FR2510124A1 - OLIGOMERATED PHENOLS, THEIR PREPARATION AND STABILIZED ORGANIC MATTER USING OLIGOMERIC PHENOLS OF THIS TYPE - Google Patents

Abstract

THE INVENTION CONCERNS OLIGOMERIC PHENOLS WHICH ARE OBTAINED BY FIXATION OF PHENOLS CARRIING FROM A MERCAPTO OR VINYL GROUP TO REACTIVE OLIGOMERS OF DIENES. THEY MEET THE FORMULA (CF DRAWING IN BOPI) IN WHICH Q AND Q REPRESENT H, OH, COOH, COOCH, COOCH, CH, CH OR A PHENYL, R REPRESENTS CL OR CN, N A NUMBER FROM 4 TO 6, S 0 OR 1, M A NUMBER FROM 30 TO 150 AND T A NUMBER FROM 3 TO 50, THE T: M RATIO BEING BETWEEN 10: 100 AND 35: 100, AND REPRESENTS A RADICAL RESPONDING TO ONE OF FORMULAS II AND III (CF DRAWING IN BOPI) APPLICATION AS STABILIZER OF ORGANIC MATERIALS.

Description

The present invention relates to novel oligomeric phenols which can

  be obtained by the addition of phenols carrying mercapto or vinyl groups on reactive oligomers of dienes, the preparation of these oligomeric phenols and their application to stabilization

  organic matter against oxidative degradation.

  tion. We already know (see for example the patent

  European Union 17 614) stabilizers carrying

  natives and mercapto which are usable for

  organic compounds, in particular for polymers, and which

  their activity after having been incorporated into the

  However, their stability in the extraction is not always satisfactory.

  a particular mode of stabilization can be used

  in which the stabilizer is grafted onto the poly-

  mother in the presence of a substance generating radicals.

  Such fixations of stabilizers on polymers are described in detail in the first published specification of patent application DE 2,509,654. However, it has been found that the presence of the stabilizers mentioned during

  preparation of polymers, may lead to

  such as interruptions of annoying chains.

  In the same publication it is also pointed out that

  such polymers modified with antioxidants may possibly

  they themselves serve as stabilizers for poly-

  However, the addition of polymeric additives of this gen-

  to basic products made of plastics can lead to great difficulties which result for example in a non-homogeneous distribution of the additive

  and an alteration of the properties of the polymer to be protected.

  Polymeric antioxidants are known to

  sterically hindered phenols (see, for example, the first published specification of the DE patent application

  2 143 362) Their stabilizing activity does not, however, satisfy

  not always meet user requirements.

  That being so, the present inventors

  found that by fixing phenols carrying mercaptan groups

  to or vinyl on reactive oligomers of dienes in

  a definite ratio of quantities we obtain new

  oligomeric phenols which, thanks to their good compatibility

  the substrates and their good dispersibility, can be incorporated without difficulty into polymers and, while having excellent performance in

  color, migration and extraction, confers

  to polymers a very good protection against

  gradation that may cause them heat and

  The subject of the invention is therefore compounds which

to formula I) t

-Q '(I)

  Wherein Q and Q 'each represent, independently of one another, hydrogen, hydroxy, -COOH, -COOCH 3, -COOC 2. H 5, -CH 3, C 2 H 5 or phenyl, R represents -Cl or -CN, n denotes a number from 4 to 6, s denotes the number O or 1, m denotes a number from 30 to 150, t denotes a number from 3 to 50, and the ratio t: m being between 10: 100 and 35: 100, and A represents a radical corresponding to one of formulas II and III RE * es' (I>)

HO * X (M)

R 6

HO (III)

R 2 S 4

  wherein R 1 and R 2 are each independently of one another, C 1 -C 8 alkyl, C 5 -C 8 cycloalkyl, C 6 -C 10 aryl, C 7 -C 10 aralkyl a C 7 -C 10 alkylaryl, R 2 may also be hydrogen in contrast to R 1, R 3 is hydrogen or C 1 -C 8 alkyl, R 4, R 5 and R 6 each represent, independently of one another, hydrogen, a radical -COOR 1 or a radical H -Y 'and R 4 may additionally contain a C 1 -C 8 alkyl,

  X, Y and Y 'each represent independently

  each of R 9 and R 10 independently of one another is a direct bond or a divalent hydrocarbon radical containing from 1 to 20 carbon atoms. of carbon, a radical which is uninterrupted or which is interrupted one or more times by -o or -S-, Z represents -O-, -S-, -N (R11) -, -CON (R11) -, -N ( R11) CO-, -OC (O) or -C (O) O and, in the case of X, may further represent a radical

0/12

  -COO H, 3 Qou, Z 'represents a bond directi -COQ' NH 3 Qou or -OC (O) -, r denotes the number O or 1, Rll represents hydrogen or R 1, and R 12 represents a radical -OR 1, -SR 1, -NHR 1 or -N (R) 2, and if A is uan group II, q = t, and if

it is a group III, q = o.

  Compounds of formula I are preferred

  in which A is a group of formula II.

  The C 1 -C 8 alkyl which has been mentioned for possible substituents is, for example, a methyl radical,

  ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-

  butyl, n-pentyl, n-hexyl, n-octyl or tetramethyl-1,1,3,3 butyl, but preferably a C 1 -C 4 alkyl, for R 2,

  R 3 and R 4 more especially methyl and for R 1 more specifically

usually a tert-butyl.

  As C 5 -C 8 cycloalkyl, R 1 or R 2

  is for example a cyclopentyl, cyclohexyl, cyclopentyl,

  heptyl or cyclo-octyl Cyclopentyl is preferred and, more preferably,

everything, cyclohexyl.

  As a C 6 -C 10 aryl, R 1 or R 2 is, for example, phenyl, α-naphthyl or p-naphthyl,

but preferably a phenyl.

  As C 7 -C 10 aralkyl, R 1 or R 2

  is for example a benzyl radical, 1-phenylethyl, -

  dimethylbenzyl or 2-phenylethyl.

  As a C 7 -C 10 alkylaryl, R 2 or R 2 is, for example, a tolyl, xylyl or 2,6-diethyl radical.

phenyl or tert-butyl-4-phenyl.

  As a divalent hydrocarbon radical containing from 1 to 20 carbon atoms, R 9 or Ro 10 may be branched or, better, unbranched alkylene, which may be uninterrupted or, depending on the number of carbon atoms, be interrupted once or several times with -O or, more especially, with -S- Such hydrocarbon radicals include, for example, the methylene, ethylene, tri-, tetra-, penta-, hexa-, hepta-, octa-, deca radicals. -, dodeca-, tetradeca- and octadecamethylenes as well as the radicals -CH 2 SCH 2, CH 2 OCH 2, -CH 2 SCH 2 CH 2, -CH 2 OCH 2 CH 2,

  CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2

22 and 2-CHCHCH CH 2 C 2.

  - (CH 2 CH 2 S) 2 -CH 2 CH 2 and -CH 2 CH 2 OCH 2 CH 2.

  The index m preferably represents a

  from 50 to 80, and a number from 7 to 28 The ratio of t

  at m is preferably between 12: 100 and 30: 100.

  Among the compounds of formula I,

  re as particularly interesting those in which s equals 0, N is equal to 4 and A represents a radical

2510124

  in one of two formulas IV and V R 1 Ho (IV) / '=' 3 R 2

R R 6

i O

HO (V)

\ -XR 4 5 (V)

  R / 3 R 2 preferably a group IV,

  in which R 1 and R 2 each independently represent

  from each other, a C 1 -C 4 alkyl, R 3 represents

  hydrogen or methyl, R 4, R 5 and R 6 represent each

  each, independently of one another, hydrogen, -COOCH 3, -COOC 2 H 5 or a radical:

R 3 / R -

DE- '-OH

_y, X = / -Y x \ R 2

  X 5, Y and Y 'each represent, inde-

  pendently of each other, a radical -R 9 -t Z-R 10 Z'-

  wherein R 9 and R 10 each independently represent

  from each other, a direct link or a radical

  linear bivalent carbon containing from 1 to 12 carbon atoms which may be uninterrupted or interrupted once or more times by -S-, Z represents -O-, -NH-, -C (O) O or -OC (O) , Z 'represents a direct bond or

-OC (O) and r is 0 or 1.

  We particularly appreciate the com

  of formula I wherein S is 0, N is 4, m is 50 to 80, test is 7 to 28 and t: m is 12: 100 to 30: 100 , Q and Q 'each represent a hydzoxy group, A represents a radical corresponding to one of formulas VI, VII and VIII R (VI)

C; 3% 2-5-

R 12 R R vl / 3

c 3 'CH 2-5-

R 1

HO ^^ \, "Y; CH, (VIII)

  R 2 in particular a group VI or VII, wherein R 1 represents a tert-butyl, R 2 a methyl or a tert-butyl, R 4 hydrogen or a radical R / 1 \ R 2 X represents a direct bond or a radical -CH 2-, CH 2 CH 2-, -CH 2 CH 2 -C (O) O-CH 2 CH 2, -CH 2 SCH 2 -OC (O) -CH 2 or -CH 2 SCH 2 -C (O) CH 2 CH 254-CH 2 CH 2, the index q denoting a number from 0 to 4, and Y represents a direct bond or a radical -CH 2, -CH 2 CH 2, -OC (O) -,

  -CH 2 -NHCO-, -CH 2 -OC (O) -, -OC (O) -CH 2-, -CH 2 CH 2 -C (O) O-,

  -CH 2 CH 2 -C (O) -O-CH 2, -CH 2 CH 2 -C (O) O-CH 2 CH 2 -OC (O) or -NHCO-.

  The oligomeric phenols of formula I which are the subject of the present invention are prepared by known methods (see, for example, the first published specification of the patent application DE 2,509,654):

  monomeric phenols carrying a mercapto group which

tooth with formula IX R 1

-S

HO- e

H O XA (IX)

  or monomeric phenols carrying a vinyl radical which correspond to the formula X

R R

  Wherein R 1, R 2, R 3, R 4, R 5, R 6, X and Y

  have the meanings previously given, on oli-

  reactive gomers of dienes of formula XI w wherein Q, Q ', R, m, N and S have the meanings given above, the molar ratio of (IX) or (X) to (XI) to be understood between 10: 100 and 35: 100,

  preferably between 15: 100 and 30: 100.

  The addition reaction is carried out in

  presence of radical initiators taken as a whole

  by azo compounds and peroxidic compounds.

  such as azo-bis-isobutyronitrile, cumyl hydroperoxide or dibenzoyl peroxide, and possibly by means of ultraviolet light in the presence of

  sensitizers or primers, without solvents or in

  an inert solvent such as benzene, toluene,

  xylenes, tetrahydrofuran, hexane or ligroin.

  Suitable diene oligomers include those containing double bonds

  in the oligomeric chain itself or in the ex-

  side chains and which have a molecular weight

  average from 1500 to 10,000, preferably from 2500 to 5000.

  Such diene oligomers are known and are prepared by known methods (see, for example, US Patent 3,796,762) from monomers containing two 1,3-conjugated double bonds, such as 1,3-butadiene, isoprene, chloroprene, 2-cyano-1,3-butadiene or 2,3-dimethyl-1,3-butadiene. Diene oligomers which have been obtained from 1,3-butadiene are preferred.

  Phenols carrying radicals are known

  mercapto or vinyl caux suitable for the preparation

  cation of the compounds according to the invention, and the homo-

  I also know how to prepare them Voicidefinis by their formulas, examples of such phenols:

(CH 3) 3 C (CH 3) 3 C

o CH 2 _H HO / CH -SH

(CH 3) 3 / H 3

(CH 3) 3 C (CH 3) 3 C

H 0 -, - \\ - HH -SH

HO ^^ <SH H 0- * * S \

_ // HC

(CH 3) 3 CHC /

(CH 3) 3 C \ H 3 C \

HO- * / -CH CH 2 -O-CH CH -SH110 CH

\ _ / 3) 2 C 2222 \ _ / 3

\ \

(CH 3) C H 3 C CH 2 SH

33 3 2

2 5 10 124

(CH 3) 3 C

0._ I-CH CH SH

Ho _CH CH

2 2 2 2

H 3 C /

(Ci 13) 3 C

HO // -CH 3

H 3 C / CH 2-SH

(CH 3) 3 C

  el, _1- q -J-Cil -SH HO Cil 2 scii 2 ci 2 2

(CH 3) 3 e

(CH 3) 3 C-,

HO c'Il SCH '-o-CH CH SCH 2 CH 2-SH

2 2 2 2

(CH 3) 3

(Cil 3) 3 C \ L (CH CH He 'Cil his

IJO-0 -CH 2 SCH 2 2 254-2 C 2 2

(CH 3) 3 C /

(Cil 3) 3 \ _.

  - // CH-CH-L (Cil Cil S -) - C 112 CH 2-SH Ho -, \ 2 2 2 2 3 (CH 3) 3 cl

(CH 3) 3 C

  It is also possible to use the following formulas: ## STR2 ##

(CH 3) 3 C /

(CH 3) 3 \

HO '- -CH 2-CH = CH 2

(CH 3) 3 C /

(CH 3) 3 c \ HO e, -CH Nli-dli = CH

2 2

(CH 3) 3 C /

CH 3) 3 C,

HO // I _CH -0 CH = CH

/ 2 2

H 3 C /

(CH 3) 3 C

O HO / -CH 2 Cil 2- 0-CH = CH 2

(CH 3) 3 e

(CH 3) 3 C

HO / -CH 2-0 -Cli = Cli 2

(CH 3) 3 C /

(CH 3 Y 3 C)

HO-, -O-CH = CH 2

(CH 3) 3 C /

  (CH 3) 3 C CH 3 (Cil 33: 0-O 2 kd-CH 2 -80-OH)

(CH C (CH

3 3 3 3

(CH 33 \

"// -1 cil -LCH CH O-CH = CH -CH

HO 2 2 2 2 2

(CH 33 CI /

(CH 33 C \

-.o -9 \\ CH -LCH CH = CH

HO CH 2 2

2 2

(CH

3 3 (Cil 3) 3 C

/ I / '\', -NH-CH = CH

- \ 2

(CH 3) 3 C / -

(CR 3) 3 C \ - / C (CH 3) 3

-OCR 1

11, -OH

HO \ / -

(CH 3) 3 CH 3 O 3 (CH 3) 3

(CH 3) 3 C-, / C (CH 3)

i / k NH- e -OH

HO -NH-CII = CH

(CH) C / C (CH 3) 3

3 3

Z 2510124

he (c 13) 3 c \

HO NH-CH = CH OCH

AT

(CH 3) 3

(CH 3) 3 C

C a

(CH 3) 3 AC /

  The invention furthermore relates to the applica-

  of the compounds of formula I as stabilizers for organic materials which can thus be stabilized against the destructive effects of oxygen, heat, light and energetic radiation, such as 3-rays and rays. examples of organic materials that

  can be stabilized advantageously with the aid of

  posed in accordance with the invention are:

  1 polymers of monoolefins and di-

  olefins, such as polyethylene (optionally crosslinked), polypropylene, polyisobutene, polybutene-1, poly-methyl-pentene, polyisoprene and polybutadiene, and polymers of cycloolefins, for example

cyclo-pentene or norbornene.

  2 Blends of the polymers mentioned under

  1), such as blends of polypropylene with poly-

  ethylene or with polyisobutene.

  3 Copolymers of mono-olefins and di-

  olefins with each other or with other vinyl monomers, such as copolymers of ethylene and propylene, copolymers of propylene and butene-1, copolymers of propylene and isobutene, copolymers of ethylene and butene- l, copolymers of propylene and butadiene,

12 2510124

  copolymers of isobutene and isoprene, copolymers

  of ethylene and alkyl acrylates, copolymers of ethylene

  and methacrylates of alkyls, copolymers of ethylene

  and vinyl acetate, copolymers of ethylene and

  and ethylene terpolymers with propylene and a diene, which may be hexadiene, dicyclopentadiene or ethylidene norbornene.

4 Polystyrene.

  Copolymers of styrene or d-methyl;

  styrene with dienes or acrylic compounds, in particular

  styrene-butadiene, styrene-acrylonitrile, styrene

ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene acrylonitrile methyl acrylate; high-resilience blends of copolymers of styrene and another polymer, such as a polyacrylate, a diene polymer or

  an ethylene-propylene-diene terpolymer; copolymers

  styrene sequencers, especially styrene-butadiene-

  styrene, styrene-isoprene-styrene, styrene-ethylene / butene-

  styrene or styrene-ethylene / propylene-styrene.

  Graft copolymers of styrene, such as styrene on polybutadiene, styrene and acrylonitrile on

  polybutadiene, styrene and maleic anhydride on poly-

  butadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylenepropylene-diene terpolymers, styrene and

  acrylonitrile on alkyl polyacrylates or poly-

  alkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, as well as their mixtures with the copolymers mentioned under 5), such as those known for example under the names of polymers

ABS, MBS, ASA and AES.

  Halogenated polymers, such as polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, homopolymers and copolymers of epichlorohydrin, more especially polymers of halogenated vinyl compounds, for example polyvinyl chloride, polyvinyl chloride, vinylidene chloride, polyvinyl fluoride and polyvinylidene fluoride; as well as their copolymers, such as vinyl chloride-vinylidene chloride, vinyl-vinyl acetal chloride, and

  vinylidene chloride-vinyl acetate.

  Polymers derived from unsaturated acids in t, t and their derivatives, such as polyacrylates

  and polymethacrylates, polyacrylamides and polyacrylamines

  nonitriles. Copolymers of the monomers mentioned under 8) with each other or with other unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-halogenide copolymers; vinyl, and terpolymers

  acrylonitrile-alkyl methacrylate-butadiene.

  Polymers derived from alcohols or amines

  inseminated animals or their acylated derivatives or their

  such as poly (vinyl alcohol), pylacetate,

  polystearate, polybenzoate and vinyl polymaleate

  polyvinylbutyral, allyl polyphthalate and polyallylmelamine. Homopolymers and copolymers of ethers

  cyclic, such as poly-alkylene glycol, poly-

  (ethylene oxide), poly (propylene oxide) and their

  copolymers with bis-glycidyl ethers.

  Polyacetals, such as polyoxymethyl

  ne, as well as polyoxymethylenes that contain

  comonomers, for example ethylene oxide.

  Polyoxides and sulfides of phenylenes.

  Polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups and from aliphatic or aromatic polyisocyanates and their precursors

  (polyisocyanates, polyols, prepolymers).

  Polyamides and copolyamides derived from

  dicarboxylic acid diamines and / or amino acids

  carboxylic acids or corresponding lactams, such as

  polyamide 6, polyamide 6, polyamide 6-6, poly-

  amide 6-10, polyamide 11, polyamide 12, poly-

  (2,4,4-trimethyl hexamethylene terephthalamide), the poly-

  (m-phenylene-isophthalamide), as well as their copolymers with polyethers, for example with polyethylene glycol, polypropylene glycol or poly-tetramethylene glycol.

  16 Polyureas, polyimides and polyamides

amide-imides.

  Polyesters derived from dicarboxylic acid

  and the corresponding lactones, such as ethylene glycol polyterephthalate, butylene polyterephthalate, poly (bis-1,4-hydroxymethyl) cyclohexane polyterephthalate, poly (bis) terephthalate, and the like. 2- (hydroxy-4-phenyl) propane, polyhydroxybenzoates, as well as block polyether ethers derived from hydroxy-grouped polyethylenes

  terminals, diols and dicarboxylic acids.

Polycarbonates.

  Polysulfones and polyether sulfones.

  Crosslinked polymers which derive, on the one hand, from aldehydes and, on the other hand, from phenols, urea or melanin, such as phenol-formaldehyde resins,

  urea-formaldehyde and melamine-formaldehyde.

  21 Drying and non-drying alkyd resins

drying.

  Unsaturated polyester resins which de-

  of copolyesters from saturated and unsaturated dicarboxylic acids and polyols as well as vinyl compounds acting as crosslinking agents, and also their

  halogenated modifications little flammable.

  Crosslinkable acrylic resins derived from substituted acrylic esters, for example

  epoxy acrylates, urethane acrylates or polyester-

  acrylates. Alkyd resins, polyester resins and acrylate resins which are crosslinked with

  melamine resins, urea resins, polyisocyanates,

or epoxy resins.

  Cross-linked epoxy resins which de-

  of polyepoxides, for example bis-glycidyl ethers,

  or cycloaliphatic di-epoxides.

  26 Natural polymers, such as cellulosic

  natural rubber and gelatin, as well as their

  chemically modified cells with preservation of the structure

  polymer, especially cellulose acetates, propionates and butyrates or cellulose ethers,

such as methylcellulose.

  27 Natural organic materials or syn-

  theories that are pure monomeric compounds or

  such compounds, for example mineral oils, animal or vegetable fats, oils and waxes,

  or oils, waxes and greases based on synthetic esters

  (for example phthalates, adipates, phospha-

  or trimellitates), as well as mixtures of

  synthetic materials with mineral oils in any weight ratios, such as those used, for example, as plasticizers for plastics or spinning auxiliaries, as well as their

aqueous emulsions.

  28 Aqueous emulsions of natural rubbers

  or synthetic, such as rubber latex

  or styrene-butadiene copolymers latex

boxylés.

  As is known, particular importance is attached to the stabilization of polyolefins, polymers of styrene and polyurethanes, and the compounds of formula I are remarkably well suited for this purpose.

  high-density and low-density polyethylenes, polypropylene

  ethylene-propylene copolymers, polystyrene,

  styrene-butadiene-acrylonitrile copolymers,

  polyesters of polyolefins or polymers of styrene, polyurethanes based on polyethers or polyesters, in the form of films, fibers, varnishes, paints, elastomers or cellular materials (foams) The compounds of formula I are suitable any especially for the stabilization of high-resilience polystyrene (IPS) and ABS The stabilization of lubricants is

also very interesting.

  Stabilizers are incorporated in the plastics in a concentration of 0.01 to 5% by

  weight, preferably from 0.1 to 2.0% by weight and more particularly

  from 0.2 to 0.6% by weight, based on the material

re to stabilize.

  The incorporation may take place after the polymerization: for example the compounds, and possibly other additives, are mixed with the melt by the methods usually applied in the industry, before or during the forming, or we apply on the

  polymer compounds in the form of solutions or dis-

  persions, and eventually the solvent is then removed

by evaporation.

  The invention therefore also relates to plastics which have been stabilized by addition of 0.01 to 5% by weight of a compound of formula I and which may optionally contain other known additives.

  The plastics thus stabilized can

  can be used in the most diverse forms, for example in the form of sheets, fibers, small strips or profiles, or as binders for

  paints, varnishes, glues or putties.

  Additional additives with which the stabilizers used according to the invention can be combined include, for example, the compounds of the following list: 1 Antioxidants 1.1 Alkylated monophenols, for example: 2,6-di-tert-butylmethyl 4-phenol, tert-butyl-2-dimethyl-4,6-phenol, di-tert-butyl-2,6-ethyl-4-phenol, 2,6-di-tert-butyl-4-n-butyl-phenol, di-tert-butyl; 2,6-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 1 '(--methyl-cyclohexyl) -2,4-dimethylphenol,

2 510124

  2,6-diadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol and

  2,6-di-tert-butyl-4-methoxymethyl-phenol.

  1.2 alkylated hydroquinones, for example di-tert-butyl-2,6-methoxyphenol, di-tert-butyl-2,5-hydroquinone and

di-tert-pentyl-2,5-hydroquinone.

  1.3 Hydrogenated diphenyl sulphides, for example thio-2,2 'bis (tert-butyl-6-methyl-4-phenol), thio-2,2' bis- (4-octylphenol), thio-4, 4 'bis (tert-butyl-6-methyl-3-phenol) and

  4,4-thio-bis (tert-butyl-6-methyl-2-phenol).

  1.4 Alkylidene bisphenols, for example 2,2'-methylene, 2,2'-methylene, 2,2'-methylene phenol, 1, 2,2-methylene, 2,2'-methylene, 2-methylene 2,2'-ethylidene 2,2'-ethylidene 4,4'-methylene 4,4'-methylen (6-tert-butyl-4-methylphenol) bis (tert 4-butyl-4-ethyl-phenol), bis-L methyl 4 (C (n-methylcyclohexyl) -6 bis- (4-methyl-6-cyclohexylphenol), bis (6-nonyl-4-methylphenol), (4,6-di-tert-butyl-phenyl), bis (4,6-di-tert-butyl-phenol), bis (tert-butyl-6-isobutyl-4-phenol), bis (di-tert-butyl) 2,6-phenol), bis (tert-butyl-6-methyl-2-phenol), bis (tert-butyl-5-hydroxy-4-methyl-2-phenyl) -1,1-butane, bis (tert-butyl) 3-methyl-5-hydroxy-2-benzyl) -2,6-methyl-phenol, tris (4-tert-butyl-4-hydroxy-2-methyl-phenyl) -1,1,3-butane,

  bis (tert-butyl-5-hydroxy-4-methyl-2-phenyl) -1,1-n

3-dodecylthio butane,

  bis-Zbis- (tert-butyl-3-hydroxy-4-phenyl) -3,3-butanoate

te 7 of ethylene glycol,

  bis (tert-butyl-3-hydroxy-4-methyl-5-phenyl) -dicyclo

  Pentadiene and bis (2-tert-butyl-2-hydroxy-2-methyl-5) terephthalate

  benzyl) -2-tert-butyl-6-methyl-4-phenylel.

  1.5 Benzyl compounds, for example: tris (di-tert-butyl-3,5-hydroxy-benzyl) -1,3,5-trimethyl-2,4,6 benzene, bis (di-tert-butyl) sulfide, 4-hydroxy-benzyl), isooctyl-4-di (tert-butyl-4-hydroxy-4-benzylthio) acetate, bis (tert-butyl-4-hydroxy-3-dimethyl-2-dithio-terephthalate Benzyl), tris (di-tert-butyl-3,5-hydroxy-4-benzyl) -1,3,5 isocyanurate,

  the isocyanurate de-tris- (tert-butyl-4-hydroxy-3-dimethyl)

  2,6-benzyl) -1,3,5, dioctadecyl (di-tert-butyl-3,5-hydroxy-4-benzyl) -phosphonate and (3,5-di-tert-butyl-4-hydroxy-4-benzyl) - phosphonate

monoethyl, calcium salt.

  1.6 Acylamino phenols, for example: 4-hydroxy-phenyl amide of lauric acid 1-hydroxy-4-phenyl-amide of stearic acid and 2,4-bisoctylthio (di-tert-butyl-3) , 5 hydroxy-4

anilino) -6 triazine-1,3,5.

  1.7 Esters derived, on the one hand, from 3,5-di-tert-butyl-3-hydroxy-3-phenylpropionic acid and, on the other hand, from alcohols with

  or more hydroxy groups, these alcohols being able to be taken from those of the following list: methanol diethylene glycol octadecanol triethylene glycol hexane-1,6-diol pentaerythritol

  neopentyl glycol tris-hydroxy-isocyanurate

ethyl thio-diethylene glycol

N, N'-bis- (hydroxyethyl) -

oxalamide

  1.8 Esters deriving, on the one hand, from the acid (tert-

  butyl-5-hydroxy-3-methyl-3-phenylpropionic phenol, and, on the other hand, alcohols with one or more hydroxyl groups, alcohols which may be chosen from those of the following list: methanol diethylene glycol octadecanol triethylene glycol hexane-1,6-diol pentaerythritol

  neopentyl-1,6-isocyanurate of tris-hydroxy-

ethyl

  thio-diethylene glycol N, N '-bis (hydroxyethyl) -

oxal amide.

  1.9 amides of (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid, for example:

  N, N'-bis-di-tert-butyl-3,5-hydroxy-4-phenylpropane

pionyl) hexamethylene diamine,

  N, N'-bis- (di-tert-butyl-3,5-hydroxy-4-phenyl)

  propionyl) -trimethylene diamine, and

  N, N'-bis- (di-tert-butyl-3,5-hydroxy-4-phenyl)

propionyl) -hydrazine.

  2 Ultraviolet absorbers and

bilisants in the light.

  2.1 2- (2-Hydroxyphenyl) benzotriazoles, for example 5'-methyl, 3'-5'-di-tert-butyl, -tert-butyl, 5 '- (1,1,3,3-tetramethyl-butyl) derivatives ), -chloro-3 ', 5'-di-tert-butylicic acid, 5-chloro 3 tert-

  butyl-5'-methyl, 3'-sec-butyl 5'-tert-butyl, -

  4'-octyloxy 3 ', 5' di-tert-pentyl, 3 ', 5' -bis- (1,1,

  3,3-tetramethylbutyl) and 3 ', 5' -bis- (U, J-dimethyl)

  benzyl) -2 (2'-hydroxyphenyl).

  2.2 2-Hydroxybenzophenones, for example derivatives

  4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, dodecyl-

  oxy-4, benzyloxy-4, trihydroxy-4,2 ', 4' and hydroxy-2 '

dimethoxy-414 '.

  2.3 Substituted benzoic acid esters,

for example

  4-tert-butylphenyl salicylate, sodium salicylate

  phenyl, octylphenyl salicylate, dibenzoyl

  resorcinol, bis- (tert-butyl-4-benzoyl) -resocinol, benzoylresorcinol and di-tert-butyl-3,5-hydroxy-4

  2,4-di-tert-butyl benzoate phenyl benzoate.

  -2.4 Acrylic esters, for example

  t-cyano, diphenyl ethyl acrylate or isocyanate

  octyl, methyl d-methoxycarbonyl-cinnamate,

  methyl or butyl cyano P-methyl-p-methoxy-cinnamate, methyl-methoxycarbonyl-p-methoxy-cinnamate and N- (β-methoxy-carbonyl cyanovinyl);

2-methylindoline.

  2.5 Nickel compounds, for example 2-thio-2'-bis-2-tetramethyl-1,1,3,3-butyl) phenol / nickel complexes, such as the 1: 1 or 1: 2 complex, eventually

  with additional coordinators such as n-butyl-

  amine, triethanolamine or N-cyclohexyl diethanol

  amine, nickel dibutyl-dithiocarbamate, nickel salts of alkyl monoesters of (4-hydroxy-3,5-di-tert-butylbenzyl) phosphonic acid, especially

  methyl ester or ethyl ester,

  nickel plexes of ketoefmes such as (2-hydroxy-4-methyl-phenyl) (undecyl) -ketonoxime, and 1-phenyl-4-lauroyl-5-hydroxy-pyrazole nickel complexes,

  possibly with additional coordinators.

  Hindered amines, for example: bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,6,6-pentamethylpiperidyl) sebacate,

  (n-butyl- (di-tert-butyl-3,5-hydroxy-4-benzyl) -

  bis (pentamethyl-1,2,2,6,6-piperidyl) malonate,

  the condensation product of hydroxyethyl-1 tetra-

  methyl-2,2,6,6-hydroxy-4-piperidine and succinic acid, the condensation product of N, N '- (2,2-tetramethyl,

  6.6 piperidyl) -hexamethylenediamine and tert-

  4-octylamino-2,6-dichloro-1,3,5-triazine and tris nitrilotriacetate (2,2,6,6-tetramethylpiperidyl). 2.7 Oxalamides, for example: dioctyloxy-4,4'-oxanilide, dioctyloxy-2,2'-di-tert-butyl-5,5-oxanilide, di-dodecyloxy-2,2 'di-tert-butyl- 5,5 'oxanilide, ethoxy2 ethyl-2' oxanilide, N, N'-bis (3-dimethylamino-propyl) -oxanilide, 2-ethoxy-tert-butyl-5-ethyl-2 'oxanilide and mixtures thereof with 2-ethoxy-2-ethyl-di-tert-butyl-5,4-oxarnilide, and mixtures of oxanilides bearing two methoxy ortho and para as well as oxanilide bearing two ethoxy in ortho and para. Metal deactivators, for example: N, N'-diphenyl oxalamide, N-salicylidene N-salicyloyl hydrazine, N, N'bis-salicyloyl hydrazine, N, N'-bis-di -tert-butyl-3,5-hydroxy-4-phenylpropionyl) hydrazine, 3-salicyloylamino-triazole-1,2,4 and

bis-benzylidene oxalohydrazide.

  Phosphites and phosphonites, for example: triphenyl phosphite, diphenyl and alkyl phosphites, phenyl and dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, triphosphite octadecyl, distearyl and pentaerythrityl diphosphite, tris- (2,4-di-tert-butyl-phenyl) phosphite, di-isodecyl and pentaerythrityl diphosphite, bis (di-tert-butyl) 2,4-phenyl) and pentaerythrityl, tristearyl triphosphite and sorbitol, and

  the diphenyl 4,4'-diphosphonite of tetrakis (di-tertak-

2,4-butylphenyl).

  Peroxide-destroying compounds, for example: -thio-dipropionic acid esters, such as lauryl, stearyl, myristyl and tridecyl esters, mercapto-benzimidazole, 2-mercaptobenzimidazole zinc salt, dibutyl- dithiocarbamate

  zinc, dioctadecyl disulphide, and tetrakis

  (13-dodecylthio) -propionate pentaerythritol.

  Polyamide stabilizers, for example copper salts associated with iodides and / or

  phosphorus compounds, and salts of divalent manganese.

  Basic co-stabilizers, for example: melamine, polyvinyl pyrrolidone, cyanoguanidine, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, salts alkali metals and alkaline earth metals of higher fatty acids, such as calcium stearate, zinc stearate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate and

tin pyrocatechlolate.

  Nucleating agents, for example 4-tert-butylbenzoic acid, adipic acid and

diphenylacetic acid.

  Fillers and reinforcing agents, for example: Calcium carbonates, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, oxides and hydroxides of metals, black

defumed and graphite.

  Other additives, for example: plasticizers, lubricants, emulsifiers, pigments, optical brighteners, impregnating agents,

  anti-static and porogens.

  The following examples illustrate the preparation

  ration and the application of the compounds according to the invention.

tion.

  EXAMPLES RELATING TO THE METHODS OF PREPARATION

  A Addition products of mercapto phenols to butadiene oligomers

General procedure.

  250 g of benzene are dissolved in 100 g.

  of a polybutadiene resin called "polybutadienharz R 45 -HT'l

  (a butadiene ologomer with end -OH groups

  Atlantic Richfield Co) and boiled under nitrogen at reflux under reflux while stirring.

  drop in 5 hours the amount of mercapto phenols

  shown in Table I in the form of a solution

  30% by weight benzene which also contains the

  lyser (in each case 2.0 g of azobisisobutyronitrile).

  The reaction mixture is then refluxed

  10 hours after filtering

  precipitate the product by adding methanol carefully

  tion. Stabilizers according to the invention

  come in the form of yellowish, very viscous oils.

T A B L E A U I

  N Phenol starting Phenol ratio Ee '= t: m

(CH 3) 3 C

  1 H-CH 2 CH 2 -CO-CH 2 CH 2 -SH 70 g -12: 100

/ 2222

(CH 3) 3 C

(CH 3) 3 CX

3 o 3 2 H- * -CH 3 70 g -16: 100

H 3 C / CH 2-SH

(CH 3) 3 C

3 HO / -CH -SH 77 g X 16: 100

\ / 2

(CH 3) 3 c /

(CH 3) 3 C

  91 g, 16:10 H HO CH 2 CH 2 O-CH 2 CH 2 -SH 91 g, 16: 100

H 3 C / 22 22

  H 3 B Addition products of phenols carrying a radical

  vinyl on butadiene oligomers.

Example 5

  By operating as in the general procedure described under A), 100 g of polybutadiene resin "Polybutadienharz R 45 HT" and 80 g of tert-butyl-2-dimethyl-4,6-acryloyloxymethyl-3-phenol are reacted.

  (for the preparation of this body see below), the report

  The addition products according to the invention are in the form of very viscous, almost colorless oils which can be used for subsequent reactions without further purification. links from

  copolymers can be demonstrated by S pectro

NMR cospie.

  2-tert-butyl-4,6-dimethyl acryloyloxy

  3-methylphenol from which one left, that is to say the compound of formula:

(CH 3) 3 C

Ho 0-: * -CH

\ _ / 3

3 CH 2 Og-CH = CH 2

  is prepared as follows.

  The mixture is refluxed for 4 hours, at 80.degree.

   C. while stirring, 33.8 g of tert-butyl-2-dimethyl-4,6-chloromethyl-3-phenol and 14.1 g of sodium acrylate

  (dry, powdery) The solvent is then removed by

  poration under reduced pressure and add toluene and water to the residue After separating the aqueous phase the dried toluene solution is evaporated and the residue is distilled under high vacuum. The boiling point is 126-130 ° C. at 0.005 mbar. Pure acrylic ester forms

  white crystals that melt at 60 C.

EXAMPLES RELATED TO APPLICATIONS

Example 6

* Stabilization of a high-resilience polystyrene.

  Twenty-two times

  high-resilience styrene which contains 8% by weight of polybutadiene (high cis-isomer content) and 0.035% by weight of 2,6-di-tert-butyl-cresol as base stabilizer, 0,05% by weight of zinc stearate as a lubricant

  and 0.1% by weight of one of the antioxidants according to the invention.

  (indicated in Tables II and III below by the numbers of the corresponding preparation examples) and the granulated product obtained is molded in 3 minutes

   C, in small test pieces 2 mm thick.

  The specimens are subjected to an aging

  In a circulating air oven, the following are determined: a) Yellowness index (IJ) according to ASTM D 1925 at 80 ° C. (measurements made on the specimens after 0, 250, 500, 750 and 1000 hours) ) and 160 C (measurements taken after 0, 60, 90, 120 and 180 minutes) (the results are shown in Table II):

T A B L E A U II

  b) the resilience in kg cm / cm 2 after aging at C (measurements made on the specimens after 15, 30, 60, 120 and 150 minutes): Stabilizer IJ at 80 C after IJ at 160 C at the end ( N from the following time in hours of the following time in the ex)) minute 0 250 1 500 750 11000 oo 1 90 1120 180 No antioxidant 0.5 18 24 36 48 O 17 37 47 73

__, -__ _ _

1 0.3 16 21 27 35 O 14 24 26 55

2 1.3 20 28 31 40 1 2518

13,221 25 I 43 l

26 2510124

T A B L E A U III

Resilience after aging

  Stabilization at 1600 C of a duration (N of the ex) in minutes, of

30 60 120 150

no anti * 10.4 oxidant

1 * * * 10.1

2 1 * * * * 13.6

I 3 1 * * _ * 12,3

the test piece does not break.

Example 7

  Stabilization of polybutadiene An unstabilized polybutadiene is dissolved in toluene so that the concentration reached is about 5% and added to the solution

  0.5% by weight of one of the antioxidants according to the invention.

  tion (these are indicated in Table IV below).

  under the numbers of the corresponding preparation examples) The rubber is then coagulated

  with hot water at 90 ° C. and dried in an oven at 40 ° C.

  After that, the rubber is molded in 20 minutes at 80 ° C.

  in specimen plates 2 mm thick.

  On the test pieces thus obtained the following tests were carried out: a) a silicone oil aging with a duration of minutes at 160 ° C., followed by a determination of the gel content G: G = EM × 100 (% where E represents the weight of the introduced sample (1 g of rubber in 100 ml of toluene) and M the weight of the evaporation residue of the filtered toluene solution,

  (b) a 24-hour extraction with ethanol

  at room temperature, followed by drying for 24 hours at 40 ° C. under reduced pressure, and then aging and determination of the content of the product.

gel as described under a).

  The results are shown in Table IV.

BOARD

IV Stabilizer Gel content (%) l

  (N of the ex) without extraction after extrac-

I

no anti

-90 95

oxidant

1 6.8 8.8

2 3.7 5.0

  l, I 1, 3 _______________t______________

Claims (7)

R E V E N D I C A T IO N S   1) Compounds corresponding to the formula ## STR1 ## in which Q and Q are each independently of each other, hydrogen, hydroxy, -COOH, -COOCH 3, -COOC 2 H 5, -CH 3, C 2 H 5 or a phenyl, represents -C 1 or -CN, denotes a number 4 to 6, denotes the number O or 1, denotes a number from 30 to 150, denotes a number from 3 to 50, and the ratio t: m being between 10: 100 and 35: 100, and represents a radical in accordance with one of formulas II and III RK \ HO Z 3 R _ R 4 a- x R R R 13   (II) (III) wherein R 1 and R 2 are each independently of one another, C 1 -C 8 alkyl, C 5 -C 8 cycloalkyl, C 6 -C 10 aryl, , a C 7 -C 10 aralkyl, a C 7 -C 10 alkylaryl, R 2 may also represent hydrogen in contrast to R 1, R 3 represents hydrogen or a C 1 -C 8 alkyl, R 4 , R 5 and R 6 each independently represent hydrogen, a radical -COOR 1 or a radical _, X = / -Y, /   and R 4 may further represent alkyl in   Cl-C 8, X, Y and Y 'each represent independently   each of R 9 and R 10 independently of each other is a direct bond or a divalent hydrocarbon radical containing from 1 to 20 carbon atoms. carbon, radical which is uninterrupted or which is interrupted one or more times by -O or -S-, Z represents -O-, -S-, -N (Rll) -, -CON (Rll) -, -N (Rll ) CO-, -OC (O) -or -C (O) O and, in the case of X, may further represent a radical R 12 -COONH 3 Qou, Z 'represents a bond say COO * NH 3 Q or _ or -OC (O) -, r denotes the number O or 1, R 1 represents hydrogen or R 1, and R represents a radical -OR 1, -SR 1, -NH or -N (R 1) , and if A is a group II, q = t, and if it is a It group, q = o.   2) Compounds of formula I according to claim 1   in which A is a group of formula II.   3) Compounds according to claim 1 wherein S is 0, N is 4 and A is a radical corresponding to one of formulas IV and V R -XS_ Due to 0- \ XR 3 (IV) R / 3 R 2 R R 6 / '=' R 4 5 R 2 3 R 2 2510124   in which R 1 and R 2 each independently represent   from each other, a C 1 -C 4 alkyl, R 3 represents   hydrogen or methyl, R 4, R 5 and R 6 represent each   each, independently of one another, hydrogen, -COOCH 3, -COOC 2 H 5 or a radical: R R / l -OH y X /   X, Y and Y 'each represent, inde-   from each other, a radical -R 9- * Z-R 104 r Z'-   wherein R 9 and R 10 each independently represent   from each other, a direct link or a radical   linear bivalent carbon containing from 1 to 12 carbon atoms   and which can be uninterrupted or interrupted once or more by -S-, Z represents -O-, -NH-, -C (O) O or -OC (O), Z 'represents a direct or   -0 ç (O) and r is 0 or 1.   4) Compounds according to claim 1 in   which A is a group of formula IV.   Compounds according to claim 1 wherein S is 0, N is 4, m is a number of 50 to 80, t is a number of 7 to 28 and the ratio t: m is between 12: 100 and 30: 100, Q and Q 'represent   each a hydroxy group, A represents a radical corresponding to   in one of the formulas VI, VII and VIII H 1 O - \ / ± X-S (VI) - R 2 R (Vii) HO -'- '-C-5- e o = C 43 \ CH -S- 3 R 2 R 1 HX / 2 4 (VIII) 4   R 2 in which R 1 represents a tert-butyl, R 2 a methyl or a tert-butyl, R 4 hydrogen or a radical / R 1/1 R 2   X represents a direct bond or a radical -CH 2, -CH 2 CH 2, -CH 2 CH 2 -C (O) O-CH 2 CH 2, -CH 2 SCH 2 -OC (O) -CH 2 or -CH 2 SCH 2-C (O) O * CH 2 CH 2 S + 4 CH 2 CH 2, the index q designating a number from 0 to 4, and Y represents a direct bond or a radical -CH 2 -, -CH 2 CH 2-, -OC (O) -,   -CH 2 -NHCO-, -CH 2 -OC (O) -, -OC (O) -CH 2-, -CH 2 CH 2 -C (O) O-,   -CH 2 CH 2 -C (O) -O-CH 2, -CH 2 CH 2 -C (O) O-CH 2 CH 2 -OC (O) or -NHCO-.   6) Comnosed according to claim 5 in   which A is a group of formula VI or VII.   7) Process for the preparation of the compounds of formula I according to claim 1, in which monomeric phenols bearing a mercapto group O which have formula IX are attached. R / * - * HSH (IX)   HO- 'R,., (X) or monomeric phenols carrying a vinyl radical which have the formula X X 4 c \ (X) R, 32 2510124   formulas in which R, R 2, R 3, R 4, R 5, R 6, X and Y have the meanings given in claim 1, on reactive oligomers of dienes corresponding to the formula XI T -Cn H 2 Wherein Q, Q ', R, m, N and S have the meanings given in claim 1, the molar ratio of (IX) or (X) to (XI) being between 10 and 10 : 100 and 35: 100,   in the presence of a suitable radical initiator and possibly   under the action of ultra-violet light.   (8) Organic materials which have been   bilayed with compounds of formula I according to the 1.