CA1232283A - Polymeric 4-hydroxyphenylthio stabilizers - Google Patents

Abstract

Polymeric 4-Hydroxyphenylthio Stabilizers Abstract of the Disclosure The title compound corresponds to the formula and are characterized in that at least one of X or Y contains a group of the formula

Description

~z3Z283 3-14581/CGC 1'50/+

Polymeric 4-Hydroxyphenylthio Stabilizers Organic polymeric materials such as plastics and resins, and lubricating and mineral oils are subject to thermal, oxidative and photo-degradation. A great variety of stabilizers are known in the art for stabilizing a diversity of substrates. Their effectiveness varies depending upon the causes of degradation and the substrate stabilized. In general, it is difficult to predict which stabilizer will be most effective and most economical for any one area of application. For example stabilizer effectiveness in reducing volatility may depend upon preventing bond session in the substrate molecule. Limiting embrittlement and retaining elasticity in a polymer or rubber may require prevention of excessive cross linking and/or chain session. Prevention of discoloration may require inhibiting reactions which yield new chromophores or color bodies in the substrate or stabilizer. Problems of process stability and incompatibility must also be considered.

It has now been determined that the polymeric 4-hydroxyphenylthio compounds of this invention possess an unusual combination of desirable properties which make them particularly effective and useful as stabilizers. The compounds are particularly effective in protecting polyolefins, high impact polystyrene, rubbers such as polybutadiene and styrene-butadiene rubber, and other elastomers wherein retention of elasticity and inhibition of cross-linking, crazing, discoloration, odor formation and exudation are basic requirements.

lZ32X83 Polyesters containing 2-hydroxyphenylthio groups are disclosed in US. Patent No. 3,832,329 as intermediates to be used e.g. for preparing polyurethane polymers, to give reagents useful for imparting chemically-bound plasticization to polymers or to be incorporated into polycarbonates to serve as cross-linking sites.

It is the primary object of this invention to provide a class of polymeric hydroxyphenylthio compounds which exhibit a broad range of improved stabilization performance characteristics.

Various other obierts and advantages of this invention will become evident from the following description thereof.

The compound of this invention correspond to the formula I

A- COY
Lo O

wherein A is alkyd of 1 to 12 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, phenol, phenol substituted by alkyd of 1 to 12 carbon atoms or a group of the formula Q-B-C-o wherein Q is a group of the formula Al -R
HO- ; -S-lZ3228~

and is alkaline of 2 to 6 carbon atoms;
Al and R2 are independently hydrogen, alkyl~of 1 eon 18 carbon atoms, cycloalkyl of S to 6 carbon atoms, phenol, phenol substituted by alkyd of 1 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted by alkyd of 1 to 12 carbon atoms X which can be the same or different in each repeating unit is alkaline of 2 to 10 carbon atoms which is unsubstituted or substituted by a group or is Arlene of 6 to 10 carbon atoms;
Y which can be the same or different in each repeating unit is alkaline of 2 to 6 carbon atoms, which is uninterrupted or interrupted by one or two oxygen atoms and is unsubstituted or substituted by a group -0-A;
Z is a direct bond or is alkyleneoxy of 2 to 6 carbon atom, whereby the oxygen atom is attached to the carbonyl group and the alkaline moiety is uninterrupted or interrupted by one or two oxygen atoms;
a is hydrogen or A;
n is 1 to 100;
If with the proviso that at least one of X or Y contains a group Q.

Cluck alkyd radicals are straight-chain or branched alkyd such as I methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, ; n-pentyl, tert.-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, 1,1,3,3-I tetramethylbutyl, decal or dodecyl. Preferred are Cluck alkyd radicals. Al and R2 as Cluck alkyd are the same as defined above for Cl-Cl2 alkyd and are additionally e.g. tridecyl, tetradecyl, hexadecyl and octadecyl.

C5-C6 cycloalkyl is cyclopentyl or cyclohexyl.
: :
C2-C6 alkaline is for example ethylene, ethylene, propylene, I; trim ethylene, 2,2-dimethylpropane-1,3-diyl, tetramethylene, pent-ethylene or hexamethylene. Alkaline interrupted by one or two oxygen atoms can be for instance 3-oxapentamethylene, 4-oxahepta-ethylene or 3,6-di-oxaoctamethylene. X as C2-C1O alkaline is the same as defined above for C2-C6 alkaline and is additionally e.g.
octamethylene or decamethylene.

' .
:: :
: . .
.

) ) ~23Z283 When Al and R2 are aralkyl, they represent for instance bouncily alpha-methylbenzyl or alpha, alpha-dimethylbenzyl.

X as C6-C1O Arlene is generally derived from phenol, toll, mustily, xylyl and 1- and 2-naphthyl.

Particularly interesting compounds are those of the formula I, wherein n is 1.

Preferred compounds are those of the formula I, wherein A is alkyd of 1 to 8 carbon atoms, phenol or a group of the formula Al . .
//
HO-- -S-CH OH -C-

2 2 11 .=. O

Al and R2 are independently alkyd of 1 to 8 carbon atoms' X which can be the same or different in each repeating unit is alkaline of 2 to 6 carbon atoms which is unsubstituted or sub-stituted by a group Q' of the formula \

HO- -S-/

wherein Al and R2 have the preferred meanings given above or is phenylene;

.~,,'.

.

Y which can be the same or different in each repeating unit is alkaline of 2 to 6 carbon atoms which is unsubstituted or sub-stituted by a group wherein A has the preferred meanings given above or Y is

3-oxapentamethylene;
Z is a direct bond, alkyleneoxy of 2 to 6 carbon atoms or 3-oxapentamethyleneoxy;
R is hydrogen or A, whereby A has the preferred meanings given above;
n is l to 50, with the proviso that if n is l at least one of X or Y contains a group Q' and if n is 2-50, at least two of A, X or Y contain a group Q'.

Particularly preferred compounds are those of the formula I, wherein A is alkyd of 1 to 8 carbon atoms or a group of the formula (Schick \

Ho-- -S-CH OH -C-\ / 2 2 Al =- O
(SHEA 1 X which can be the same or different on each repeating unit it alkaline of 2 to 6 carbon atoms, 1,2-phenylene or a group of the formula lZ32283 -OH -OH-S
MY\
if (Schick i C(CH3)3 OH
Y which can be the same or different on each repeating unit is alkaline of 2 to 6 carbon atoms, 3-oxapentamethylene or a group of the formula -OH -OH-OH -O-A
wherein A has the preferred meaning given above;
Z it a direct bond, ethyleneoxy or 3-oxapentamethyleneoxy;
R is hydrogen or A, whereby A has the preferred meaning given above;
n is 2 to 25, with the proviso that at least two of A, X or Y contain a group of the formula (C 3)3 -//
HO- ; -S-=--(Schick The polymers of this invention can be prepared by the addition of II

Al //
HO- ; ASH (II) ;=~

wherein Al and R2 have the meanings given above, to polymers obtained by reaction of an alcohol with an epoxide and an adored, at least one of which containing an unsaturated carbonyl moiety.
A further possibility is that II can be first added to the unsaturated carbonyl moiety and then polymerized. Therefore II
can first be added to at least one of the monomers listed below and then polymerized into the additives of this invention.

The saturated alcohols which can be used include primary and secondary alcohols and phenols containing 1 to 12 carbon atoms, e.g.
methanol, ethanol, propel alcohol, bottle alcohol, cyclohexanol, and the like.

The unsaturated alcohols include e.g. hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxyethyl crotonate, and the like.

Suitable saturated epoxies include those containing 2 to 6 carbon atoms, e.g. ethylene oxide, propylene oxide, epichlorohydrin, cyclohexene oxide, bottle glycidyl ether, and the like.

Among the unsaturated epoxies useful herein are e.g. the glycidyl esters of unstriated carboxylic acids represented by the formula O O
/\ 11 CH2--CH-CH20C-C=CH

1~3Z283 where R3 and R4 are independently methyl or hydrogen. Suitable esters include 2,3-epoxypropyl acrylate, 2,3-epoxypropyl methacrylate and 2,3-epoxypropyl crotonate.

The preferred androids used in the preparation of the polymers of the present invention are those containing 4 to 12 carbon atoms, particularly succinic android, phthalic android, malefic android and the like.

Acid terminated polymers may be reacted with the Unsaturated epoxies described above and then II added. The hydroxy terminated prepolymers can be transesterified e.g. with acrylate esters and II
then added.

A particularly desirable embodiment is to transesterify a compound of the formula Al -- R R O

Ho -S-CH-CH-COCH3 /-=-wherein Al and R2 have the meanings given above, R5 is hydrogen or methyl and R6 is hydrogen, methyl or ethyl, with preformed polymers with reactive hydroxyl groups.

All the described reactions, which are condensation, esterification or transesterification reactions can be carried out by methods well known to the skilled in the art.

~232Z83 _ 9 _ Compounds of this invention are particularly effective in stabilize in organic materials such as plastics, polymers and resins in addition to mineral and synthetic fluids such as lubricating oils, circulating oils, and the like.

Substrates in which the compounds of this invention are particularly useful are polyolefins such as polyethylene and polypropylene, polystyrene, including impact polystyrene, butadiene rubber, AS
resin, SIR, isoprene, as well as natural rubber.

In general, polymers which can be stabilized include:

1. Polymers of monooelfines and dolphins, for example polyp ethylene (which optionally can be cross linked), polypropylene, polyisobutylene, polybutene-l, polymethylpentene-l, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene.

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene.

3. Copolymers of monoolefines and dolphins with each other or with other vinyl monomers, such as, for example, ethylene/propylene, propyene/butene-l, propylene/isobutylene, ethylene/butene-l, propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates, ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/
acrylic acid copolymers and their salts (monomers) and terpolymers of ethylene with propylene and a dine, such as hexadiene, duskily-pentadiene or ethylidene-norbornene.

4. Polystyrene, poly-(p-methylstyrene).

5. Copolymers of styrenes or ~-methylstyrene with dines or acrylic derivatives, such as, for example, styrene/butadiene, styrenes acrylonitrile, styrene/ethyl methacrylate, styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate; mixtures of high , .

impact strength from styrenes copolymers and another polymer, such as, for example, from a polyacrylate, a dine polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrenes such as, for example, styrene/butadiene/styrene, styrenes isoprene/styrene, styrene/ethylene/butylene/styrene or styrenes ethylene/propylene/styrene.

6. Graft copolymers of styrenes such as, for example, styrenes on polybutadiene, styrenes and acrylonitrile on polybutadiene, styrenes and alkyd acrylates or methacrylates on polybutadiene, styrenes and acrylonitrile on ethylene/propylene/diene terpolymers, styrenes and acrylonitrile on polyacrylates or polymethacrylates, styrenes and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 5), for instance the copolymer mixtures known as AS-, MOBS-, AS- or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, sheller-noted rubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrine home- and copolymers, polymers from halogen-containing vinyl compounds as for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, as for example, vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

8. Polymers which are derived from unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polyacrylamide and polyacrylonitrile.

9. Copolymers from the monomers mentioned under 8) with each other or with other unsaturated monomers, such as, for instance, acrylo-nitrile/butadien, acrylonitrile/alkyl acrylate, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

10. Polymers which are derived from unsaturated alcohols and amine, or azalea derivatives thereof or azaleas thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl Stewart, polyvinyl bonniest, polyvinyl Malta, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. ~omopolymers and copolymers of cyclic ethers such as polyp alkaline glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxy-ethylenes which contain ethylene oxide as a comonomer.

13. Polyphenylene oxides and sulfides, and mixtures of polyp phenylene oxides with polystyrene.

14. Polyurethane which are derived from polyethers, polyesters or polybutadiens with terminal hydroxyl groups on the one side and aliphatic or aromatic polyisocyanates on the other side, as well as precursors thereof (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from dominoes and dicarboxylic acids and/or from aminocarboxylic acids or the core-sponging lactams, such a polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-2,4,4,-trimethyl-hexamethylene terephthalamid or poly-m-phenylene isophthalamide, as well as copolymers thereof with polyethers, such as for instance, with polyethylene glycol, polypropylene glycol or polytetramethylene glycol 8 .

16. Pullers, polyamides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and dills and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate, pull-,, hydroxyphenyl)-propane~ terephthalate and polyhydroxybenzoates as well as block-copolyether-esters derived from polyethers having hydroxyl end groups.

18. Polycarbonates and polyester-carbonates.

19. Polysulfones, polyethersulfones and polyetherketones.

20. Cross linked polymers which are derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and mailmen/
formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins which are derived from Capella-esters of saturated and unsaturated dicarboxylic acids with polyp hydric alcohol and vinyl compounds as cross linking agents, and also halogen-containing modifications thereof of low inflammability.

23. Thermosetting acrylic resins, derived from substituted acrylic esters, such as epoxy-acrylates, urethane-acrylates or polyester-acrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture with mailmen resins, urea resins, polyisocyanates or epoxide resins as cross linking agents.

25. Cross linked epoxide resins which are derived from polyepoxides, for example from bis-glycidyl ethers or from cycloaliphatic dip epoxies.

,~"
".

26. Natural polymers, such as cellulose, rubber, gelatin and derivatives thereof which are chemically modified in a polymer-homologous manner, such as cellulose acetates, cellulose preappoints and cellulose butyrates, or the cellulose ethers, such as methyl-cellulose.

27. Mixtures of polymers as mentioned above, for example PP/EPDM, Polyamide 6/EPDM or AS, PVC/EVA, PVC/ABS, PVC/MBS, SCABS
PBTP/ABS.

28. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellithates) and also mixtures of synthetic esters with mineral oils in any weight ratios, which materials may be used as plasticizer for polymers or as textile spinning oils, as well as aqueous emulsions of such materials.

29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or lattices of carboxylated styrene/butadiene copolymers.

In general, the stabilizers of this invention are employed in from about 0.01 to about 5 % by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is from about 0.05 to about 2 I, and especially 0.1 to about 1 I.

The stabilizers of the instant invention may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The stabilized polymer compositions of the invention may optionally also contain various conventional additives, such as the following:

1. Antioxidant 1.1. Alkylated monophenols, for example, 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-tert.butyl-4-i-butylphenol 2,6-di-cyclopentyl-4-methylphenol 2-(a-methylcyclohexyl)-4,6-dimethylphenol 2,6-di-octadecyl-4-methylphenol 2,4,6-tri-cyclohexylphenol 2,6-di-tert.butyl-4-methoxymethylphenol 1.2. Alkylated hydroquinones, for example, 2,6-di-tert.butyl-4-methoxyphenol 2,5-di-tert.butyl-hydroquinone 2,5-di-tert.amyl-hydroquinone 2,6-diphenyl-4-octadecyloxyphenol 1.3. Hydroxylated thiodiphenyl ethers, for example 2,2'-thio-bis-(6-tert.butyl-4-methylphenol) 2,2'-thio-bis-(4-octylphenol) 4,4'-thio-bis-(6-tert.butyl-3-methylphenol) 4,4'-thio-bis-(6-tert.butyl-2-methylphenol) 1.4. Alkyliden-bisphenols, for example, 2,2'-methylene-bis-(6-tert.butyl-4-methylphenol) 2,2'-methylene-bis-(6-tert.butyl-4-ethylphenol) 2,2'-methylene-bis-[4-methyl-6-(a-methylcyclohexylphenol 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol) 2,2'-methylene-bis-(6-nonyl-4-methylphenol) 2,21-methylene-bis-[6-(~-methylbenzyl)-4-nonylphenNoel 2,2'-methylene-bis-[6-(a,a-dimethylbenzyl)-4-nonylphenol]
2,2'-methylene-bis-(4,6-di-tert.butylphenol) 2,2'-ethylidene-bis-(4,6-di-tert.butylphenol) 2,2'-ethylidene-bis-(6-tert.butyl-4-isobutylphenoll) 4,4'-methylene-bis-(2,6-di-tert.butylphenol) 4,4'-methylene-bis-(6-tert.butyl-2-methylphenol) 1,1-bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-bubutane 2,6-di-(3-tert.butyl-5-methyl-2-hydroxybenzyl)-4-mmethyl phenol 1,1~3-tris-(5-tert.butyl-4-hydroxy-2-methylphenyl)button 1,1-bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-3--n-dodecylmercapto-butane ethylenglycol-bis-[3,3-bis-(3'-tert butyl-4'-hydroxyphenyl)-butyrat]
di-(3-tert.butyl-4-hydroxy 5-methylphenyl)-dicyclopentadien di-~2-(3'-tert.butyl-2'-hydroxy-5'-methyL-benzyl)--6-tert.butyl-4-methylphenyl]-terephthalate.

1.5. Benzylcompounds, for example, 1,3,5-tri-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,4,,6-trimethyl-benzene-di-(3,5-di-tert.butyl-4-hydroxybenzyl)-sullfide 3,5-di-tert.butyl-4-hydroxybenzyl-mercapto-acetic acid-isooctyl ester bis-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)ditthiol-terephthalate 1,3,5-tris-(3,5-di-tert.butyl-4-hydroxybenzyl)-isoocyanurate 1,3,5-tris-(4-tert.butyl-3-hydroxy-2,6-dimethylbennzyl)-isocyanurate 3,5-di-tert.butyl-4-hydroxybenzyl-phosphoric acid-dioctadecyl ester 3,5-di-tert.butyl-4-hydroxybenzyl-phosphoric acid-monoethyl ester, calcium-salt 1.6. Acylaminophenols, for example, 4-hydroxy-lauric acid aniline 4-hydroxy-stearic acid aniline 2,4-bis-octylmercapto-6-(3,5-tert.butyl-4-hydroxyaanilino)-s-tria-zinc octyl-N-(3,5-di-tert.butyl-4-hydroxyphenyl)-carbamminute ~23Z;~83 1.7. Esters of ~-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionic acid with mandrake or polyhydric alcohols, for example, methanol diethyleneglycol octadecanol triethyleneglycol 1,6-hexanediol pentaerythritol neopentylglycol tris-hydroxyethyl isocyanurate thiodiethyleneglycol di-hydroxyethyl oxalic acid doomed 1.8. Ester of~-(5-tert.butyl-4-hydroxy-3-methylphenyl)propionicc acid with mandrake or polyhydric alcohols, for example, methanol diethyleneglycol octadecanol triethyleneglycol 1,6-hexanediol pentaerytritol neopentylglycol tris-hydroxyethyl isocyanorate thiodiethyleneglycol di-hydroxyethyl oxalic acid doomed 1.9. Asides of ~-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionic acid for example, N,N^-di-(3,5-di-tert.butyl-4-hydroxyphenylpropionyyl)-hexamethylendi-amineN,N'-di-(3,5-di-tert.butyl-4-hydroxyphenylproopionyl)-trimethylendi-amine N,N'-di-(3,5-di-tert.butyl-4-hydroxyphenylpropionyyl)-hydrazine 2. US absorbers and light stabilizers 2.1. 2-(2'-~ydroxyphenyl)-benztriazoles, for example, the methyl-, 3',5'-di-tert.butyl-, 5'-tert.butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert.butyl-, sheller'-tert.butyl-5'-methyl-, 3'-sec.butyl-5'-tert.butyl-, 4'-octoxy-, 3',5'-di-tert.amyl-, 3',5'-bis-(a,a-dimethylbenzyl)-derivative.

lZ32283 2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy, dyslexia-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxyderivative.

2.3. Esters of optionally substituted benzoic acids for example, phenol salicylate, 4-tert.butyl-phenylsalicilate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert.butylbenzoyl)-resor-sunnily,benzoylresorcinol,3,5-di-tert.-butyl-4-hydroxybenzzoic acid 2,4-di-tert.butyl-phenyl ester and 3,5-di-tert.-butyl-4-hydroxy-benzoic acid hexadecyl ester.

2.4. Acrylates, for example, a-cyano-B,~-diphenylacrylic acid ethyl ester or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-~-methyl-p-methoxy-cinnamic acid methyl ester or bottle ester, a-carbomethoxy-p-methoxy-cinnamic acid methyl ester, No carbomethoxy-~-cyanovinyl)-2-methyl-indoline.

2.5 Nickel compounds, for example, nickel complexes of Thea-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-di-ethanolamine, nickel dibutyldi-thiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert.butylbenzyl-phosphoric acid monoalkyl esters, such as of the methyl, ethyl or bottle ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl undecyl ketonoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxy-pyrazol, optionally with additional ligands.

2.6. Starkly hindered amine, for example bis-(2,2,6~6-tetramethylpiperidyl)-sebacate bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl Masonic acid bus-(1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperiiodine and succinic acid, condensation product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and 4-tert.octylamino-2,6-dichloro-1,3,5-s-treason,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetlate-~Z3ZZt33 tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,44-butane-tetra-carbonic acid, 1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethyl-piperazinone).

2.7. Oxalic acid doomed, for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert.butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert.butyl-2'-ethylox-aniline and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert.butylox-aniline and mixtures of ortho-and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid doomed, N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloyl-hydrazine,N,N'-bis-t3,5-di-tert.butyl-4-hydroxyphenylpropionnil)-hydrazine, 3-salicyloylamino-1,2,4-triazole, bis-benzyliden-oxalic acid deodorized.

4. Phosphates and phosphonites, for example, triphenyl phosphate, tiphenylalkyl phosphates, phenyldialkyl phosphates, tri-(nonyl-phenol) phosphate, trilauryl phosphate, trioctadecyl phosphate, di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert.butylphenyl) phosphate, di-isodecylpentaerythritol diphosphite, di-(2,4-di-tert.-butylphenyl)pentaerythritol diphosphite, tristearyl-sorbite in-phosphate,tetrakis-(2,4-di-tert.butylphenyl)-4,4'-biphenylylion diphosphonite.

5. Compounds which destroy peroxide, for example, esters of B-thio-dipropionic acid, for example the laurel, stroll, myristyl or tridecyl esters, mercapto-benzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc-dibutyl-dithiocarbamate, dioctadecyl-disulfide,pentaerythritol-tetrakis-(B-dodecylmercapto)-propiinnate.

6. Polyamide stabilizers, for example, copper salts in combination with iodizes and/or phosphorus compounds and salts of diva lent manganese.

~23228:~

7. Basic co-stabilisers, for example, mailmen, polyvinylpyrroli-done, dicyandiamide, triallyl sonority, urea derivatives, hydrazine derivatives, amine, polyamides, polyurethane, alkali metal salts and alkaline earth metal salts of higher fatty acids for example Cay Stewart, Zen Stewart, My Stewart, No ricinoleate and K palpitate, antimony pyrocatecholate or zinc pyrocatecholate.

8. nucleating agents, for example, 4-tert.butyl-benzoic acid, adipic acid, diphenylacetic acid.

9. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fires, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

10. Other additives for example, plasticizers, lubricants, emulsi-liens, pigments, optical brighteners, flame proofing agents, anti-static agents and blowing agents and thiosynergists such as dilaurylthiopropionat or distearylthiodipropionate.

Preferred additives to be used together with the compounds of the present invention are costabilizers selected from the group consisting of antioxidant, light stabilizers, metal deactivators, phosphates, phosphonites and thiosynergists.

The following examples illustrate the embodiments of this invention.
In these examples, all parts given are by weight unless otherwise specified.

Example 1: In a 500 ml flask equipped with an acetone-dry ice Dower condenser a mixture of 7.41 grams n-butyl alcohol, 49.03 grams malefic android, 29.04 grams propylene oxide, 0.69 gram tetrabutyl-ammonium chloride, and 0.49 gram paramethoxyphenol is heated and held at 75C until the acid number is 1.0 my KOH/gram polymer (approximately 13 hours). IT I in chloroform): 1740 cm (ester carbonyl), 1640 cm 1 (double bond). A compound of the formula CH3(CH2)3 R-CH=CH IClOCH
L SHEA

n 5 is obtained.

Example lay The procedure of Example 1 is repeated using 9.8 grams instead of 49.03 grams of malefic android and 5.8 grams instead of 29.04 grams of propylene oxide. A compound of the formula CH3(CH2)30-R-CH=CH-R-OCH2CHOH

it obtained.

Example 2: In a 100 ml flask under nitrogen, a solution of 8,54 grams of the polymer of Example 1 in 2.5 mls Tulane is treated with a solution of 11.92 grams 2,6-di-t-butyl-4-mercaptophenol in 25 mls Tulane followed by 0.20 gram triethylamine. The solvent is removed in vacua and the polymer is purified by dry-column cremate-graph. The IT spectra showed no unsaturation at 1640 cm . The compound has the formula 1232Z~33 CH3(CH2)3 8 Showoff 8 2 L S SHEA ¦ n !".
! I n 5 /~/\
(Schick i C(CH3)3 OH
Anal. Caulked- for [C2lH30o5s]n So 7-8-Found: S, 7.5.

Examiner pa: The procedure of Example 2 it repeated using 2.3 gram of the compound of Example lo instead of 8.54 grams of the compound of Example 1 and 2.38 grams instead of 11.92 grams of Dwight-butyl-4-mercaptophenol. A compound of the formula CH3(CH2)30-C-CH2-CH-COCH2CHOH

Jo i /~/\
(Schick I C(CH3)3 OH
is obtained.

Example 3: The procedure of Example 1 is repeated using 2.22 grams n-butyl alcohol, 14.71 grams of malefic android, 19.3 grams of bottle glycidyl ether 0.20 gram tetrabutylammonium chloride and 0.04 gram para-methoxyphenol until an acid number of 1.7 my KOH/gram is obtained. The compound has the formula CH3(CH2)3 -OH SHEA -CO-CH2CHO
CH20(CH2)3CH3 n n 5 Example 4: The procedure of Example 2 is repeated using 12.1S grams of the polymer of Example 3, 11.92 grams 2,6-di-t-butyl-4-mercapto-phenol, and 1.0 gram triethylamine. The crude polymer is purified by dry-column chromatography. IT I solution in chloroform) spectrum shows an ester carbonyl at 1740 cm and no unsaturation. The compound has the formula _ _ .
4 9 - CCH2-fH-CO-CH2CHO -H
O S O Chicago n !".

(Schick i C(CH3)3 n 5 OH
Anal. Caulked. S, 6.6.
Found: S, 6Ø

Example 5: The procedure of Example 1 is repeated using 11.61 grams of 2-hydroxyethyl acrylate, 38.44 grams of glycidyl acrylate,

30.02 grams succinic android, 0.4 gram bouncily triethylammonium chloride and 0.08 gram 2~6-di-t-butyl-4-methylphenol until an acid number of 1.4 my KOH/gram is obtained. IT (1% solution in sheller-form): 1630 cm (unsaturation). The compound has the formula ~41~

- 2_ -C~2=cHco(cH2)2(~(c~l2)2cocH2cH
O O CH20C-CH=CH2 _ _ n n - 3 Example 6: The procedure of Example 2 is repeated using 16.01 grams of the polymer of Example 5, 19.07 grams of 2,6-di-t-butyl-4-mercaptophenol and OHS gram triethylamine. The crude polymer is purified Sty dry-column chromatography. IT spectrum shows no unswept-ration. The compound has the formula Of _ _ CH2CH2CO(CH2)20 _ --C(CH2)2C0CH2CHo -H
S 0 0 CH20CCH2CH2 n O S
R\
--I 11 R\

(SCHICK/ / \C(CH3)3 ! if OH (SCHICK i C(C~3)3 n - 3 OH
Anal. Caulked: S, 7.3.
Found: S, 6.9.

Example 7: The procedure of Example 1 is repeated using 11.6 grams hydroxyethyl acrylate, 38.4 grams glycidyl acrylate, 29.4 grams malefic android, 0.4 gram benzyltriethylammonium chloride, and ~232~8;3 0.08 gram 2,6-di-t-butyl-4-methylphenol until an acid number of 0,90 is obtained. IT (1% solution in chloroform): 1735 cm (carbonyl), 1640 cm (double bond). The compound has the formula O O O

CH2=CHCO(CH2)20 - - C-CH=CH-COCH2fHO -H
fH2 OKAY
O n n 3 Example 8: The procedure of Example 2 is repeated using 7.9 grams of the copolymer of Example 7, 16.7 grams of 2,6-di-t-butyl-4-mercapto-phenol, and 0.5 gram triethylamine. The crude polymer is purified by dry-column chromatography. The IT spectrum shows no unsaturation.
The compound has the formula O - O O - , If 11 11 fH2-CH2CO(CH2)20- - CfHCH2COCH2THO -H

S S fH2 , OUCH -OH n //\ //\ Al 2 1 2 O S
l 11 1 11 1 3)3 I C(CH3)3 (Schick (SHEA I/ \
OH OH
/~/\
(Schick I C(CH3)3 n 3 OH
Anal. Caulked.: S, 9.1.
Found: S. 8.7.

Example 9: A mixture of 19.13 gram of dim ethyl Detroit-butyl-4-hydroxyphenylthio) succinate, 4.51 trams of 1,4-butanediol, and 0.24 gram of tetrabutyl titan ate is heated under nitrogen to 130C and evolved methyl alcohol collected with an acetone dry ice trap. The pressure is gradually reduced to 0.1 mm Hug and the temperature is raised to 160-C. The product is dissolved in 100 ml hot tetrahydrofuran to which 14 ml of water is added, filtered, the solvent removed in vacua, and the residue triturated with hexane.
The resultant polymer of the formula C 3~8_CH2fH_lcl_o-(cH2)4 0 Lulls I \. n l 11 n 15 /~/\
(Schick i C(CH3)3 OH
is dried to give 13.6 grams of a white solid, melting at 66-79C.

Anal- Caulked- for ~C22H325s~n I 64-7; Ho 7-9; So 7-8-Fount: C, 64.9; H, 8.1; S, 7.8.

Example 10: Stabilization of impact polystyrene In the laboratory procedure utilized herein, a solution of eight weight percent polybutadiene rubber (Firestone - DINE 55~) dissolved in styrenes monomer is prepared on a roller mill. The indicated amount of stabilizer is also introduced at this point.
500 Pam of zinc Stewart is added to aid in removing the sample from the bottle after the polymerization. The bottle is screwed into the polymerization apparatus which is equipped with a double helical ribbon stirrer. Since most commercial ITS bulk polymerizations are ~Z322~33 thermally initiated processes, no initiator is used in the labor-tory process. A nitrogen atmosphere is established and then the reactor is heated to 121C within 1/2 hour. Heating is continued at lZlC with efficient stirring until there is a 30 to 35% monomer conversion (2-1/2 hours). The stirring rate is controlled to yield a two to four sum rubber particle size. The bottles are removed from the polymerization apparatus, blanketed with nitrogen, capped and then placed in a fluidized bed sand bath to complete the polymeric ration. The bottles are heated in the bath in the following fashion:
one hour at 100C to equilibrate the temperature, one hour to reach 140C and then an additional eight hours with the temperature increasing at the rate of 10C per hour to a maximum of 220C. After the resin has cooled, the bottle is broken and the glass is removed.
The average weight of the polymer block is slightly over 600 grams.
The block is then placed into a vacuum oven at 200C and a vacuum of 1 mm applied as the polymer is heated for 45 minutes in order to remove all volatile. The block is removed from the oven, immediate-lye placed in a heat (SKYE) hydraulic press and then pressed into a thick slab between two sheets of aluminum foil (three minutes heating, five minutes in a cold press). The slab is split with a band saw and the pieces are granulated.

All batches are extruded at 205C and then poulticed. The pellets are compression molded at 205C into 125 mix (3,2 mm) tensile bars.
The bars are then aged at 150C on glass plates placed on rotating shelves in a forced air oven. The specimen yellowness index is determined on the bars at various intervals according to ASTM
D-1925-63T. Correspondingly, the bars are periodically measured for percent elongation in the Instron Tensile Testing Apparatus (Instron Engineering Corporation, Massachusetts) at a pull rate of 5 mm/minute according to ASTM D-638.

~232283 Oven Aged Samples at 150C
Hours at 150C
Additive Cone. 1/2 11-1/2 2 % Elongation None - 33 7 7 3 3 Compound of Example 60.1%45 52 48 19 Compound of Example 80.1%61 17 - 10 9 Yellowness Index None - 7 18 30 38 43 Compound of Example 60.1%-2 4 8 10 Compound of Example 80.1%4 8 17 20 22 Example 11: Stabilization of polypropylene (Light stability) Unstabilized polypropylene powder (Hercules Prefix issue thoroughly blended with 0.2%, by weight, of additive. The blended materials are then milled on a two roll mill at 182C for 5 minutes, after which time the stabilized polypropylene is sheeted from the mill and allowed to cool. The milled polypropylene is then cut into pieces and compression molded on a hydraulic press at 220C
(175 psi) into 5 mix (0.13 mm) films. The sample is exposed in a fluorescent sunlight/black light chamber until failure. Failure is determined when the films show the first signs of decomposition (e.g. cracking or brown edges).

Additive Hours to failure None 200-300 Compound of Example 2 380 Compound of Example 4 410 Compound of Example 6 450 Compound of Example 8 360 *Trade Mark , Jo , ...

123;~283 example 12: Stabilization of polypropylene (Oxidation stability The oxidation stability of milled polypropylene containing 0.2% of additive as well as that of the synergized formulation containing 0.1% of additive in the presence of 0.3% distearylthiodipropionate (DSTDP) on plaques of 25 mix (0.64 mm) thickness is determined by exposing said plaques to air in a forced draft oven at 150C. The plaques are considered to have failed on showing the first signs of decomposition (e.g., cracking or brown edges).

Hours to failure 0.1% Additive Additive 0.2~ Additive+ 0.3~ DSTDP
Base Resin < 20 < 20 Compound of Example 2330 580 Compound of Example 4410 570 Compound of Example 6170 240 Compound of Example 8130 320 Examples 10-12 thus indicate the significantly better performance of the instant compounds as compared to the base resin.

Summarizing, it is seen that this invention provides a group of compounds which have an outstanding stabilizing activity in a variety of organic materials. Variations may be made in proportions, procedures and materials without departing from the scope of the invention as defined by the following claims.

.

Claims (9)

What is claimed is:

1. A compound of the formula I

wherein A is alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alkyl of 1 to 12 carbon atoms or a group of the formula wherein Q is a group of the formula and B is alkylene of 2 to 6 carbon atoms;
R1 and R2 are independently hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alkyl of 1 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms or said aralkyl substituted by alkyl of 1 to 12 carbon atoms;
X which can be the same or different in each repeating unit is alkylene of 2 to 10 carbon atoms which is unsubstituted or substituted by a group Q or is arylene of 6 to 10 carbon atoms;

Y which can be the same or different in each repeating unit is alkylene of 2 to 6 carbon atoms, which is uninterrupted or interrupted by one or two oxygen atoms and is unsubstituted or substituted by a group -O-A;
Z is a direct bond or is alkyleneoxy of 2 to 6 carbon atoms, whereby the oxygen atom is attached to the carbonyl group and the alkylene moiety is uninterrupted or interrupted by one or two oxygen atoms;
R is hydrogen or A;
n is 1 to 100;
with the proviso that at least one of X or Y contains a group Q.

2. The compound of claim 1 of the formula I, wherein n is 1.

3. The compound of claim 1 of the formula I, wherein A is alkyl of 1 to 8 carbon atoms, phenyl or a group of the formula R1 and R2 are independently alkyl of 1 to 8 carbon atoms;
X which can be the same or different in each repeating unit is alkylene of 2 to 6 carbon atoms which is unsubstituted or substi-tuted by a group Q' of the formula wherein R1 and R2 have the preferred meanings given above or is phenylene;
Y which can be the same or different in each repeating unit is alkylene of 2 to 6 carbon atoms which is unsubstituted or sub-stituted by a group -O-A

wherein A has the preferred meanings given above or Y is 3-oxapentamethylene;
Z is a direct bond, alkyleneoxy of 2 to 6 carbon atoms or 3-oxapentamethyleneoxy;
R is hydrogen or A, whereby A has the preferred meanings given above;
n is 1 to 50, with the proviso that if n is 1 at least one of X or Y contains a group Q' and if n is 2-50, at least two of A, X or Y contain a group Q'.

4. The compound of claim 1 of the formula I, wherein A is alkyl of 1 to 8 carbon atoms or a group of the formula X which can be the same or different on each repeating unit is alkylene of 2 to 6 carbon atoms, 1,2-phenylene or a group of the formula Y which can be the same or different on each repeating unit is alkylene of 2 to 6 carbon atoms, 3-oxapentamethylene or a group of the formula wherein A has the preferred meaning given above;
Z is a direct bond, ethyleneoxy or 3-oxapentamethyleneoxy;
R is hydrogen or A, whereby A has the preferred meaning given above;
n is 2 to 25, with the proviso that at least two of A, X or Y contain a group of the formula

5. A composition of matter comprising an organic material subject to oxidative, thermal and actinic degradation stabilized with an effective stabilizing amount of a compound of claim 1.

6. The composition of claim 5 containing additionally a costabilizer selected from the group consisting of antioxidants, light stabilizers, metal deactivators, phosphites, phosphonites and thiosynergists.

7. The composition of claim 5, wherein the organic material is a synthetic polymer.

8. The composition of claim 7, wherein said polymer is selected from the group consisting of polyolefins, impact polystyrene, butadiene rubber, acrylonitrile/butadiene/styrene, styrene/butadiene rubber.

9. A method for stabilizing an organic material against oxidative, thermal and actinic degradation which comprises incorporating into said organic material an effective stabilizing amount of a compound of claim 1.