclohexyl, phenyl or benzyl, R4 is hydrogen, C1-C4alkyl, C6-C12alkoxy, acetyl or benzyl;
R5 and R6, independently of one another, are hydrogen or C1-C8alkyl, or R5 and R6, together with the carbon atom to which they are bonded, form a C5-C8cycloalkylidene ring;
A is or -CH2CH2-?-O-Y-O-?-CH2CH2- , X is oxygen, Y is C2-C8alkylene or C4-C12alkylene which is interrupted by oxygen; and n is a number from 2 to 10.
7. A compound according to claim 1, in which R1 is hydrogen, R2 is hydrogen, C1-C4alkyl or cyclohexyl, R3 is hydrogen, R4 is hydrogen or C1-C4alkyl, R5 and R6, independently of one another, are hydrogen or C1-C4alkyl, or R5 or R6, to-gether with the carbon atom to which they are bonded, form a cyclohexylidene ring;
Ais , X is oxygen, and n is a number from 2 to 10.
8. A process for the preparation of an oligomeric compound of the formula II according to claim 1, which comprises frst reacting a bisphenol of the formula VI or a mixture of bis-phenols of the formula VI
(VI) in which the general symbols are as defined in claim 1, with phosphorus trichloride to give a compound of the formula VII
(VII) in which the general symbols are as defined in claim 1; and subsequently reacting the compound of the formula VII with an HALS compound of the formula V or a mixture of HALS compounds of the formula V
(V) in which the general symbols are as defined in claim 1.
9. An oligomeric product obtainable by reacting a bisphenol of the formula VI or a mix-ture of bisphenols of the formula VI with phosphorus trichloride and an HALS compound of the formula V or a mixture of HALS compounds of the formula V
(VI) (V) in which the general symbols are as defined in claim 1.
10. A composition comprising a) an organic material which is subjected to oxidative, thermal or light-induceddegradation and b) at least one compound of the formula I or II according to claim 1 or at least one oligomeric product according to claim 9.
11. A composition according to claim 10, additionally comprising further additives in addition to components (a) and (b).
12. A composition according to claim 11, wherein the further additives are phenolic anti-oxidants, light stabilizers and/or processing stabilizers.
13. A composition according to claim 11, wherein the further additive is at least one compound of the benzofuran-2-one type.
14. A composition according to claim 10, wherein component (a) is a natural, semisynthe-tic or synthetic polymer.
15. A composition according to claim 10, wherein component (a) is a thermoplastic polymer.
16. A composition according to claim 10, wherein component (a) is a polyolefin.
17. A composition according to claim 10, wherein component (a) is polyethylene or poly-propylene.
18. A process for the stabilization of an organic material against oxidative, thermal or light-induced degradation, which comprises incorporating or applying at least one com-pound of the formula I or II defined in claim 1 or at least one oligomeric product accor-ding to claim 9 into or to this material.
CA002146824A 1994-04-13 1995-04-11 Monomeric and oligomeric bisphenyl-hals phosphites as stabilizers Abandoned CA2146824A1 (en)

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GB9506381D0 (en) 1995-05-17
FR2718743B1 (en) 1997-08-22
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GB2288398B (en) 1998-09-09
DE19513541A1 (en) 1995-10-19
JPH07285979A (en) 1995-10-31
IT1273538B (en) 1997-07-08
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ITMI950745A1 (en) 1996-10-12
KR950032242A (en) 1995-12-20

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