BE1012645A5 - Monomeric and oligomeric bisphosphites as polymer stabilisers - Google Patents

Abstract

Formulations are described containing a halogenated polymeric substance,and at least one formula I phosphite in which n is a number from 1 to 6, Ris a divalent bridge possessing one of the formulas, m is a number from 1 to5, R1, R2, R3 and R4 represent independently from each other a C4-C22 alkyl,C7-C9 phenylalkyl, C5-C8 cycloalkyl or (C1-C4 alkyl) C5-C8 cycloalkylremainder, where R1 and R2 and/or R3 and R4 together represent a C2-C9alkylene remainder or a formula group and new compounds according to formulaI and their use as stabilisers.<IMAGE>

Description

       

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   Bisphosphites monomers and oligomers as stabilizers for polymers
The present invention relates to compositions containing a halogenated polymeric material, in particular a homopolymer or a copolymer of vinyl chloride, and at least one organic bisphosphite monomer or oligomer, the use of the latter for the stabilization of said polymer material against degradation, due in particular to oxidation, heat and / or light; and novel monomeric and oligomeric bisphosphites, compositions containing them and their use for the stabilization of polymers and lubricants.



   Bisphosphites derived from dialcohols are known in large numbers in the literature. Examples are patent documents US-A-3,047,608, US-A-3342767, US-A-3,205,250, US-A-3,283,037, US-A-3,592,858, EP-A-635512 , EP-A-635511, DE-A-3009634, DE-A-2330979, DD-A-229995, JP-A-52-145452, JPA-57-65743, JP-A-53-67755, JP-A -55-71744 and JP-A-53-40719. Phosphites are generally known as formatting stabilizers for polyolefins, elastomers, poly (vinyl chloride) and other polymers and are of great practical importance. The aforementioned patent publications therefore also describe the bisphosphites known as stabilizers for a whole series of polymer substrates, and some of them also as stabilizers for poly (vinyl chloride) (PVC).



   Due to the increased requirements for the activity and compatibility of stabilizers with the environment, there is still a need to discover and optimize stabilizers and stabilizer systems, even in the field of organic phosphites.



   It has been found that a well-defined group of bisphosphites is particularly suitable as stabilizers or cost-stabilizers, in particular for halogenated polymers, for example PVC.



   The present invention therefore relates to a composition containing (i) a halogenated polymeric material, and (ii) at least one phosphite of formula 1
 EMI1.1
 where n is a number from 1 to 6,

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 EMI2.1
 R is a divalent bridge having one of the formulas
 EMI2.2
 
 EMI2.3
 - CH H-CH-or (breakage)
 EMI2.4
 
 EMI2.5
 m is a number from 1 to 5, RI, R2, R3 and R4 independently of one another represent a C4-C22 alkyl, C7-C9 phenylalkyl, C5-C8 cycloalkyl or (C, -CJ- alkyl C5-C8 cycloalkyl, or
 EMI2.6
 RI and R2 and / or R3 and R4 together represent a C2-C9 alkylene residue or a group of formula

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 EMI3.1
 
 EMI3.2
 provided that a) the composition does not contain a stabilizer containing Ba,

   Zn and / or Ca when
 EMI3.3
 RI + R2 and R3 + R4 represent a group of formula C (CHg) and R is a - CH group BRI or BR2, and that b) m is different from 2 when R ,, R;, R and R4 are identical and represent alkyl radicals in C, 2-C22 and R is a group BR2.



   The alkyl and alkylene residues, as they appear in the general meanings of the substituents, can be linear or branched. Examples are the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl and heneicosyl radicals. . Examples of alkylene groups (Ri + R2, R3 + R4) are ethylene, propylene, 2-methylpropylene, 2,2-dimethylpropylene, 2-methyl-2-n-propyl-
 EMI3.4
 propylene and 2-ethyl-2-n-butylpropylene. In this case, it is formed with the group
 EMI3.5
 .... 0- 'preferably a 6-link cycle.



  0-
 EMI3.6
 A C 4 -C cycloalkyl residue which is unsubstituted or substituted by C 4 -C 4 alkyl represents for example a cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl or cycloheptyl residue. Cyclohexyl, methylcyclohexyl and dimethylcyclohexyl are preferred.



   A phenylalkyl residue at Cy-Cg is, for example, a benzyl, phenethyl, a-methylbenzyl or a, a-dimethylbenzyl residue.



   Component (i) is in particular a chlorinated polymer, especially a homopolymer or a copolymer of vinyl chloride, for example a poly (vinyl chloride).



   In formula I, n preferably represents a number from 1 to 5, in particular from 1 to 4, for example from 1 to 3, and is especially equal to 1.



   Preferred compositions according to the invention contain compounds of formula I in which R1, R2, R3 and R4 independently of one another represent a Cg-C alkyl or C7-C9 phenylalkyl radical, or R, and R2 and / or R3 and R4 together represent a CZ-C9 alkylene residue, in particular those in which

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 m is equal to 1 or 2 and R1, R2, R3 and R, independently of one another, represent a C6-CIS alkyl or C7-C9 phenylalkyl radical, or R, and R2 and / or R3 and R, together represent a C2-C9 alkylene residue.



   Preferred R bridges in formula I are those of formula BRI, BR3 and BR4 or of formula BRI, BR2 and BR3, in particular those of formula BRI. In the latter case, R ,, R2, R3 and R, represent in an appropriate manner, independently of each other, a C6-C15 alkyl or phenyl-C7-Cg residue, in particular C-C alkyl.



   In compounds of formula I which are particularly advantageous in
 EMI4.1
 practical, the substituents R ,, R, R; and Rt or R; + R and R + R4 are identical.



  When, in the compounds of formula I, the bridge to the formula Brui, R1, R, Rj and R preferably represent a CC alkyl, phenylalkyl in CyCjj or cycloalkyl in C-Cs, or R, and R and / or R and R together represent a CZ-C9- alkylene residue
In general, particularly advantageous compositions according to the invention contain compounds of formula I in which R ,, R2, R3 and Rt
 EMI4.2
 represent a Cg-C alkyl, C-Cg phenylalkyl or CsC cycloalkyl residue.



   The compounds of formula I are excellent stabilizers for halogenated polymeric materials and are particularly suitable for stabilizing them against the negative influence of heat, oxygen and / or light, in particular UV light. They therefore act as thermal stabilizers, antioxidants and light stabilizers. It is necessary to bring out in particular their action of thermal stabilizers which allows a conventional shaping of said polymers with the least possible damage.



   The compositions according to the invention generally contain, suitably, 0.005 to 10, in particular 0.01 to 10, preferably 0.01 to 5, for example 0.05 to 3, and especially 0.05 to 2% by mass of compounds of formula I relative to the polymer to be stabilized.



   As halogenated, in particular chlorinated, polymeric materials (constituent (i)), there may be mentioned for example: polymers of vinyl chloride, vinyl resins containing in their structure vinyl chloride units, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and dicarboxylic acids

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 unsaturated or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, superchlorinated polymers and copolymers of vinyl chloride,

   copolymers of vinyl chloride and vinylidene chloride with aldehydes, ketones and other unsaturated products, such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; polymers of vinylidene chloride and copolymers thereof with vinyl chloride and other polymerizable compounds; polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and α-substituted acrylic acid; polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated rubbers; chlorinated polymers of ethylene; polymers and superchlorinated polymers of chlorobutadiene and its copolymers with vinyl chloride;

   and mixtures of these polymers with each other or with other polymerizable compounds.



   Other examples are graft polymers of PVC with EVA, ABS and MBS. Preferred substrates are also mixtures of the abovementioned homo-and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic polymers and / or elastomers, in particular mixtures with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.



   As chlorinated polymer, polyvinyl chloride is particularly preferred, in particular in the form of suspension polymer, bulk polymer and emulsion polymer.



   In addition, in the context of this invention, consideration is also given to constituent (i) in particular recycled products of chlorinated polymers, which are the same polymers as those described more precisely above, and which have undergone alteration during shaping, use or storage. Particularly preferred is recycled PVC. Recycled products can also contain small quantities of foreign substances such as, for example, paper, pigments, glues, which are often difficult to remove. These foreign substances can also come from contact with different materials during use or shaping, such as, for example, remains of blowing agents, portions of paint, metallic traces, remains of initiator or else traces of water.



   The compositions according to the invention generally contain other conventional additives, for example, as constituent (iii), lubricants, plasticizers, pigments, non-stick agents, modifying agents,

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 shaping aids, blowing agents, antistatic agents, biocides, anti-stars, dyes, flame retardants, fillers, antioxidants, light stabilizers and / or other shaping stabilizers .



   As additional components (iii), there may be mentioned additives from the groups of organic or inorganic compounds of zinc, alkali metals, alkaline earth metals and / or aluminum, sterically hindered amines, other organic amines, organotin or / and organoantimony compounds, polyols, epoxides, hydrotalcites, zeolites, dawsonites, 1,3diketones, esters of 3-ketocarboxylic acids and / or perchlorates.



   In the following, examples are given of some groups of additives which can be taken into account as constituents (iii), alone or in combination: a) compounds of zinc and other metals
As regards the organic zinc compounds, which preferably contain a Zn-0 bond, these are, for example, zinc enolates, zinc phenolates and / or zinc carboxylates.

   The latter are compounds from the series of aliphatic, saturated or unsaturated C1-C22 carboxylates, aliphatic, saturated or unsaturated C2-C22 carboxylates, substituted by at least one OH group and / or the chain of which is interrupted by one or more several oxygen atoms (oxaacids), cyclic and bicyclic carboxylates of 5 to 22 carbon atoms, unsubstituted phenylcarboxylates, substituted by at least one OH group and / or substituted by C1-C16 alkyl of phenyl (alkyl in Cj-Ct) carboxylates or phenolates optionally substituted by alkyl in CCCI2, or abietic acid.



  The Zn-S compounds are, for example, Zn mercaptides, Zn mercaptocarboxylates and esters of Zn-mercaptocarboxylic acids.



   Special examples of zinc salts of monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enantic acid, octanoic acid, l neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristylic acid, palmitic acid, lauric acid , isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, ricinoleic acid, 3, 6-dioxaheptanoic acid, acid 3 , 6, 9 trioxadecanoic acid, behenic acid, benzoic acid,

   p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid,

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 tolylic acid, dimethylbenzoic acid, ethylbenzoic acid, npropylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid, cinnamic acid, mandelic acid, glycolic acid;

   zinc salts of dicarboxylic acids or their monoesters such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, pentane-1 acid, 5-dicarboxylic acid, hexane-1, 6-dicarboxylic acid, heptane-1, 7-dicarboxylic acid, octane-1, 8-dicarboxylic acid, 3,6,9-trioxadecane-1, 10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, malic acid, salicylic acid, a polyglycoldicarboxylic acid (n = 10.12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid;

   and di- or triesters of tri- or tetracarboxylic acids such as hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid or also so-called superbasic zinc carboxylates or zinc lauryl mercaptide, thioglycolate zinc, zinc thiosalicylate, zinc bis-i-octylthioglycolate, zinc mercaptopropionate, zinc thiolactate, zinc thiomalate, zinc bis-octylmercaptopropionate, zinc bisisooctylthiolactate and zinc bis-laurylthiomalate.



   As regards the zinc enolates, they are preferably enylates of acetylacetone, benzoylacetone, dibenzoylmethane, and enolates of esters of acetoacetic acid or of benzoylacetic acid, as well only dehydracetic acid. In addition, inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate or zinc sulfide can also be used.



   Neutral or basic zinc carboxylates of a carboxylic acid of 1 to 22 carbon atoms (zinc soaps) are preferred, such as, for example, benzoates or alkanoates, preferably C 6 alkanoates, stearate, oleate, laurate, palmitat, behenate, versatate, hydroxystearates and hydroxyoleates, ricinoleate, dihydroxystearates, p-tert-butylbenzoate, or (iso) octanoate. Stearate, oleate, versatate, benzoate, p-tert-butylbenzoate and 2-ethylhexanoate are particularly preferred.



   In addition to the above-mentioned zinc compounds, organic compounds of aluminum, magnesium, calcium, barium, potassium or sodium can also be taken into account, the anionic residues corresponding to the groups indicated for the zinc compounds. Preferred compounds of this type include aluminum, calcium, barium, potassium or magnesium carboxylates such as, for example, basic aluminum monostearate,

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 basic aluminum distearate, aluminum tristearate, calcium stearate, aluminum octoate, aluminum 2-ethylhexanoate, calcium 2-ethylhexanoate, barium 2-ethylhexanoate, 2-ethylhexanoate potassium, aluminum laurate, calcium oleate, barium oleate, calcium t-butylbenzoate, basic aluminum acetates,

   as well as aluminum or magnesium enolates such as, for example, aluminum acetylacetonate, magnesium acetylacetonate, and aluminum or magnesium alkylates, and the corresponding barium compounds. Mention should also be made of the oxides, hydroxides, carbonates and basic carbonates of the abovementioned metals, as well as their mixed salts with organic acids. Examples are NaOH, KOH, CaO, Ca (OH) MgO, Mg (OH) z CaCO3, MgCO3, dolomite, huntite, and fatty acid salts of Na, K, Ca, or Mg.



  In the case of the carboxylates of alkaline earth metals and of Zn, their addition products can also be used with MO or M (OH) 2 (M = Ca, Mg, Ba, Sr or Zn), so-called "superbasic" compounds .



   The metallic compounds described or their mixtures can be used in amounts of, for example, between 0, 0001 and 10, advantageously between 0.001 and 5, preferably between 0.01 and 3, for example between 0.01 and 1 part by mass, for 100 parts by mass of halogenated polymer. They can also be in the form of mixed salts (co-precipitated). b) other phosphites
Examples are trioctyl, tridecyl, tridodecyl, tritridecyl, tripentadecyl, trioleyl, tristearyl, triphenyl, tricresyl, tris-nonylphenyl, tris-2,4-t-butylphenyl or tricyclohexyl phosphites .



   Other suitable phosphites are different mixed aryl and dialkyl or alkyl and diaryl phosphites such as phenyl and dioctyl, phenyl and didecyl, phenyl and didodecyl, phenyl and ditridecyl, phenyl and ditetradecyl, phenyl and dipentadecyl, octyl and diphenyl, decyl and diphenyl, undecyl and diphenyl, dodecyl and diphenyl, tridecyl and diphenyl, tetradecyl and diphenyl, pentadecyl and diphenyl, oleyl and diphenyl, stearyl and diphenyl and dodecyl and bis (2,4-di-t-butylphenyl).



   It is also advantageous to use phosphites of different diols or polyols, for example tetraphenyldipropylene glycol diphosphite, phosphite
 EMI8.1
 polydipropylene glycol-phenyl, tetramethylolcyclohexanoldecyl diphosphite, tetramethylolcyclohexanol-butoxyethoxyethyl diphosphite, tetramethylolcyclohexanol-nonylphenyl diphosphite, bis- diphosphite

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 nonylphenyl-di (trimethylolpropane), bis-2-butoxyethyledi diphosphite (trimethylolpropane), trishydroxyethylisocyanurate-hexadecyl triphosphite, didecylpentaerythritol diphosphite, distearypentpenteryteryphritol diphosphite diphosphite diphosphite ,

   and mixtures of these
 EMI9.1
 phosphites and mixtures of aryl and alkyl phosphites having the statistical composition (HC, -C6H, 0) P (OC3H) or [CgH17-C6H4-O] 2P [i-CgH170] or (HC-CgHOCnH), .



   The organic phosphites can be used in an amount for example between 0.01 and 10, advantageously between 0.05 and 5 and in particular between 0.1 and 3 parts by mass per 100 parts by mass of component (i). c) polyols
As compounds of this type, particular consideration is given to:

   pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bis-trimethylolethane, trimethylolpropane, bis-trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasine, mannitol, xylitol , lactose, leucrose, tris (hydroxyethyl) isocyanurate, palatinitol, tetramethylolcyclohexanol (TMCH), tetramethylolcyclopentanol, tetramethylolcyclopyranol, glycerol, diglycerol, polyglycerol, thiodiglycerol, or dihydrate 1-0 - D-glycopyranosyl-D-mannitol, as well as poly (vinyl alcohol) and cyclodextrins; and condensation products of these polyols with, for example, dipentaerythritol adipate, glycerol oleate, glycerol trioleate, etc.

   TMCH, pentaerythritol, dipentaerythritol, sorbitol and disaccharide alcohols are preferred.



   The polyols can be used in an amount of, for example, between 0.01 and 20, advantageously between 0.1 and 20, and in particular between 0.1 and 10 parts by mass per 100 parts by mass of constituent (i). d) 1, 3-dicarbonylated compounds
Examples of 1,3-dicarbonylated compounds are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthioheptanedione-2,4, benzoylacetone, benzyl acetyl palmitoyl-benzoylmethane, stearoyl-benzoylmethane, isooctanoyl-benzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoylp-chlorobenzoylmethane, hydroxy

   4-methoxybenzoylbenzoylmethane, bis 4-methoxybenzoyl) methane, 1-benzoyl-1-acetylnonane,

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   benzoyl-acetyl-phenyhmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tertbutylbenzoyl) methane, bcnzoyi-fbrmylmethane, benzoyl-phenylacetylmethane, bis (cyclohexanol) methane, di (pival) methyl, ethyl, hexyl, octyl, dodecyl or octadecyl, ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl benzoylacetate, ethyl, propyl stearoylacetate , butyl, hexyl or octyl and dehydracetic acid and its salts of zinc, alkali metals, alkaline earth metals or aluminum.



   The 1,3-dicarbonylated compounds can be used in an amount of, for example, between 0.01 and 10, advantageously between 0.01 and 3 and in particular between 0.01 and 2 parts by mass per 100 parts by mass of constituent ( i). e) thiophosphites and thiophosphates
By thiophosphites and thiophosphates is meant compounds of the general type (RS) 3P, (RS) 3P = O and (RS) 3P = S, as described for example in patent documents DE-A-2809492, EP-A -090770 and EP-A-573394.

   Examples are hexyl trithiophosphite, octyl trithiophosphite, lauryl trithiophosphite, benzyl trithiophosphite, tris [carboxy-ioctyloxy] methyl trithiophosphite, S, S, S-S-tris (i-octyloxycarbon) trithiophosphate ), S, S, S-tris (2-ethylhexyloxycarbonyImethyl) trithiophosphate, S, S, S-tris (1-hexyloxycarbonylethyl) trithiophosphate, S, S, S, S-tris trithiophosphate [1- (2- ethylhexylcarbonyl) ethyl], S, S, S-tris trithiophosphate [2- (2-ethylhexylcarbonyl) ethyl].



   The thiophosphites and thiophosphates can be present in the halogenated polymer in an amount advantageously between 0.01 and 20, preferably between 0.1 and 5, in particular between 0.1 and 1% by mass. f) esters of mercaptocarboxylic acids
Examples of these compounds are: esters of thioglycolic acid, thiomalic acid, mercaptopropionic acid, mercaptobenzoic acids or thiolactic acid, as described in patent documents FR-A-2459816 , EP-A-90748, FR-A-2552440 and EP-A-365483. The mercaptocarboxylic acid esters also include the corresponding polyol esters and their partial esters.



   They can be present in the halogenated polymer in an amount advantageously between 0.01 and 10, preferably between 0.1 and 5, in particular between 0, 1 and 1% by mass. g) epoxides and esters of epoxidized fatty acids:
Mention should be made here above all of fatty acid esters of natural origin such as

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 soybean oil or rapeseed oil.



   The epoxidized compounds are used in amounts for example greater than 0.1 part per 100 parts by mass of composition, advantageously from 0.1 to 30, preferably from 0.5 to 25 parts by mass per 100 parts of constituent (i ). Other examples are epoxidized polybutadiene, epoxidized linseed oil, epoxidized fish oil, epoxidized tallow, methylbutyl or 2-ethylhexyl epoxystearate, tris (epoxypropyl) isocyanurate, l castor oil, epoxidized sunflower oil, 3-phenoxy-1,2-epoxypropane, diglycidyl ether of bisphenol A, vinyl cyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexanecarboxylate 3,4-epoxycyclohexylmethyl.



   It is also possible to take into consideration, as epoxides, derivatives of bisphenol A and bisphenol F as described for example in patent documents US-A-5,492,949, US-A-5,519,077 and US-A-5 543,449. G) dihydropyridines and polydihydropyridines
As monomeric dihydropyridines, one can take into account compounds such as those described in patent documents FR-A-2039496, EP-A-2007, EP-A-362012, EP-A-24754 and EP-A-716123. We prefer those of formula
 EMI11.1
 in which Z is C02CH3, COHs, CO2nCH, or-C02C2H4-S-nCl2H2.



   As polydihydropyridines, we especially take into account the compounds of general formula
 EMI11.2
 in which T represents an unsubstituted C1-C12 alkyl residue, L has the same meaning as T, m and n are numbers from 0 to 20,

  <Desc / Clms Page number 12>

   k is equal to 0 or 1, R and R're independently of one another represent an ethylene, propylene, butylene or an alkylene- or cycloalkylenebismethylene group of the type - (CpH2p-X-) tCpHp-, p is a number from 2 to 8, t is a number from 0 to 10, and X is oxygen or sulfur.



   Such compounds are described in more detail in patent document EP-A-286887. The (poly) dihydropyridines can be used in the halogenated polymer in an amount advantageously between 0.001 and 5 and in particular between 0.005 and 1 part by mass per 100 parts of polymer.



   Thiodiethylene bis (5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3carboxylate) and 1,4-dihydro-2,6-dimethyl-3,5-dicarbododecyloxypyridine are particularly preferred. h) perchlorates
Examples are those of formula M (CI04) n in which M is Li, Na, K, Mg, Ca, Ba, Zn, Al, Ce or La. The index n is, according to the valence of M, equal to 1 , 2 or 3. Perchlorates can be complexed with alcohols or ether-alcohols. The different perchlorates can also be used in different common preparation forms, for example in the form of a salt or an aqueous solution of a salt or of the free acid fixed on a support such as PVC, calcium silicate, a zeolite or a hydrotalcite, or obtain them by chemical reaction of a hydrotalcite with perchloric acid.



   Perchlorates can be used in an amount of, for example, between 0.001 and 5, advantageously between 0.01 and 3, particularly preferably between 0.01 and 2 parts by mass per 100 parts by mass of component (i). i) hydrotalcites and zeolites
The chemical composition of these compounds is known to those skilled in the art, for example from patent documents DE-A-3843581, US-A-4000100, EP-A-062813, WO-A-93 / 20135.



   The compounds of the hydrotalcite series can be described by the general formula III,
 EMI12.1
 in which M2 + represents one or more metals from the group consisting of Mg, Ca, Sr, Zn and Sn, M3 + is Al or B,

  <Desc / Clms Page number 13>

 An represents an anion of valence n, n is equal to 1 or 2, 0 <x # 0.5, m is a number from 0 to 20.



   Preferably, An represents OH-, ClO4-, HCO3-, CH3COO-, C6H5COO-,
 EMI13.1
 CO, ', SO,', HSO, -, - COO-COO, (CHOHCOO), ', (CH. COO), CH. CHOHCOO-, HPO- or HPO-.



   Hydrotalcites containing LiOH or Li2CO3 inclusions ("solid solutions") can also be used;
Examples of hydrotalcites are Al203. 6MgO.Co2.12H2O; Mg4.5Al2 (OH) 13.CO3. 3.5H, 0; 4MgO. Al, 03. CO2. 9:20 AM; 4MgO. Al2O3.CO2.6H2O; ZnO. 3MgO. Alz03. COz. 8-9HzO; and ZnO. 3MgO. Al2O3.CO2.5-6-H2O.



   The compounds of the zeolite series (alkali or alkaline earth metal aluminosilicates) can be represented by the general formula (IV)
 EMI13.2
 in which n is the charge of the cation M; M is an element of the first or second main group, like Li, Na, K,
Mg, Ca, Sr or Ba, or is Zn, y: x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to 30.



   For example, structures can be found in the Atlas of Zeolite by W. M.



  Meier and D. H. Olson, Butterworth-Heinemann, 3rd edition 1992.



   Examples of zeolites are sodium aluminosilicates having the formulas
 EMI13.3
 Na12AI12Si1204s'27 H20 [zeolite A], Na6A16Si6024'2 NaX. 7.5 H2O, X = OH, halogen, CI04 [sodalite]; NagAIsSiOHO; NasAljjSiOHO; Na16Al16Si240S0'16 H2O; NaI6AlI6Si32096'16 H2O; N8. s6Als6Si13603s4. 250 H2O [zeolite Y]; Nag6AIs6Si10603s4. 264 H2O [zeolite X]; and X and Y zeolites having an Al / Si ratio of 1/1; or the zeolites obtainable by exchange of all or part of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na, K) 10Al10Si22O64.20 H2O; CaNa, [(A102) 12 (SiO2]. 30 H2O; K9Na3 [(AlO2) 12 (SiO2) 12.27 H2O.



   Other suitable zeolites are:

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 Na, Ale03. (2 to 5) SiO ,. (3.5 to 10) HO [zeolite P] Na, A Al, 03. 2 SiO2. (3.5 to 10) H, 0 [zeolite MAP] or the zeolites obtainable by exchange of all or part of the
 EMI14.1
 Na atoms by Li, K or H atoms, such as (Li, Na, K, H). Si. 20 H, 0; K <, Na, [(A10,) ,, (SiO]. 27 H, 0; K4AlO. 6 H2O [zeolite KF], NasAl. Si4O6. 24 H0 [zeolite D], as described by Barrer et al.,. / Chem. Soc. 1952, 1561-71, and in US Patent 2,950,952.



   The following zeolites can also be taken into consideration: Koffrétite, described in patent document EP-A-400 961; zeolite R, described in patent document GB-A-841812; zeolite LZ-217, described in US-A-4,503,023; zeolite LZ-218 without calcium, described in patent document US-A-4,333,869; zeolite T, zeolite LZ-220, described in patent document US-A-4,503,023;

   Na3K6Al9Si27O72.21 H2O [zeolite L]; zeolite LZ-211, described in patent document US-A-4,503,023; zeolite LZ-212, described in patent document US-A-4,503,023; zeolite 0, zeolite LZ-217, described in patent document US-A-4,503,023; zeolite LZ-219, described in patent document US-A-4,503,023; zeolite Rho, zeolite LZ-214, described in patent document US-A-4,503,023; zeolite ZK-19, described in Am. Mineral. 54,1607 (1969); zeolite W (K-M), described by Barrer et al. J. Chem. Soc. 1956, 2882; NaoAlSiO. 98 H2O [zeolite ZK-5, zeolite Q]; and AlPO4 compounds having a zeolite structure.



   Particularly preferred are the types of zeolite P of formula i
 EMI14.2
 in which x is a number from 2 to 5 and y is a number from 3.5 to 10, and M is an alkali metal atom, and more particularly the zeolite MAP of formula IVa in which x is equal to 2 and y is a number of 3.5 to 10. These are in particular Na-P zeolites, that is to say that M is Na. This zeolite is generally found in the form of the Na-P-1, Na-P-2 and Na-P-3 variants, which are distinguished by their cubic, tetragonal or orthorhombic structure (R. M. Barrer, B. M. Munday, J. Chem. Soc.



    A 1971,2909-14). In the literature which has just been cited, the preparation of the zeolites P-1 and P-2 is also described. Zeolite P-3 is, according to this literature, fairly
 EMI14.3
 rare and therefore of little practical interest. The structure of zeolite P-1 corresponds to the structure of gismondite known from the Atlas of Zeolite Structures cited above. In recent literature (patent document EP-A-384,070), a distinction is made between cubic P type zeolites (zeolite B or Pc) and tetragonal zeolites (zeolite P1). We quote

  <Desc / Clms Page number 15>

 also more recent type P zeolites with Si: Al ratios lower than 1.07: 1. In this case they are zeolites called MAP or MA-P for "Maximum Aluminum P".

   Depending on the preparation process, zeolite P may contain small amounts of other zeolites. A very pure zeolite P has been described in patent document WO-A-94/26662.



   Within the framework of the invention, it is also possible to use sodium aluminosilicates in the finely divided state, insoluble in water, which have been precipitated and crystallized in the presence of inorganic or organic dispersing agents soluble in water. They can be incorporated into the reaction mixture either before or after precipitation or crystallization.



   Zeolite Na-A, zeolite Na-P, zeolite Na-X and zeolite Na-Y are preferred.



   Hydrotalcites and zeolites can be natural mineral products or compounds prepared by synthesis.



   Hydrotalcites and / or zeolites can be used in amounts of, for example, between 0.1 and 50, advantageously between 0.1 and 10 and in particular between 0.1 and 5 parts by mass per 100 parts by mass of halogenated polymer. . j) alkali metal aluminocarbonates (dawsonites)
These compounds can be represented by the formula V
 EMI15.1
 
 EMI15.2
 in which M is H, Li, Na, K, Mg1 / 2, Ca,, Sr or Zn,; Z is CO2, SO2, (CI207) zu BO, SO (thiosulfate), or C202 (oxalate); when M is Mgou Ca, m is a number between 1 and 2, and, in other cases, m is a number between 1 and 3; n is a number between 1 and 4; o is a number between 2 and 4; and p is a number between 0 and 30.



   The aluminosal compounds of formula (V) which can be used can be natural mineral products or compounds prepared by synthesis. Metals can be partially exchanged with each other. The aluminosal compounds mentioned are crystalline, partially crystalline or amorphous, or may be in the form of dried gels. The aluminosal compounds can also exist in the form of rare crystalline modifications. A process for the preparation of such compounds is described in patent document EP 394670. Examples of natural aluminosal compounds are indigirite, tunisite, alumohydrocalcite, para-

  <Desc / Clms Page number 16>

 alumohydrocalcite, strontiodressérite and hydrosrontiodérérite. Other examples of aluminosal compounds are
 EMI16.1
 potassium aluminocarbonate {(K20).

   (Al203). (C02) 2. 2H2O}, sodium aluminothiosulfate {(Na2O). (Al203). (S202) 2. 2H2O}, potassium aluminosulfite {(KOnAOSOHO}, calcium aluminum oxalate {(CaOAO. O. SHO}, magnesium aluminotetraborate {(MgO).)!!}, { ([MgNaO). (Al, 03). (CO2) 2. 4, 1H, 0}, {([M &, 2Nao, 6J20). (Al203). (C02) 2. 4, 3H2O}, and { ([Mg .. 3Nao 4, 0). (Al, 03). (CO2) 2, 2. 4, 9H20}.



   The compounds of mixed aluminosalts can be obtained by methods known per se by cation exchange, preferably from the compounds of aluminosalts of alkali metals or by combined precipitation (see for example patent document US Pat. No. 5,055,284).



   The aluminosal compounds of the above formula are preferred in
 EMI16.2
 which M is Na or K; Z is CO, SO or (ClOy),; m is a number from 1 to 3, n is a number from 1 to 4; o is a number from 2 to 4 and p is a number from 0 to 20. Z is particularly preferably CO.



   Furthermore, the compounds which can be represented by the following formulas are preferred: M2O. Al203. (COJ2. PH2O (la), (M20) 2. (Al203) 2. (CO2) 2. pH, 0 (Ib), M20. (Al203) 2. (CO. PH20 (lc),
 EMI16.3
 where M is a metal like Na, K, Mg,, Ca, Sr, or Zn,, and p is a number from 0 to 12.



   Sodium aluminodihydroxycarbonate (DASC) and the homologous potassium compound (DAPC) are particularly preferred.



   Instead of the dawsonites, it is also possible to use silicates having ion exchange properties such as, for example, bentonites, magadiite, haremite.



   The dawsonites can be used in an amount of, for example, between 0.01 and 50, advantageously between 0.1 and 10, particularly preferably between 0.1 and 5 parts by mass per 100 parts by mass of halogenated polymer. k) antioxidants
As antioxidants, we take for example:

   1. alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-

  <Desc / Clms Page number 17>

 butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-nbutylphenol, 2, 6-di-tert-butyl-4 -isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4methylphenol, 2,4,6-tricyclohexylphenol, 2, 6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundéc-l'-yl) phenol, 2, 4-dimethyl-6- (l'-methylheptadéc-l'-yl) phenol, 2,4-dimethyl-6- (l'-methyltridéc-l'-yl) phenol and their mixtures.



  2. alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-tertbutylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.



  3. hydroquinones and alkylated hydroquinones. for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-ditert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5di-tert-butyl- stearate 4-hydroxyphenyl, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.



  4. tocopherols, for example a-tocopherol, ss-tocopherol, y-tocopherol, c-tocopherol and their mixtures (vitamin E).



  5. hydroxyl thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4methylphenol), 2, 2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert- butyl-3methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-secamylphenol), disulfide of 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl).



  6. alkylidenebisphenols. for example 2,2'-methylenebis (6-tert-butyl-4methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl- 6- (a-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'methyleneenebis (4, 6-di-tert-butylphenol), 2,2'-ethylidenebis (4, 6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2,2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4- nonylphenol], 4,4'- methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6tert-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 (5tert-butyl-4-hydroxy-2-methylphenyl) butane, 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmcrcaptobutane, bis [ 3, 3-bis (3'-tert-butyl-4'-hydroxyphenyl) ethylene glycol butyrate, bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2 (terephthalate) 3'-tert-butyl-2'-hydroxy-5'-methyl-
 EMI17.1
 benzyl) -6-tert-butyl-4-methylphenyl], 1, 1-bis (3, 5-dimethyl-2-hydroxyphenyl) -

  <Desc / Clms Page number 18>

 butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl- 4-hydroxy-2-methylphenyl)

  -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.



  7. O-, N- and S-benzylated compounds, for example the oxide of 3,5, 3 ', 5'-tetra-tertbutyl-4,4'-dihydroxydibenzyle, 4-hydroxy-3,5- octadecyl dimethylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis sulfide (3,5-di-tert-butyl-4hydroxybenzyle), isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.



  8. hydroxybenzylated malonates, for example 2,2-bis (3,5-di-tert-butyl-2hydroxybenzyl) dioctadecyl malonate, 2- (3-tert-butyl-4-hydroxy-5-methyl-benzyl ) dioctadecyl malonate, 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) didodecylmercaptoethyl malonate, 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl ) di [4- (I, I, 3,3-tetramethylbutyl) phenyl malonate].



  9. hydroxybenzylated aromatic compounds. for example 1, 3, 5-tris (3,5-di-tertbutyl-4-hydroxybenzyl) -2, 4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4hydroxybenzyl ) -2, 3,5, 6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.
 EMI18.1
 



  10. triaziniq compounds. ues, for example 2, 4-bis (octylmercapto) -6- (3, 5-di-tertbutyl-4-hydroxyanilino) -1, 3, 5-triazine, 2-octylmercapto-4, 6-bis (3 , 5-di-tert-butyl-4-hydroxyanilino) -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, 1,3,5tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3, 5 -di-tert-butyl-4-hydroxyphenylethyl) -1, 3, 5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1, 3, 5 -triazine, 1, 3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.



  11. benzylphosphonates. for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate dioctadecyl, dioctadecyl 5tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.



  12. acylaminophenols, for example 4-hydroxyanilide of lauric acid, 4hydroxyanilide of stearic acid, N- (3,5-di-tert-butyl-4-hydroxyphenyl) - octyl carbamate.



  13. esters of ss- (3. 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono or polyalcohols, for example with methanol, ethanol, octanol,

  <Desc / Clms Page number 19>

 octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, Nbis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6,7trioxabicyclo [2. 2.2] octane.



  14. esters of p-f5-tert-butyl-4-hydroxv-3-methylphenvnpropionic acid with mono or polyalcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-
 EMI19.1
 bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7trioxabicyclo [2. 2.2] octane.



  15. esters of p-f3 acid. 5-dicyclohexvl-4-hvdroxyphenynpropiomque with mono- or polyalcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol , 1,2propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol,
 EMI19.2
 trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7trioxabicyclo [2. 2.2] octane.



  16. esters of 3,5-di-tert-butyl-4-hydrohenylacetic acid with mono or polyalcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6- hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis ( hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2.2] octane.



  17. p- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amides, for example 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-hydroxyphenylpropionyl ) hydrazine.



   One can also optionally use a mixture of antioxidants of different structures.



   Antioxidants can be used in an amount for example

  <Desc / Clms Page number 20>

 between 0.01 and 10, advantageously between 0.05 and 5 and in particular between 0.05 and 3 parts by mass per 100 parts by mass of halogenated polymer.



  1) UV absorbers and other light stabilizers
Examples are: 1. 2- (2'-hydroxyphenen benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl -2'-hydroxyphenyl) benzotriazole,
 EMI20.1
 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'- (1, 1, 3, 3tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'- sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'- hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di -tert-amyl- 2'-hydroxyphenyl) - benzotriazole, 2- (3 ', 5'-bis (a, a-dimethylbenzyl)

   -2 '-hydroxyphenyl) benzotriazole, a mixture of 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) -5chlorobenzotriazole, of 2- (3'-tert-butyl- 5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'- hydroxyphenyl) -5-chlorobenzotriazole, from 2- (3'-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2- methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2- octyloxycarbonylethyl) phenyl) benzotriazole, of 2- (3'-tert-butyl-5'- [2- (2-ethylhexyl-
 EMI20.2
 oxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3 '-dodecyl-2'-hydroxy-5'methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5' - (2-isooctyloxycarbonylethyl) phenyl) benzotriazole, 2,

   2'-methylenebis [4- (1, 1, 3, 3-tetramethylbutyl) -6- (benzotriazole-2-yl) phenol]; the trans-esterification product of 2- [3'-tertbutyl-5'- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300; [RCH2CH2COO (CH2) - with R = 3'-tert-butyl-4'-hydroxy-5'- (2H-benzotriazole-2-yl) phenyl.
 EMI20.3
 



  2. 2-hydroxybenzophenones, for example 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy- derivatives 4,4'-dimethoxy.



  3. esters of optionally substituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylrésorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylrésorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di- octadecyl tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.



  4. acrylates, for example α-cyano-ss, ethyl or isooctyl p-diphenylacrylate,

  <Desc / Clms Page number 21>

 methyl a-carbomethoxycinnamate, methyl or butyl a-cyano-p-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate, N- (ss-carbomethoxy-p-cyanovinyl ) -2-methylindoline.



  5. nickel compounds, for example complexes of nickel with 2,2'thiobis [4- (1,1, 3,3-tetramethylbutyl) phenol], such as the 1: 1 complex or the 1: 2 complex, with optional additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, dibutylnickel dithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-ditert-butylbenzylphosphonic acid, such as methyl or ethyl esters, nickel complexes with ketoximes such as 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes with 1-phenyl-4-lauroyl-5-hydroxypyrazole, possibly with other ligands.



  6. diamides of oxalic acid, for example 4, 4'-dioctyloxyoxanilide, 2,2'diethoxyoxanilide, 2,2'-dioctyloxy-5, 5'-di-tert-butyloxanilide, 2,2 '-didodecyloxy- 5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl- 2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, mixtures of oxanilides disubstituted by methoxy at o and p, and by ethoxy at o and p.



  7. 2- (2-hydroxyphenyl) -1. 3. 5-triazines, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6 -bis (2,4dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4 , 6-bis (4-methylphenyl) - 1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) - 1,3,5 triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propyloxy) phenyl] -4,6bis (2,

     4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) - 1, 3,5-triazine.



  8. sterically hindered amines, which are generally compounds of the series of alkyl- or polyalkylpiperidines containing at least one group 2,2, 6,6tetramethylpiperidine or 1,2, 2,6, 6-pentamethylpiperidine and / or a group AYN in which A and Y represent, independently of each other, a C 1 -C 6 alkyl radical, C 3 -C 6 alkenyl, Cs-C cycloalkyl or Cy-Cg phenylalkyl, or together form a CC alkylene residue possibly interrupted by 0, NH or CH3-N. Sterically hindered amines are, for example, N, N'-diacetylN, N'-bis [2, 2, 6, 6-tetramethylpiperidine-4-yl] ethylenediamine;

   N, N'-bis [2,2,6,6tetramethylpiperidine-4-yl] oxamide; N, N'-bis [2, 2,6, 6-tetramethylpiperidine-4-yl] -

  <Desc / Clms Page number 22>

 phthalamide; N, N'-bis [2,2,6,6-tetramethylpiperidine-4-yl] benzene-1,3-dicarboxamide; N, N'-bis [2,2,6,6-ttramethylpiperidine-4-yl] adipamide; N, Ndiacetyl-N, N'-bis [2,2,6,6-tetramethylpiperidine-4-yl] propylene-1,3-diamine; N, Ndiformyl-N, N'-bis [2,2,6,6-tetramethylpiperidine-4-yl] hexylene-1,6-diamine; N, N-diacetyl-N, N'-bis [2,2,6,6-tetramethylpiperidine-4-yl) hexylene-1,6-diamine; the adipate
 EMI22.1
 bis 4-hydroxy-2, 2, 6, 6-tetramethylpiperidinyl];

   poly (4'-tert-octylamino-2 ', 6'N, N'-bis [2, 2, 6, 6-tetramethylpiperidine-4-yl] hexamethylene-1, 6-diamino [1, 3, 5] triazine); poly (4'-morpholino-2 ', 6'-N, N'-bis [2, 2, 6, 6-tetramethylpiperidine-4-yl] hexamethylene-1, 6-diamino 3, 5] triazine); poly (4'-cyclohexylamino-2'-N, N'bis [2, 2, 6, 6-tetramethylpiperidme-4-y!] hexamethylene-1,6-diammo [1,3,5] triazine); poly (4'-piperidinyl-2 ', 6'-N, N'-bis- [2, 2, 6, 6-tetramethylpiperidine-4-yl] hexamethylene- 1, 6-diamino- [1, 3, 5 ] triazine); tris (2-hydroxy-3-N- [2, 2, 6, 6-tetramethylpiperidine-4yl] aminopropyl) isocyanurate; lcN, N ', N ", N'" - tetrakis (2 ', 4'-bis [1, 2, 2, 6, 6-pentamethylpiperidine-4-yl-butylamino] -1, 3, 5-tnazmyl) - l ", 2" -bis- [3 '"- methylammopropylamino] ethane; tris [2'-di-i-propylamino-ethylamino] - [1, 3, 5] triazine;

   N, N'-bis [2'di-i-propylaminoethyl] adipamide; tris [2, 2,6, 6-tetramethylpiperidine-4-yl-amino] - [1, 3, 5] triazine; tris [3'-diethylamino-propylamino] - [1, 3, 5] triazine; 2 '- [2,2,6,6tetramethylpiperidine-4-yl-amino] -4', 6'-diamino [1, 3, 5] triazine; 2 ', 4'-bis- [2, 2,6, 6-tetramethylpipenedin-4-yl-ammo] -6'-diethylammo [1,3,5] tnazine; the 2 ', 4'-bis- [2, 2,6,
 EMI22.2
 6-tetramethylpiperidine-4-yl-amino] -6'-morpholino [1, 3, 5] triazine; poly (N, N *, N ', N' "- tetrakis [2, 2, 6, 6-tetramethylpiperidine-4-yl] acetyl-hexamethylenediamino-acetyl-hexamethylenediamine).



   The concentration of UV absorbers and light stabilizers in the compositions according to the invention is preferably within the same range as that indicated above for the antioxidants. m) plasticizers
As organic plasticizers, consideration is given, for example, to those of the following groups:

   A) esters of phthalic acid:
Examples of such plasticizers are dimethyl, diethyl, dibutyl, dihexyl, di (2-ethylhexyl), di-n-octyl, diisooctyl, di-isononyl, di-isononyl, di-isodecyl phthalates -isotridecyl, dicyclohexyl, di (methylcyclohexyl), dimethylglycol, dibutylglycol, benzylbutyl and diphenyl and mixtures of phthalates such as C7-C9 and C9-CII alkyl phthalates obtained essentially from alcohols linear, C-C8 n-alkyl phthalates, o and Cs-Cjo n-alkyl phthalates.

   Among these, we prefer

  <Desc / Clms Page number 23>

 dibutyl, dihexyl, di (2-ethylhexyl), di-n-octyl, diisooctyl, di-isononyl, di-isodecyl, di-isotridecyl and benzyl and butyl phthalates, as well as mixtures of above-mentioned alkyl phthalates. Di (2-ethylhexyl), di-isononyl and di-isodecyl phthalates, also known under the usual abbreviations DOP (dioctyl phthalate, di- (2-ethylhexyl) phthalate), DINP (di-isononyl phthalate ), DIDP (di-isodecyl phthalate), are particularly preferred.



  B) esters of aliphatic dicarboxylic acids, in particular esters of adipic acid, azelaic acid and sebacic acid.



   Examples of such plasticizers are di (2-ethylhexyl) adipate, di-isooctyl adipate (mixture), di-isononyl adipate (mixture), di-isodecyl adipate (mixture), benzyl and butyl adipate, benzyl and octyl adipate, di (2-ethylhexyl) azelate, di (2-ethylhexyl) sebacate and diisodecyl sebacate (mixture). Di (2-ethylhexyl) adipate and diisooctyl adipate are preferred.



  C) esters of trimellitic acid, for example tri (2-ethylhexyl) trimellitate, tri-isodecyl trimellitate (mixture), tri-isotridecyl trimellitate, tri-isooctyl trimellitate (mixture) and C6-Cg trialkyl, Cg-Cto trialkyl, C7-C9 trialkyl and C9-Cl1 trialkyl trimellitates. These latter trimellitates are formed by esterification of trimellitic acid with the corresponding alkanol mixtures. The preferred trimellitates are the tri (2-ethylhexyl) trimellitate and the trimellitates obtained from the mixtures of alkanols indicated.



  Common abbreviations are TOTM (trioctyl trimellitate, tri (2-ethylhexyl) trimellitate), TIDTM (triisodecyl trimellitate) and TITDTM (triisotridecyl trimellitate).



  D) epoxy plasticizers
They are essentially epoxidized unsaturated fatty acids such as, for example, epoxidized soybean oil.



  E) polymeric plasticizers
The raw materials most used for the preparation of polymeric plasticizers are: dicarboxylic acids such as adipic acid, phthalic acid, azelaic acid and sebacic acid; diols such as 1,2propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol and diethylene glycol.



  F) esters of phosphoric acid
Examples of such phosphoric acid esters are tributyl phosphate, tri (2-ethylbutyl) phosphate, tri (2-ethylhexyl) phosphate,

  <Desc / Clms Page number 24>

 trichloroethyl phosphate, 2-ethylhexyl and diphenyl phosphate, cresyl and diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Preference is given to tri (2-ethylhexyl) phosphate and Reofos 50 and 95 (eg firm FMC).



  G) chlorinated hydrocarbons (paraffins) H) hydrocarbons
 EMI24.1
 I) monoesters, for example butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and esters of alkylsulfonic acids.



  J) glycolic esters. for example diglycol benzoates.



   Definitions and examples of plasticizers from groups A) to J) can be found in the following textbooks: Taschenbuch der Kunsstoffadditive, published by R. Gächter and H. Müller, Editions Carl Hanser, 1989, chapter 5, pages 341-442.



  PVC Technology, published by W. V. Titow, 4th edition, Elsevier Publishers, 1984, chapter 6, pages 147-180.



   It is also possible to use mixtures of different plasticizers.



   The plasticizers can be used in an amount of, for example, between 5 and 120, advantageously between 10 and 100 parts by mass per 100 parts by mass of PVC. n) lubricants
For example, lignite wax, fatty acid esters, PE waxes, amide waxes, chloroparaffins, glycerol esters, solid or liquid paraffinic waxes or alkali metal soap are taken into consideration. earthy, or silicone-based lubricants as described in patent document EP-A-225261. Usable lubricants are also described in Taschenbuch der Kunsstoffadditive, published by R. Gächter and H. Müller, Editions Carl Hanser, 3rd edition, 1989, pages 478-488.

   Lubricants can also be mixed with stabilizers before addition to the polymeric material. o) charges
Fillers (Handbook of PVC-Formulating by EJ Wickson, John Wiley & Sons, New York 1993, pages 393-449) and reinforcing agents (Taschenbuch der Kunsstoffadditive, published by R. Gächter and H. Müller, Editions Carl Hanser, 3rd edition, 1989, pages 549-615) can be for example: calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, glass fibers, talc, kaolin, chalk, mica, metal oxides and hydroxides, carbon black or

  <Desc / Clms Page number 25>

 graphite. We prefer chalk. p) pigments
Suitable products are known to those skilled in the art.

   Examples
 EMI25.1
 of inorganic pigments are TiO2, carbon black, FeO, SbO, (Ti, Ba, Sb) dz CrO, spinels like cobalt blue and cobalt green, Cd (S, Se), overseas blue . TiO2 is also preferred, also in micronized form. Organic pigments are for example azo pigments, phthalocyanine type pigments, quinacridone type pigments, perylene type pigments, pyrrolopyrrolidone type pigments and anthraquinone type pigments. More details can be found in Handbook of PVC-Formulating by E. J.

   Wickson, John Wiley & Sons, New York 1993, pages 449-474. q) organotin compounds
For the organotin compounds, these are for example organotin oxides, organotin sulfides, organotin carboxylates, organotin mercaptocarboxylates, organotin mercaptides and / or esters of organotin mercaptocarboxylic acids such as, for example, dibutyltin oxide, dioctyltin maleate, the hemiester of maleic acid with dibutyltin, bis-dibutyltin oxide and 2-ethylhexanoate and other compounds SnO such as those described for example in patent document EP-A-573394.



   As organotin mercaptides, account is taken, for example, of compounds of general formula RSn (SA) 4-n in which the residue R represents inter alia a methyl, butyl, octyl, lauryl or butoxycarbonylethyl group, n takes the value 1 or 2 and the residue A is, for example, a decyl, dodecyl, alkoxycarbonylmethyl or alkoxycarbonylethyl residue, the alkoxy residue representing a linear or branched C 1 -C 6 alkoxy residue or CC cycloalkoxy. Examples of such tin compounds are dimethyltin bis-i-octyloxycarbonylmethylmercaptide, dibutyltin dilaurylmercaptide, dioctyltin bis-2-ethylhexyloxycarbonylmethylmercaptide, dimethyltin bismercaptoethylstearmethyltetoxycarbetetramethyltetoxycarbethyltetoxycarbetetoxycarbetoxycarbetyltetoxycarbetetoxycarbetetoxycarbetetoxycarbetyltetoxycarbetetoxycarbetetoxycarbetetoxycarbetetoxycarbetetoxycarbetetoxycarbetetriethyltetraethylcetriethyltetra-carbetetoxycarbetetoxycarbetetoxycarbetetoxycarbonate

   the sulfide of the monomethyltin mercaptoethyloleate and the sulfide of the dimethyltin bis-mercaptoethylstearate. r) organic nitrogen compounds
Suitable organic nitrogen compounds are, for example, ureas and thioureas, aminobenzenesulfonates, esters of aminobenzoic acids, aminobenzamides, cyanamides, dicyandiamide, guanidines,

  <Desc / Clms Page number 26>

 guanamines, melamines, indoles, aminocrotonates, tetrazoles, triazoles, substituted aminotriazoles, m-aminophenols, aminouracils, pyrroles, aminopyrroles, such as, among others, the compounds described for example
 EMI26.1
 in patent documents DE-A-746 081, US-A-2 557 474, DD-A-652, DE-A- 871 834, EP-A-174 412, DE-A-1 162 073, US- A-2 367 483, GB-A-923 319, DE-A- 863 512, DE-A-2 524 659, DE-A-1 544 768,

   DE-A-1 134 197, EP-A-2 756, DE-A- 3048659, DE-A-3 602367, EP-A-48222, EP-A-41479, EP-A-65934, EP-A- 22,087, EP-A-465,405 and EP-A-390,739.



   Preferred compositions according to the invention contain as additional constituents (iii) a zinc compound of formula ZnRR in which R; and R are identical or different and represent a residue (C 1 -C alkyl) -COO, phenyl-COO, phenyl-COO substituted by C 1 -C alkyl, (cycloalkyl
 EMI26.2
 Cs-Cs) -COO, OH, Cl, (C 1 -C 22 alkyl) -0-C (0) - (CH2) p-S- or Fty-C-CH = C-R ,, or il 1
0 0 together form 0, S or C03, R7 and Rs represent a hydrocarbon residue and p is a number from 1 to 3; and / or a sterically hindered amine containing one or more 2,2, 6,6-tetramethylpiperidine groups; and / or an organotin compound from the series of organotin sulfides, mercaptides or mercaptocarboxylates;

   and / or an organic nitrogen compound from the series of esters of 3-aminocrotonic acid, of 2phenylindoles, of pyrroles or of aminouracils.



   Another object of the present invention is the use of phosphites of formula I for the stabilization of a halogenated polymeric material, in particular of poly (vinyl chloride), and a method of stabilization of a halogenated polymeric material, characterized in that at least one compound of formula I is incorporated therein



   The compounds of formula I and optionally other additives can be added to the polymer by a known process by mixing said compounds and possibly other additives with the halogenated polymer by means of known devices such as mixers, calenders, kneaders, extruders, crushers and the like. In this case, they can be added alone or as a mixture, or even in the form of a so-called master mixture. The polymer compositions of the present invention can be brought into the desired form by known methods. These processes are, for example, rolling, extrusion, injection molding, sintering or spinning, or even blow molding or transformation according to the plastisol process. The compositions can also be transformed into foams.



   The compositions according to the invention are suitable for example for semi-rigid and flexible formulations such as, for example for formulations

  <Desc / Clms Page number 27>

 flexible, for covering with wires, insulation of cables, floor coverings, pipes and sealing profiles. In the form of semi-rigid formulations, the polymer compositions according to the invention are suitable for decorative sheets, foams, sheets for agriculture, pipes, sealing profiles, office sheets, profiles. and extruded panels, sheets and panels for floors, coated fabrics and artificial leathers, as well as sheets for crash cushions (for use in the automotive field).

   In the form of rigid formulations, the compositions according to the invention are suitable for hollow bodies (bottles), packaging sheets, stamping sheets, bubble sheets, sheets for collision cushions (automotive), tubes. , foams, heavy profiles (window frames), wall profiles with openings, construction profiles, fittings, fittings and carcasses of devices (computers, household appliances), as well as other molded articles by injection. Examples of uses of the stabilized compositions according to the invention as plastisols are artificial leathers, coated fabrics, floor coverings, textile coverings, carpets, strip covers, sheets for collision cushions and protection pads. underbody for automobiles.



   Examples of sintering uses of the stabilized polymer compositions according to the invention are molding in hollow molds or coating on a strip.



   The compounds of formula 1 are known, for example from some of the publications indicated at the beginning, or they can be prepared by analogy to the methods which are described in these publications or in Houben-Weyl, Methoden der Organischen Chemie, volume XII / 2 , pages 53-62 and 73-78, Editions G. Thieme, Stuttgart, 1964. This preparation is carried out for example by reaction of phosphorus trichloride with a diol of formula HO-R-OH and an alcohol or a mixture of alcohols of formula R, OH, ROH, ROH and / or ROH, preferably in non-polar solvents and in the presence of bases, in particular tertiary amines, as acceptors of HCl.



   The preparation of compounds of formula 1 is carried out in a particularly suitable manner by reaction of a triaryl phosphite, for example triphenyl phosphite or tris-nonylphenyl phosphite, with a diol of formula HO-R-OH and an alcohol or a mixture of alcohols of formula R, OH, ROH, R30H and / or R4OH. It is then advantageously worked in the presence of a trans-esterification catalyst, for example of a base such as a hydroxide or an alkylate of

  <Desc / Clms Page number 28>

 alkali metal, for example Na methylate. In both methods, the molar ratio of phosphorus trichloride or triaryl phosphite: diol: alcohol is about 2: 1: 4, with slight excess of either component being possible.



   To prepare compounds of formula I in which R, and R2 and / or R3
 EMI28.1
 and R4 together form an alkylene residue, it may also be advantageous to react
 EMI28.2
 R - 0 0-H, a cyclic compound of formula, P-Hal and / or Hal-P (Hal represents F-0 0-F
 EMI28.3
 a halogen atom, in particular chlorine), for example a chlorophosphorinane
 EMI28.4
 C) optionally alkylated of formula P-C), with a diol of formula HO-R-OH. the
 EMI28.5
 In this reaction, it is advantageous to use a base as an acceptor of hydrogen chloride, for example a tertiary amine. It is preferably carried out in the presence of a solvent, for example toluene, heptane or tetrahydrofuran.



   To prepare compounds of formula I in which n> 1, the transesterification process described above is used and the molar ratio of the triaryl phosphite constituents, HO-R-OH and R1OH, R2OH, R3OH, is correspondingly adapted, R4OH.



   In the course of preparation, mixtures of phosphites of formula I are often formed naturally, which can be separated, if necessary, by conventional physical separation methods such as, for example, chromatography, recrystallization, and so on. after. However, such mixtures can also be incorporated directly into the compositions according to the invention.



   Further details on the preparation of compounds of formula I can be found in the preparation examples given below.



   The present invention also relates to new compounds of formula 1 in which R is a bridge of formula BR3, BR4 or BR6 and the other generic symbols have the definition given for formula I.



   In this case, the compounds of formula I are preferred in which R ,, R2, R3 and R4 or R, + R2 and R3 + R4 are identical.



   In these new compounds, n is in particular a number from 1 to 4, preferably from 1 to 3, and is above all equal to 1.



   Mention should be made in particular of the new compounds of formula I in which R is a bridge of formula BR3, BR4 or BR6, and R;, R, R and R are Cg-Cis alkyl radicals or or RI and R2 and / or R3 and R4 together form a CC alkylene residue.

  <Desc / Clms Page number 29>

 



   Another object of the present invention consists of new compounds of formula I in which n is a number from 2 to 6, R is a BRI, BR2 or BR5 bridge and the other generic symbols have the definition given for formula I, and conditions a) and b), given at the beginning for formula I, are not valid. Mention should in particular be made of the new compounds of this type in which n is between 2 and 5 and those in which R ,, R R3 and R4 are Cg-C1g alkyl radicals or RI and R2 and / or R3 and R4 form together a C 1 -C 6 alkylene residue.



   The new compounds of formula 1 which have just been described are remarkably suitable for the stabilization of organic materials against degradation due to oxidation, heat or light.



   Examples of such materials are: 1. polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly (4-methylpent-l-ene), polyisoprene or polybutadiene as well as cycloolefin polymers such as, for example, cyclopentene or norbornene; or polyethylene (which may optionally be crosslinked), for example high density polyethylene (HDPE), high density polyethylene with high molecular weight (HDPE-HMW), high density polyethylene with very high molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (VLDPE).



   The polyolefins, namely the polymers of monoolefins, which are mentioned by way of examples in the preceding paragraph, in particular polyethylene and polypropylene, can be prepared by various processes, in particular by the following methods: a) by radical route (usually under high pressure and high temperature); b) using a catalyst, the catalyst usually containing one or more metals from groups IVb, Vb, VIb or VIII. These metals usually have one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyl, alkenyl and / or aryl groups, which may have a 1t or a coordination type.

   These metal complexes can be free or fixed on a support, for example on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be active as such in the polymerization, or can be used

  <Desc / Clms Page number 30>

 other activators such as, for example, metal alkyl compounds, metal hydrides, metal alkyl halides, metal metal oxides or metal alkyloxanes, the metals being elements of groups la, Ha and / or ma. The activators can for example be modified with other ester, ether, amine or silyl ether groups.

   These catalyst systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta),
TNZ (DuPont), metallocenes or single site catalysts (SSC).



  2. mixtures of polymers mentioned under 1), for example mixtures of polypropylene and polyisobutylene, polypropylene and polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).



  3. copolymers of monoolefins and diolefins together or with other vinyl monomers, for example ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE), propylene / but-1-ene, propylene / isobutylene copolymers, ethylene / but-l-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, copolymers
 EMI30.1
 ethylene / heptene, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers,

   ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene / acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidenenorbomene;

   and mixtures of such copolymers with each other and with the polymers mentioned under 1) above, for example mixtures of polypropylene with ethylene / propylene copolymers, LDPE with ethylene / vinyl acetate copolymers, LDPE with ethylene copolymers / acrylic acid, of LLDPE with ethylene / vinyl acetate copolymers and of LLDPE with ethylene / acrylic acid copolymers, and polyalkylene / carbon monoxide copolymers with alternating or random structure and their mixtures with other polymers such as, for example , polyamides.



  4. hydrocarbon resins (for example CS-C9) including their hydrogenated derivatives (for example adhesive resins) and mixtures of polyalkylenes and starch.
 EMI30.2
 



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



  6. copolymers of styrene or of α-methylstyrene with dienes or

  <Desc / Clms Page number 31>

 acrylic derivatives, for example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / acrylate and alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate copolymers; mixtures with high impact resistance consisting of copolymers of styrene and another polymer such as, for example, a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer;

   and styrene block copolymers such as, for example, styrene / butadiene / styrene block copolymers, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.



  7. graft copolymers of styrene or of α-methylstyrene, for example of styrene on polybutadiene; styrene on poly (butadiene / styrene) or poly (butadiene / 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 poly (alkyl acrylates) or poly (alkyl methacrylates);

   styrene and acrylonitrile on acrylate / butadiene copolymers; as well as their mixtures with the copolymers listed under 6), for example those which are known under the name of ABS, MBS, ASA or AES polymers.



  8. halogenated polymers such as, for example, polychloroprene, chlorinated rubber, an isobutylene / chlorinated or brominated isoprene copolymer (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and epichlorohydrin copolymers, in particular polymers of halogenated vinyl compounds, for example poly (vinyl chloride), poly (vinylidene chloride), poly (vinyl fluoride), poly (vinylidene fluoride); as well as their copolymers such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.



  9. polymers which are derived from a, ss-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates, poly (methyl methacrylates) made impact resistant by modification with butyl acrylate, polyacrylamides and polyacrylonitriles.



  10. copolymers of the monomers mentioned under 9) with one another or with others

  <Desc / Clms Page number 32>

 unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate copolymers, acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate terpolymers.



  He. polymers which are derived from unsaturated alcohols and amines or from their acylated derivatives or from their acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate and poly benzoate vinyl), poly (vinyl maleate), polyvinyl butyral, poly (allyl phthalate) or polyallyl melamine, and their copolymers with the olefins mentioned in point 1.



  12. homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, poly (ethylene oxide), poly (propylene oxide) or their copolymers with bisglycidyl ethers.



  13. polyacetals, such as polyoxymethylene, and polyoxymethylenes which contain comonomers such as, for example, ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.



  14. poly (phenylene oxides and sulfides) and mixtures thereof with styrene polymers or polyamides.



  15. polyurethanes which are derived on the one hand from polyethers, polyesters and polybutadienes having terminal hydroxy groups and on the other hand from aliphatic or aromatic polyisocyanates, as well as their precursors.



  16. polyamides and copolyamides which are derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6 / 10,6 / 9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained from m-xylene, a diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid, and optionally an elastomer as modifying agent, for example poly (2,4, 4-trimethylhexamethyleneterephthalamide) or poly (m-phenylene-isophthalamide) );

   block copolymers of the aforementioned polyamides with polyolefins, copolymers of olefins, ionomers or elastomers chemically bonded or grafted; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during shaping (RIM polyamide systems).



   17. polyureas, polyimides, poly (amide-imides), polyetherimides,

  <Desc / Clms Page number 33>

 
 EMI33.1
 polyesterimides, polyhydantoins and polybenzimidazoles.



  18. polyesters which are derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or corresponding lactones, for example poly (ethylene terephthalate), poly (butylene terephthalate), poly (terephthalate 1 , 4-dimethylolcyclohexane) and polyhydroxybenzoates, as well as block copoly (ethers-esters) which are derived from polyethers having terminal hydroxy groups; and also polyesters modified with polycarbonates or MBS.



  19. polycarbonates and polyestercarbonates.



  20. polysulfones, polyethersulfones and polyetherketones.



  21. crosslinked polymers which are derived on the one hand from aldehydes and on the other hand from phenols, urea or melamine, such as phenol / methylenehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.



  22. siccative and non-siccative alkyd resins.



  23. unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyols and vinyl compounds as crosslinking agents, as well as their low-flammable halogenated derivatives.



  24. crosslinkable acrylic resins which are derived from substituted acrylates, for example epoxyacrylates, urethane-acrylates or polyester-acrylates.



  25. alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.



  26. crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example products of diglycidyl ethers of bisphenol A, diglycidyl ethers of bisphenol F, which have been crosslinked using conventional hardeners such as , for example, anhydrides or amines, with or without accelerators.



  27. natural polymers such as cellulose, natural rubber, gelatin, and their chemically modified derivatives to homologous polymers, for example cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers such as methylcellulose ; as well as rosin resins and their derivatives.



  28. mixtures (polyblends) of the aforementioned polymers, for example, PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / PUR thermoplastic, PC / PUR thermoplastic, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and its copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or

  <Desc / Clms Page number 34>

 PBT / PET / PC.



  29. natural and synthetic organic substances which may represent pure monomeric compounds or mixtures of these compounds, for example mineral oils, animal or vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters (eg phthalates, adipates, phosphates or trimellitates) and mixtures of synthetic esters with mineral oils in any mass ratios, such as those used in spinning preparations, and their aqueous emulsions.



  30. aqueous emulsions of natural or synthetic rubbers such as, for example, a natural rubber latex or latexes of styrene / butadiene carboxylated copolymers.



  31. petroleum and coal distillation residues such as, for example, asphalt, bitumen or bituminous compositions for road surfaces.



   The organic material to be protected is preferably a natural, semi-synthetic or synthetic polymer, in particular a synthetic polymer. Thermoplastic polymers are particularly preferred, especially poly (vinyl chloride) or polyolefins, for example polyethylene and polypropylene (PP).



   The invention therefore also relates to compositions containing a synthetic or semi-synthetic organic polymer and at least one new phosphite of formula I as defined above, its use for the stabilization of said polymers, and a process for stabilization of synthetic or semi organic polymers -synthetics, characterized in that at least one new phosphite of formula 1 is incorporated therein. Examples of polymers to be stabilized are found in the preceding enumeration (n 1-28 and 30). Polyolefins, polyurethanes, polycarbonates, polyamides and elastomers are preferred here.



   The new compounds of formula I are contained in the compositions according to the invention in an amount advantageously between 0.01 and 10, for example between 0.05 and 5, preferably between 0.05 and 3, but in particular between 0 , 1 and 2% by mass. It may also be one or more of the compounds of formula I, and the percentages by mass refer to the total amount of these compounds.



   The incorporation into the materials can be carried out, for example, by mixing or by applying the compounds of formula I and possibly other additives by methods common in the art. The incorporation can be done before or during the shaping, or by application of the dissolved or dispersed compounds on the polymer, with possibly a subsequent evaporation of the solvent. In the case

  <Desc / Clms Page number 35>

 elastomers, they can also be stabilized in the form of latex. The compounds of formula 1 can also be incorporated into the polymers by adding them before, during or immediately after the polymerization of the corresponding monomers or before crosslinking. It is also possible to add the compounds of formula I as such, but also in encapsulated form (for example in waxes, oils or polymers).

   In the case of addition before or during the polymerization, the compounds of formula 1 can also act as agents for adjusting the chain length of the polymers (chain imitators).



   The compounds of formula 1 and their mixtures can also be added to the synthetic materials to be stabilized in the form of masterbatches containing these compounds, for example at a concentration of 2.5 to 25% by mass.



   The incorporation of the compounds of formula I can advantageously be carried out by the following methods: - in the form of an emulsion or dispersion (for example addition to a latex or a polymer in emulsion) - in the form of a dry mixture during the mixing of the additives or mixtures of polymers - by direct addition in the forming apparatus (for example in the extruder, the internal mixer, etc.) - in the form of a solution or a melt.



   The polymer compositions according to the invention can be used in different forms or in the form of different products, for example in the form of sheets, fibers, strips, molding compositions, profiles, or as binders for paints, glues or mastics.



   As already mentioned, the organic materials to be protected are semi-synthetic or synthetic organic polymers, preferably synthetic.



  Particularly advantageous protection is given to thermoplastic materials, in particular polyolefins. It is especially important to note the excellent activity of the compounds of formula I as stabilizers for shaping (heat stabilizers). To this end, they are advantageously added to the polymer before or during its shaping.



   However, it is also possible to stabilize other polymers (for example elastomers), or lubricants or hydraulic fluids against the degradation induced for example by light and / or by heat and oxidation. Elastomers are found in the above list of possible organic materials.



   In another aspect, the invention relates to compositions which

  <Desc / Clms Page number 36>

 contain a lubricant, a hydraulic fluid or a fluid for the treatment of metals and at least one phosphite of formula I, the use of these phosphites as additives in lubricants and the aforementioned functional fluids, and a method for improving the properties of the use of lubricants, hydraulic fluids or fluids for the treatment of metals, characterized in that at least one phosphite of formula I is added thereto



   Lubricants, hydraulic fluids and fluids for the treatment of metals taken into account are for example based on mineral or synthetic oils or their mixtures. Lubricants are well known to those skilled in the art and are described in the corresponding specialized literature, for example in Dieter Klamann, Schmierstoffe und verwandte Produkte (Editions Chemie, Weinheim, 1982), in Schewe-Kobek, Das Schmiermittel-Taschenbuch "(Edition Dr. Alfred Hüthig, Heidelberg, 1974), and in Ullmanns Enzyklopädie der technischen Chemie, volume 13, pages 85-94 (Editions Chemie, Weinheim, 1977).



   In addition to the compounds according to the invention, the compositions according to the invention, in particular when they contain organic polymers, preferably synthetic, may contain other common additives, for example stabilizers. Examples of such additives are: 1. Antioxidants 1.1.

   alkylated monqphenols, for example 2, 6-di-tert-butyl-4-methylphenol, 2tert-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-isobutylphenol, 2,6-dicyclopentyl-4methylphenol, 2- (a-methylcyclohexyl) -4,6 -dimethylphenol, 2,6-dioctadecyl-4methylphenol, 2,4, 6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols such as, for example, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundéc-l'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadéc-l ' -yl) phenol, 2,4-dimethyl-6- (1'-
 EMI36.1
 methyltridec-l'-yl)

   phenol and mixtures thereof.



  1. 2. alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.



  1.3. alkylated hydroquinones and hydroquinones, for example 2,6-di-tertbutyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl -4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3 stearate , 5-di-tert-butyl-4-hydroxyphenyl, bis (3,5-di-tert-butyl-4- adipate)

  <Desc / Clms Page number 37>

 hydroxyphenyl).



  1. 4. tocopherols, for example a-tocopherol, ss-tocopherol, y-tocopherol, 8-tocopherol and their mixtures (vitamin E).



  1.5. hydroxyl thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl- 3methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-secamylphenol), 4,4'-bis disulfide (2 , 6-dimethyl-4-hydroxyphenyl).



  1.6. alkylidenebisphenols, for example 2,2'-methylenebis (6-tert-butyl-4methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis 4- methyl-6- (a-methyl1cyc1ohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2 'methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol ), 2,2'-methylenebis [6- (amethylbenzyl) -4-nonylphenol], 2,2'-methylenebis 6- (a, a-dimethylbenzyl) -4- nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6tert-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 (5tert-butyl-4-hydroxy-2-methylphenyl) butane , 1,1-bis (5-tert-butyl-4-hydroxy-2methylphenyl) -3-n-dodecylmercaptobutane, bis [3, 3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate d ethylene glycol, bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methyl-) terephthalate
 EMI37.1
 benzyl) -6-tert-butyl-4-methylphenyl], 1, 1-bis (3, 5-dimethyl-2-hydroxyphenyl) butane, 2, 2-bis (3, 5-di-tert-butyl- 4-hydroxyphenyl) propane, 2, 2-bis (5-tert-butyl- 4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl - 4-hydroxy- 2-methylphenyl)

     pentane.



  1.7. 0- compounds. N- and S-benzylated, for example 3,5,3 ', 5'-tetra-tertbutyl-4,4'-dihydroxydibenzyl, 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, 4 -3,5-di-tert-butylbenzylmercapto-tridecyl acetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis dithioterephthalate (4-tert-butyl-3-hydroxy-2 , 6-dimethylbenzyl), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.



  1.8. hydroxybenzylated malonates, for example dioctadecyl 2,2-bis (3,5-di-tert-butyl-2hydroxybenzyl) malonate, 2- (3-tert-butyl-4-hydroxy-5-methyl-benzyl) malonate dioctadecyl, 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) didodecylmercaptoethyl malonate, 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate di 4- (1, 1, 3,3-tetramethylbutyl) phenyl].

  <Desc / Clms Page number 38>

 



  1.9. hvdroxybenzylated aromatic compounds. for example 1, 3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2, 4, 6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4hydroxybenzyl ) -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-hydroxyanilino) -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, 1,3,5tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3, 5 -di-tert-butyl-4-hydroxyphenylethyl) -1, 3,5-triazine, 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5 -triazine, 1, 3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl)

   isocyanurate.



  1.11. benzylphosphonates, for example 2,5-di-tert-butyl-4-hydroxy-
 EMI38.1
 dimethyl benzylphosphonate, 3,5 di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate dioctadecyl, 5tert-butyl-4-hydroxy-3-methylbenzylphosphonate dioctadecyl, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 1.12. acylammophenols. for example 4-hydroxyanilide of lauric acid, 4-hydroxyanilide of stearic acid, N- (3,5-di-tert-butyl-4-hydroxyphenyl) - octyl carbamate.



  1.13 esters of p-r3 acid. 5-di-tert-butyl-4-hydroxyphenynpropionic with mono or polyalcohols, for example with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide , 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6,7-
 EMI38.2
 trioxabicyclo [2. 2.2] octane.



  1.14. esters of ss- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono or polyalcohols, for example with methanol, ethanol, noctanol, isooctanol, l octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-

  <Desc / Clms Page number 39>

 
 EMI39.1
 phospha-2, 6, 7-trioxabicyclo [2. 2.2] octane.



  1. 15. esters of ss- (3. 5-dicyclohexyl-4-hydroxphenphenpropionic acid with mono or polyalcohols, for example with methanol, ethanol, octanol, octadecanol, 1 , 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, Nbis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol,
 EMI39.2
 trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7trioxabicyclo [2. 2.2] octane.



  1. 16. esters of 3. 5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyalcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol,
 EMI39.3
 pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2.2] octane.



  1.17. p- acid amides <3.5-di-tert-butyl-4-hvdroxvphenynpropionique. for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene- diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.



  1.18. ascorbic acid (vitamin C).



  1.19. amino antioxidants, for example N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p -
 EMI39.4
 phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, Nbis (1-methylheptyl) -p-phenylenediamine, N, N -dicyclohexyl-p-phenylenediamine, N , N'-diphenyl-p-phenylenediamine, N, N'-di (napht-2-yl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N - (1, 3 -dimethylbutyl) - N'-phenyl-p- phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, Ncyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido ) diphenylamine, N, N'-dimethyl-N,

       N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, an octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4-nbutylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4dodecanoylaminophenol, 4-octadecanol di (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenyl-

  <Desc / Clms Page number 40>

 methane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di [(2-methylphenyl) amino] ethane,

     1, 2-di (phenylamino) -
 EMI40.1
 propane, (o-tolyl) biguanide, di 4- (1 ', 3'-dimethylbutyl) phenyl] amine, an octylated N-phenyl-1-naphthylamine, a mixture of tert-butyl / tert-octyldiphenylamines mono- and dialkylated, a mixture of mono-and dialkylated nonyldiphenylamines, a mixture of mono-and dialkylated dodecyldiphenylamines, a mixture of mono-and dialkylated isopropyl / isohexyldiphenylamines, a mixture of mono-and dialkylated tert-butyldiphenylamines, 2,3 -3, 3-dimethyl-4H-I, 4-benzothiazine, phenothiazine, a mixture of tert-butyl / tert-octylphenothiazines mono- and dialkylated, a mixture of tert-octylphenothiazines mono-and dialkylated, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,

     4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidine-4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidine-4-yl) sebacate , 2,2,6,6-tetramethylpiperidine-4-one, 2,2,6,6-tetramethylpiperidine-4-ol.



  2. UV absorbers and light stabilizers.



  2.1. 2- (2'-hydroxyphenv benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole ,
 EMI40.2
 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'- (1, 1, 3, 3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5- chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert -amyl-2'-hydroxyphenyl) -
 EMI40.3
 benzotriazole, 2- (3 ', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole,

   a mixture of 2- (3'-tert-butyl- 2'-hydroxy- 5'- (2-octyloxycarbonylethyl) phenyl) -5chlorobenzotriazole, 2- (3-tert-butyl-5'- [2- (2- ethylhexyloxy) carbonylethyl] -2'- hydroxyphenyl) -5-chlorobenzotriazole, of 2- (3'-tert-butyl-2'-hydroxy-5'- (2- methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, of 2- ( 3'-tert-butyl-2'-hydroxy- 5'- (2-methoxycarbonylethyl) phenyl) benzotriazole, of 2- (3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'- [2- (2- ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-
 EMI40.4
 hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5'- (2isooctyloxycarbonylethyl) phenyl) benzotriazole, 2, 2'-methylenebis 4- (1,

   1, 3, 3tetramethylbutyl) -6- (benzotriazole-2-yl) phenol]; the transesterification product of 2- [3'-tert-butyl-5'- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotnazole with polyethylene glycol 300; [R-CH, CHCOO (CHL- with R = 3'-tert-butyl-4-hydroxy-5'- (2H-benzotriazole-2-yl) phenyl.

  <Desc / Clms Page number 41>

 



  2.2. 2-hydroxybenzophenones, for example 4-hydroxy, 4-methoxy, 4octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy- 4,4' derivatives -dimethoxy.



  2.3. esters of optionally substituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3 2,4-di-tert-butylphenyl, 5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert- octadecyl butyl-4hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.



  2.4. acrylates, for example a-cyano-p. ethyl or isooctyl p-diphenylacrylate, methyl a-carbomethoxycinnamate, a-cyano-ss-methyl-p-
 EMI41.1
 methyl or butyl methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N- (ss-carbomethoxy-P-cyanovinyl) -2-methylindoline. 2.5. nickel compounds, for example nickel complexes with 2,2'thiobis 4- (1, 1, 3, 3-tetramethylbutyl) phenol], such as the 1: 1 complex or the 1 complex:

   2, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, dibutylnickel dithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-ditert-butylbenzylphosphonic acid, such as methyl or ethyl esters, nickel complexes with ketoximes such as 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes with 1-phenyl-4-lauroyl-5-hydroxypyrazole, possibly with others ligands.



  2.6. sterically hindered amines, for example bis (2,2,6,6tetramethylpiperidine-4-yl) sebacate, bis (2,2, 6,6-tetramethylpiperidine-4-yl) succinate, bis sebacate ( 1, 2,2, 6, 6-pentamethylpiperidine-4-yl), bis sebaçate (loctyloxy-2, 2,6, 6-tetramethylpiperidine-4-yl), n-butyl-3, 5-di- bis (1,2,2,6,6,6-pentamethylpiperidyl) tert-butyl-4-hydroxybenzylmalonate, the condensation product of l-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N, N'-bis (2,2,6,6-tetramethyl-4piperidyl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3,5- s-triazine, the nitrilotriacetate of tris (2,2, 6,

     6-tetramethyl-4-piperidyl), 1,2,4,4-butanetetracarboxylate of tetrakis (2,2,6,6-tetramethyl-4-piperidyl), 1, 1'- (1, 2-ethanediyl) -bis (3.3, 5.5-tetramethylpiperazinone), 4-benzoyl-2,2, 6,6-tetramethyl-
 EMI41.2
 piperidine, 4-stearyloxy-2, 2, 6, 6-tetramethylpiperidine, 2-n-butyl-2- (2-hydroxy- 3, 5-di-tert-butylbenzyl) malonate bis (1, 2, 2 , 6, 6-pentamethylpiperidyl), 3-n-

  <Desc / Clms Page number 42>

 octyl-7,7, 9, 9-tetramethyl-I, 3, 8-triazaspiro [4.

   5] decane-2,4-dione, bis sebacate (loctyloxy-2,2,6,6-tetramethylpiperidyl), bis succinate (l-octyloxy-2,2,6,6-tetramethylpiperidyl), the product of condensation of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-1, 3,5-triazine, the product of condensation of 2-chloro-4,6-di (4-n-butylamino-2, 2,6, 6-tetramethyl-
 EMI42.1
 piperidyl) -1,3.5-triazine and 1,2-bis (3-aminopropylamino) ethane, the condensation product of 2-chloro-4,6-di (4-n-butylamino-1,2), 2, 6, 6-pentamethylpiperidyl) - 1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl- 7, 7, 9, 9-tetramethyl-1 , 3, 8-triazaspiro [4.

   5] decane-2, 4-dione, 3-dodecyl-1- (2, 2, 6, 6tetramethyl-4-piperidyl) pyrrolidine-2, 5-dione, 3-dodecyl-1 - (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) pyrrolidine-2, 5-dione, a mixture of 4-hexadecyloxy and 4-stearyloxy-2,2, 6, 6-tetramethylpiperidine, the condensation product of N, Nbis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1, 3, 5-triazine, the condensation product of 1, 2-bis (3aminopropylamino ) ethane and 2,4,6-trichlor-1, 3,5-triazine, as well as 4butylamino-2,2,6,6-tetramethylpiperidine (RN CAS [136504-96-6]);

   N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4piperidyl) -n-dodecylsuccinimide 2-undecyl -7.7, 9, 9-tetramethyl-1-oxa-3, 8-diaza- 4-oxospiro [4, 5] decane, the reaction product of 7,7, 9, 9-tetramethyl-2-cycloundecyl- l-oxa-3, 8-diaza-4-oxospiro [4, 5] decane and epichlorohydrin.



  * 2.7. diamides of oxalic acid, for example 4,4'-dioctyloxyoxanilide, 2,2'diethoxyoxanilide, 2,2'-dioctyloxy-5, 5'-di-tert-butyloxanilide, 2,2'- didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2 ' -ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, mixtures of oxanilides disubstituted by methoxy at o and p, and by ethoxy at o and p.



  2.8. 2- (2-hydroxyphenyl) -1. 3. 5-triazines, for example 2,4,6-tris (2-hydroxy-4octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4 , 6-bis (4-methylphenyl) -
1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -
 EMI42.2
 1, 3, 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) - 1, 3, 5-triazine,

   2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propyloxy) phenyl] -4, 6- bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- [2 -hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dodecyloxy /

  <Desc / Clms Page number 43>

 tridecyloxy-2-hydroxypropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -
1, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propyloxy) phenyl] -4, 6bis (2, 4-dimethylphenyl) -1, 3,5-triazine , 2- (2-hydroxy-4-hexyloxy) -4, 6-diphenyl-
1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine 2,4,4

     6-tris [2-hydroxy-4- (3-butyloxy-2-hydroxy-propyloxy) phenyl] -1, 3, 5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6 -phenyl-1, 3,5-triazine.



  3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5 -ditert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2, 4-triazole, bis (benzylidene) dihydrazide of oxalic acid, oxanilide, dihydrazide of isophthalic acid, bis (phenylhydrazide) of sebacic acid, N, N'diacetyldihydrazide of adipic acid, N, N'-bis-salicyloyldihydrazide of oxalic acid, N, N'-bis-salicyloyldihydrazide of thiopropionic acid .



  4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl and alkyl phosphites, phenyl and dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris (2,4-ditert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6- diphosphite) di-tert-butyl-4methylphenyl) pentaerythritol, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4, 6-tri-tert diphosphite -butylphenyl) pentaerythritol, the tristearylsorbitol triphosphite, the tetrakis 4,2'-biphenylenediphosphonite (2,

  4-di-tert-butylphenyl), 6-isooctyloxy- 2,4, 8, 10-tetra-tert-butyl-12H-dibenzo [d, g] -1, 3,2-dioxaphosphocine, 6-fluoro- 2,4, 8, 10-tetra-tert-butyl-12-methyldibenzo [d, g] -1, 3, 2-dioxaphosphocine, methyl phosphite and bis (2,4-di-tert-butyl-6 -methylphenyl), ethyl phosphite and bis (2,4-di-tert-butyl-6-methylphenyl).
 EMI43.1
 



  5. Hydroxylamines, for example N, N-dibenzylhydroxylamine, N, Ndiethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine N- dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N- heptadecy 1- N-octadecylhydroxylamine, an N, N-dialkylhydroxylamine of hydrogenated tallow fatty amines.



  6. Nitrones, for example N-benzyl-a-phenylnitrone, N-ethyl-a-methylnitrone, N-octyl-a-heptylnitrone, N-lauryl-a-undecylnitrone, Ntetradecyl-a-tridecylnitrone, N-hexadecyl-a-pentadecylnitrone, N-octadecyl-a-

  <Desc / Clms Page number 44>

 heptadecylnitrone, N-hexadecyl-a-heptadecylnitrone, N-octadecyl-a-pentadecylnitrone, N-heptadecyl-a-heptadecylnitrone, N-octadecyl-a-hexadecylnitrone, nitrones derived from N, N-dialkines from fatty amines of hydrogenated tallow.



  7. Thio synergistic compounds, for example dilauryl thiodipropionate or distearyl thiodipropionate.



  8. Compounds which destroy peroxides, for example esters of thiodipropionic acid, for example lauryl, stearyl, myristylic or tridecyl esters, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dibutylzinc dithiocarbamate, disulfide of dioctadecyl, pentaerythritol tetrakis (ss-dodecylmercapto) propionate.



  9. Polyamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.



  10. Basic costabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, pyrocatecholate antimony or tin pyrocatecholate.



  11. Nueling agents, for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably of alkaline earth metals; organic compounds such as mono or polycarboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, for example ionic copolymers ("ionomers").



  12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulphate, oxides and metal hydroxides, carbon black, graphite, sawdust and powders or fibers of other natural products, synthetic fibers.



  13. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, fluidity additives, catalysts, leveling agents, optical brighteners, flame retardants, antistatic agents, blowing agents.

  <Desc / Clms Page number 45>

 



  14. Benzofuranones and indolinones, for example those described in patent documents 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 316622, DE-A- 4316876, EP-A-0589839 or EP-A-0591102, or 3- [4- ( 2-acetoxyethoxy) - phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2 -one, 3, 3'-bis [5, 7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5, 7-di-tert -butyl-3- (4-ethoxyphenyl) benzo-
 EMI45.1
 furan-2-one, 3- (4-acetoxy-3, 5-dimethylphenyl) -5, 7-di-tert-butylbenzofuran-2one, 3- (3,

   5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one.



   The following examples explain the invention in more detail. Unless otherwise indicated, the data in parts or in percentages relate to the mass, as in the claims and the rest of the description.



  Example 1 Tetra-tndecyl / pentadecyt-dianhydrosorbitot diphosphite
310.3 g (1.0 mol) are introduced into a reaction apparatus well rinsed with dry nitrogen, equipped with a stirrer, a thermometer, a distillation bridge and a receiving flask. ) triphenyl phosphite, 73.1 g (0.5 mol) of 1.4, 3.6-
 EMI45.2
 dianhydrosorbitol, 422.0 g (2.0 mol) of a mixture of tridecanol / pentadecanol (ACROPOL-35) and 2.7 g (0.05 mol) of sodium methylate, heated to 110 ° C. in space one hour and stirred for 3 hours at 110 C.



  After having cooled to 80 ° C., most of the liberated phenol is distilled under vacuum while slowly raising the temperature to 150 ° C., and the rest of the phenol is separated in one hour by an oil pump at 150 ° C. and under about 0, 1 mbar.



   2 g of filter aid are added to the residue and filtered. 502.3 g of a light yellow liquid are obtained, the structure and analysis results of which are given in Table 1 below, Example 1.



   By following a procedure analogous to the preceding procedure, the phosphites indicated in table 1, examples 2-7, are obtained using the diols and monoalcohols or their corresponding mixtures.

  <Desc / Clms Page number 46>

 



  Table 1
 EMI46.1
 
 <tb>
 <tb> example <SEP> #
 <tb> phosphite <SEP>: <SEP> R1 <SEP> P-O-R-O <SEP> P
 <tb> #
 <tb> (n <SEP> = <SEP> 1)
 <tb> R <SEP> RI, <SEP> R2, <SEP> R3, <SEP> R4 <SEP> yield <SEP>% <SEP> P
 <tb> 20
 <tb>% <SEP> from <SEP> the <SEP> th. <SEP> nD <SEP> calc./found
 <tb> 1 <SEP> # <SEP> R1 = R2 = R3 = R4 = <SEP> 97 <SEP> 1.4700 <SEP> 6.01 / 5, <SEP> 88
 <tb> C13H27 / CnH31-
 <tb> 2 <SEP> [CH-CH2] 2O <SEP> R1 = R2 = R3 = R4 = <SEP> 88 <SEP> 1.4620 <SEP> 7.53 / 7.59
 <tb> CH3 <SEP> i-C10H21-
 <tb> 3 <SEP> # <SEP> R1 = R2 = R3 = R4 = <SEP> 90 <SEP> 1.4627 <SEP> 6.19 / 6, <SEP> 05
 <tb> CH3 <SEP> C12H25 / C14H29-
 <tb> 4 <SEP> # <SEP> R1 = R2 = R3 = R4 = <SEP> 84 <SEP> 1.4645 <SEP> 8.17 / 8.76
 <tb> i-C8H17-
 <tb> 5 <SEP> # <SEP> R1 = R2 = R3 = R4 = <SEP> 83 <SEP> 1, <SEP> 4837 <SEP> 7, <SEP> 00/7, <SEP> 22
 <tb> # <SEP> i-C10H21-
 <tb> 6 <SEP> # <SEP> R1 = R2 = R3 = R4 = <SEP> 84 <SEP> 1.4793 <SEP> 8.57 / 8,

  81
 <tb> C4H9-CH-CH2C2Hs
 <tb> 7 <SEP> - (CH2-CH2O) 2-CH2CH2- <SEP> R1 = R2 = R3 = R4 = <SEP> 100 <SEP> 1,417
 <tb> n-CH ,,
 <tb>
 i denotes a mixture of isomers.



  Example 8
 EMI46.2
 6 Bis-neopentylglycol-dihydroxymethyltricylo [5, 2, 1, 0] decyl phosphite
49.08 g (0.25 mol) of 3 (4), 8 (9) -dihydroxymethyltricyclo [5,2,1,02,6] decane and 55 are introduced into a device prepared as in Example 1 62 g (0.55 mol) of triethylamine with 250 ml of tetrahydrofuran (THF) and 84.29 g (0.50 mol) of 2-chloro-5 are added dropwise over 30 minutes, 5- dimethyl- [1, 3] dioxaphosphorinane in 100 ml of THF, with stirring and cooling.
 EMI46.3
 



  The temperature is maintained at 35 C. It is then stirred at 60 C for 2 hours and, after cooling to room temperature, the precipitated triethylamine hydrochloride is filtered off. The solvent is distilled on a rotary evaporator,

  <Desc / Clms Page number 47>

 the residue is distilled up to 60 ° C. under 0.1 mbar and, after adding 1 g of filter aid (Celite), it is filtered to obtain a clear filtrate. 98.3 g of a colorless liquid are obtained, the structure and analysis results of which are given in Table 2 below, Example 8.



   By following a procedure analogous to the preceding procedure, the phosphites indicated in Table 2, Examples 9-16, are obtained using the diols and the corresponding chlorophosphorinanes.



   Table 2
 EMI47.1
 
 <tb>
 <tb> example <SEP> #
 <tb> phosphite <SEP>: <SEP> R1-O + P-O-R-O + P
 <tb> #
 <tb> 0-R,
 <tb> (n <SEP> = <SEP> 1)
 <tb> R <SEP> R1, <SEP> R @, <SEP> R3, <SEP> R4 <SEP> yield <SEP>% <SEP> P
 <tb>% <SEP> from <SEP> the <SEP> th. <SEP> nD20 <SEP> calc./found
 <tb> 8 <SEP> # <SEP> Rt + R2 = R3 + = <SEP> 85 <SEP> 1.5045 <SEP> 13.45 / 13, <SEP> 38
 <tb> #
 <tb> 9 <SEP> # <SEP> R1 + R2 = R3 + R4 = <SEP> 83 <SEP> 1.4698 <SEP> 15.55 / 15, <SEP> 12
 <tb> CH3 <SEP> #
 <tb> 10 <SEP> # <SEP> # <SEP> 97 <SEP> 1.4770 <SEP> 19.72 / 19.53
 <tb> 11 <SEP> # <SEP> R1 + R2 = R3 + R4 = <SEP> 97 <SEP> Tf56-15, <SEP> 10 / 15.08
 <tb> # <SEP> 580C
 <tb> CH3
 <tb> 12 <SEP> # <SEP> R1 + R2 = R3 + R4 = <SEP> 93 <SEP> Tf <SEP> 133- <SEP> 16, <SEP> 29-16.39
 <tb> # <SEP> 140 C
 <tb> CH3
 <tb> 13 <SEP> # <SEP> # <SEP> 95 <SEP> Tf <SEP> 85- <SEP> 15.17 / 14,

  98
 <tb> # <SEP> 89 C
 <tb> CHV
 <tb>
 

  <Desc / Clms Page number 48>

 Table 2 (continued)
 EMI48.1
 
 <tb>
 <tb> example <SEP> r-R2 <SEP> #
 <tb> phosphite <SEP>: <SEP> R1-O + P-O-R-O + P
 <tb> #
 <tb> O-R4
 <tb> (n <SEP> = <SEP> 1)
 <tb> R <SEP> R1, <SEP> R2, <SEP> R3, <SEP> R4 <SEP> yield <SEP>% <SEP> P
 <tb> 20
 <tb>% <SEP> from <SEP> the <SEP> th. <SEP> nD <SEP> calc./found
 <tb> 14 <SEP> R1 + R2 = R3 + R4 = <SEP> 86 <SEP> 1.4775 <SEP> 16.73 / 16, <SEP> 15
 <tb> #
 <tb> CH3
 <tb> 15 <SEP> R1 + R2 = R3 + R4 = <SEP> 87 <SEP> 1.4773 <SEP> 14.95 / 14, <SEP> 38
 <tb> # <SEP> #
 <tb> 16 <SEP> # <SEP> R1 + R2 = R3 + R4 =
 <tb> #
 <tb>
 
By following a procedure analogous to the procedure of Examples 1 to 8, it is possible to obtain the phosphites presented in Tables 3 to 8 below.



   Table 3
 EMI48.2
 
 <tb>
 <tb> example <SEP> #
 <tb> phosphite <SEP>: <SEP> #
 <tb> #
 <tb> (n = l)
 <tb> R <SEP> R1, <SEP> R2, <SEP> R3, <SEP> R4
 <tb> 17 <SEP> # <SEP> R1 + R2 <SEP> = <SEP> R3 + R4 <SEP> =
 <tb> #
 <tb> 18 <SEP> # <SEP> R1 + R2 = R3 + R4 =
 <tb> #
 <tb>
 

  <Desc / Clms Page number 49>

 
 EMI49.1
 Table 3 (continued)
 EMI49.2
 
 <tb>
 <tb> example <SEP> #
 <tb> phosphite <SEP>:

    <SEP> #
 <tb> #
 <tb> (n <SEP> = <SEP> 1)
 <tb> R <SEP> R1, <SEP> R2, <SEP> R3, <SEP> R4
 <tb> 19 <SEP> # <SEP> # <SEP> R1 + R2 <SEP> = <SEP> R3 + R4 <SEP> =
 <tb> #
 <tb> i-CsH7-
 <tb> 20 <SEP> R1 + R2 <SEP> = <SEP> R3 + R4 <SEP> =
 <tb> # <SEP> #
 <tb> 21 <SEP> # <SEP> R1 + R2 <SEP> = <SEP> R3 + R4 <SEP> =
 <tb> #
 <tb> 22 <SEP> RI + R2 <SEP> R3 + R4 <SEP> =
 <tb> #
 <tb> C. <SEP> HA-
 <tb> 23 <SEP> # <SEP> R1 + R2 <SEP> = <SEP> R3 + R4 <SEP> =
 <tb> #
 <tb> 24 <SEP> # <SEP> R1 = R2 = R3 = R4 =
 <tb> #
 <tb> 25 <SEP> # <SEP> R1 <SEP> = <SEP> R2 <SEP> = <SEP> R3 + R4 <SEP> =
 <tb> #
 <tb> 26 <SEP> # <SEP> R1 <SEP> = <SEP> R2 <SEP> = <SEP> R3 + R4 <SEP> =
 <tb> C13 / 15H27 / 31- <SEP> #
 <tb>
 

  <Desc / Clms Page number 50>

 
 EMI50.1
 Table 4
 EMI50.2
 
 <tb>
 <tb> example <SEP> phosphite:

    <SEP> #
 <tb> (n <SEP> = <SEP> 2)
 <tb> R <SEP> R1, <SEP> R2, <SEP> R3, <SEP> R4
 <tb> 27 <SEP> # <SEP> R1 <SEP> = <SEP> R2 <SEP> = <SEP> R3 <SEP> = <SEP> R4 <SEP> =
 <tb> #
 <tb> 28 <SEP> R1 <SEP> = <SEP> R2 <SEP> = <SEP> R3 <SEP> = <SEP> R4 <SEP> =
 <tb> # <SEP> n-C8H17
 <tb> 29 <SEP> R1 = <SEP> R2 <SEP> = <SEP> R3 <SEP> + <SEP> R4 <SEP> =
 <tb> # <SEP> C12H25 <SEP> C13H27 <SEP> #
 <tb> 30 <SEP> # <SEP> R1 = R2 = R3 = R4 = <SEP> nD20 <SEP> = <SEP> 1.4589
 <tb> i-C10H21
 <tb> 31 <SEP> # <SEP> R1 = R2 = R3 = R4 = <SEP> nD20 <SEP> = <SEP> 1.4594
 <tb> C13H27 / C15H31
 <tb>
 

  <Desc / Clms Page number 51>

 
 EMI51.1
 Table 5
 EMI51.2
 
 <tb>
 <tb> example <SEP> #
 <tb> phosphite <SEP>:

    <SEP> #
 <tb> #
 <tb> (n <SEP> = <SEP> 3)
 <tb> R <SEP> R1, <SEP> R2, <SEP> R3, <SEP> R4
 <tb> 32 <SEP> # <SEP> R1 <SEP> = <SEP> R2 <SEP> = <SEP> R3 + R4 <SEP> =
 <tb> i-C8H17 <SEP> #
 <tb> 33 <SEP> # <SEP> R1 <SEP> = <SEP> R2 <SEP> = <SEP> R3 + R4 <SEP> =
 <tb> # <SEP> #
 <tb> 34 <SEP> # <SEP> R1 <SEP> = <SEP> R2 <SEP> = <SEP> R3 <SEP> = <SEP> R4 <SEP> =
 <tb> #
 <tb> 35 <SEP> # <SEP> R1 = R2 = R3 = R4 = <SEP> nD20 <SEP> = <SEP> 1.4595
 <tb> i-C10H21
 <tb> 36 <SEP> R1 = R2 = R3 = R4 =
 <tb> #
 <tb> - <SEP> #
 <tb> #
 <tb> Table <SEP> 6
 <tb> 5
 <tb> example <SEP> O-R2 <SEP> O-R3
 <tb> phosphite <SEP>: <SEP> #
 <tb> O-R4
 <tb> (n <SEP> = <SEP> 4)
 <tb> R <SEP> R1, <SEP> R2, <SEP> R3, <SEP> R4
 <tb> 37 <SEP> R1, <SEP> R2, <SEP> R3, <SEP> R4 <SEP> =
 <tb> # <SEP> i-C18H37 <SEP> / <SEP> #
 <tb> in <SEP> a <SEP> report <SEP> molar <SEP> from <SEP> 2 <SEP>:

    <SEP> 4
 <tb>
 

  <Desc / Clms Page number 52>

 
 EMI52.1
 Table 7
 EMI52.2
 
 <tb>
 <tb> example <SEP> O-R2 <SEP> O-R
 <tb> phosphite <SEP>: <SEP> #
 <tb> #
 <tb> (n <SEP> = <SEP> 5)
 <tb> R <SEP> R1, <SEP> R2, <SEP> R3, <SEP> R4
 <tb> RI, <SEP> R2, <SEP> R3, <SEP> R4 <SEP> =
 <tb> 38 <SEP> # <SEP> #
 <tb> CH3
 <tb> CH3
 <tb> 39 <SEP> # <SEP> R1 = R2 = R3 = R4 = <SEP> nD20 <SEP> = <SEP> 1, <SEP> 4607
 <tb> CH3 <SEP> i-C10H21
 <tb> 40 <SEP> [CH2CH2O] 2CH2CH2- <SEP> R1, <SEP> R2, <SEP> R3, <SEP> R4 <SEP> =
 <tb> 2-butyloctyl / n-dodecyl <SEP> in <SEP> a
 <tb> report <SEP> molar <SEP> from <SEP> 3 <SEP>: <SEP> 4
 <tb> Table <SEP> 8
 <tb> 5
 <tb> example <SEP> #
 <tb> phosphite <SEP>:

    <SEP> #
 <tb> #
 <tb> O-R4
 <tb> (n <SEP> = <SEP> 6)
 <tb> R <SEP> R1, <SEP> R2, <SEP> R3, <SEP> R4
 <tb> 41 <SEP> # <SEP> R1 = <SEP> R2 <SEP> = <SEP> R3 <SEP> + <SEP> R4 <SEP> =
 <tb> C12H25 <SEP> C13H27 <SEP> #
 <tb> 42 <SEP> # <SEP> R1 = R2 = R3 = R4 = <SEP> nD20 <SEP> = <SEP> 1.4604
 <tb> CH3 <SEP> i-C10H21
 <tb> 40 <SEP> R1 = R2 = R3 = R4 =
 <tb> # <SEP> i-C8H17
 <tb>
 

  <Desc / Clms Page number 53>

 Example 44
Plasticized for 5 minutes in a cylinder mixer at 190 C 100 parts of S-PVC (value K 65-71), 20 parts of dioctyl phthalate and 2 parts of a barium / zinc stabilizer containing 2-ethylhexanoate Ba, p-tertbutylbenzoate from Ba, zinc oleate and basic nonylphenolate from Ba, and 23.6% of a phosphite according to the invention (corresponding to 0.5 part per 100 parts of PVC) according to the table 9,

   then the sheet obtained (0.3 mm) is subjected to a thermomechanical stress in the long-term rolling test until the appearance of a strong dark coloration (breaking time). Samples are taken at 5 minute intervals to measure the degree of coloration (yellowness index = YI). The activity of the stabilizing system is determined by measuring the values of YI according to standard ASTM D 1925-70 at 5 and 30 minutes and by measuring the rupture time (see Table 9).



   Table 9
Long-term rolling test
YI index of yellowing; thermal stability (breaking time)
 EMI53.1
 
 <tb>
 <tb> phosphite <SEP> according to <SEP> YI <SEP> YI <SEP> stability <SEP> thermal
 <tb> example <SEP> 5 <SEP> [min] <SEP> 30 <SEP> [min] <SEP> time <SEP> from <SEP> rupture <SEP> [min]
 <tb> 2 <SEP> 4.7 <SEP> 12.1 <SEP> 68
 <tb> 8 <SEP> 5.2 <SEP> 12.2 <SEP> 69
 <tb> 14 <SEP> 4.9 <SEP> 10.1 <SEP> 70
 <tb> 15 <SEP> 4.9 <SEP> 9, <SEP> 8 <SEP> 74
 <tb>
 
 EMI53.2
 The lower the value of YI, the more effectively the stabilizing system prevents yellowing and degradation of the organic polymer material. The time necessary for the appearance of a massive coloration (rupture time) indicates the long-term thermal stability.



   A stabilizer is all the more active as the coloring under thermal stress is delayed.



  Example 45
A mixture of 100 parts of E + S PVC (K value 80), 50.1 parts of plasticizer mixture consisting of dibutyl and dioctyl phthalate, 3.7 parts of an epoxidized fatty acid ester, is transformed into plastisol. 1.1 part of a stabilizer of the butyltin mercaptopropionate type (main constituent: dibutyltin isooctylmercaptopropionate) and 1.6 part of a phosphite according to the invention, and it is gelled on a PVC floor covering support at 200 C to form a sheet

  <Desc / Clms Page number 54>

 0.5 mm thick, and a static heat coloring test is carried out at 200 ° C. To this end, the yellowing index is determined at determined time intervals according to standard ASTM D 1925-70. The results are collated in Table 10 below.



   Table 10
Static heat test at 200 C
YI index of yellowing
 EMI54.1
 
 <tb>
 <tb> phosphite <SEP> according to <SEP> duration <SEP> from <SEP> test <SEP> [minutes]
 <tb> example <SEP> 0 <SEP> 5 <SEP> 7 <SEP> 9 <SEP> 11 <SEP> 13
 <tb> 2 <SEP> 20, <SEP> 1 <SEP> 13.9 <SEP> 16.8 <SEP> 22.7 <SEP> 29.5 <SEP> 49.8
 <tb> - <SEP> 37 <SEP> 43 <SEP> 53 <SEP> 58 <SEP> 64 <SEP> 68
 <tb>
 Example 46
 EMI54.2
 A mixture of 100 parts of S-PVC (value K 68), 3 parts of chalk (OMYALITE 95T), 0.6 part of calcium stearate, 2.7 parts is plasticized for 5 minutes in a cylinder mixer at 190 ° C. a stabilizer consisting of an epoxy resin, NaClO4 # H2O (applied on a chalk / Ca silicate support), a hydrocarbon wax and of 1,3-dimethyl-6-aminouracil, and 0.4 parts of a phosphite according to the invention.

   Strips of samples of the sheet obtained (0.3 mm) are submitted
 EMI54.3
 at a thermal stress in the Thenno-Takter apparatus of Mathis for 40 minutes at 190 C. The yellowing index (YI) is then measured according to standard ASTM D 1925-70. The results of the measurements are collated in Table 11.



   Table 11
Static heat test at 190 C
YI index of yellowing
 EMI54.4
 
 <tb>
 <tb> phosphite <SEP> according to <SEP> duration <SEP> from <SEP> test <SEP> [minutes]
 <tb> example <SEP> 0 <SEP> 5 <SEP> 10 <SEP> 15 <SEP> 20 <SEP> 30 <SEP> 40
 <tb> 2 <SEP> 19.1 <SEP> 21.7 <SEP> 22.9 <SEP> 26.8 <SEP> 32.3 <SEP> 55.3 <SEP> 97.1
 <tb>
 Example 47
A mixture of 100 parts of S-PVC (value K 60), 18 parts of dioctyl phthalate as plasticizer, 2 parts of an epoxidized fatty acid ester, 0, is plasticized for 5 minutes in a cylinder mixer at 1900C. 8 parts of a phosphite according to the invention and 1.5 parts of a Ca / Zn stearate (- 3/2). We submit tapes

  <Desc / Clms Page number 55>

 samples of the calendered sheet obtained (0.3 mm)

   to a static heat test in a Thenno-Takter of Mathis at 180 C and, after 6 minutes, the yellowing index (YI) is measured according to standard ASTM D 1925-70 (start of coloring) . The results are collated in Table 12.



   Table 12
Static heat test at 190 C
YI index of yellowing
 EMI55.1
 
 <tb>
 <tb> phosphite <SEP> according to <SEP> example <SEP> start <SEP> from <SEP> the <SEP> coloring
 <tb> YI <SEP> (6 <SEP> minutes)
 <tb> - <SEP> 27, <SEP> 9
 <tb> 2 <SEP> 12.2
 <tb> 15 <SEP> 6.7
 <tb>



    

Claims (43)

 Claims 1. Composition containing (i) a halogenated polymeric material, and (ii) at least one phosphite of formula 1  EMI56.1  where n is a number from 1 to 6,  EMI56.2  R is a divalent bridge having one of the formulas  EMI56.3    EMI56.4  - CH2-0-CH2ou  EMI56.5    m is a number from 1 to 5,  <Desc / Clms Page number 57>    R1, R2, R3 and R4 independently of one another represent a C4C22 alkyl, C7-C9 phenalkyl, C1-C8 cycloalkyl or (C1-C4 alkyl) -C5-C8 cycloalkyl, OR RI and R2 and / or R3 and R4 together represent a C2-C9 alkylene residue or a group of formula  EMI57.1  provided that a) the composition does not contain a stabilizer containing Ba,  Zn and / or Ca when RI + R2 and R3 + R4 represent a group of formula  EMI57.2  and R is a BRI or BR2 group, and that b) m is different from 2 when RI, R2, R3 and Rt are identical and represent C12-C22 alkyl radicals and R is a BR2 group; and at least one component (iii) which is an organotin compound selected from organotin sulfides, organotin mercaptides or organotin mercaptocarboxylates. 2. Composition according to claim 1, containing as constituent (i) a homopolymer or a copolymer of vinyl chloride. 3. Composition according to claim 1, in which n is between 1 and 4. 4. Composition according to claim 3, in which n is between 1 and 3. 5. Composition according to claim 3, in which n is equal to 1. 6. Composition according to claim 1, in which RI, R2, R3 and Rt represent, independently of each other, a C6-C22 alkyl or C7-C9 phenylalkyl residue, or RI and R2 and / or R3 and R4 together represent a remains C2-C9 alkylene. 7. The composition as claimed in claim 6, in which m is equal to 1 or 2 and RI, R2, R3 and Rt independently of one another represent a C6-C] $ alkyl or C7-C9 phenylalkyl, or RI and R2 and / or R3 and R4 together represent a C2-C9 alkylene residue. 8. Composition according to claim 1, in which R is a divalent bridge of formula BRI, BR3 or BR4. 9. Composition according to claim 1, in which R is a divalent bridge of formula BRI, BR2 or BR3.  <Desc / Clms Page number 58> 10. Composition according to claim 1, in which R is a divalent bridge of formula BRI. 11. Composition according to claim 10, in which RI, R2, R3 and R independently of one another represent a C6-C1S alkyl or phenylalkyl in Cy-Cg residue. 12. Composition according to claim 1, in which RI, R2, R3 and Rt are identical. 13. Composition according to claim 1, in which RI + R2 and R3 + R) are identical. 14. The composition as claimed in claim 10, in which RI, R2, R3 and Rt represent a Cs-Cn alkyl, C7-Cg phenylalkyl or C5-Cg cycloalkyl radical, or RI and R2 and / or R3 and R4 represent together a C2-C9 alkylene residue. 15. The composition as claimed in claim 1, in which R1, R2, R3 and R4 represent a C6-C22 alkyl, C7-C9 phenylalkyl or Cs-Cg cycloalkyl residue. 16. Composition according to claim 1, containing the phosphite of formula 1 in an amount of 0.01-10% by mass relative to the constituent (i). 17. Composition according to Claim 1, in which the component (iii) is a lubricant, plasticizer, pigment, non-sticking agent, modifying agent, shaping aid, blowing agent, anti-static agent, biocide, anti-haze product, colorant, flame retardant, filler, antioxidant, light stabilizer and / or other shaping stabilizer. 18. A method for stabilizing polymeric materials containing halogens, which comprises incorporating therein at least one composition as defined in claim 1. 19. The method of claim 18, wherein the polymeric material is polyvinyl chloride. 20. A phosphite of formula 1  EMI58.1  where n is a number from 1 to 6, R is a divalent bridge having one of the formulas  <Desc / Clms Page number 59>    EMI59.1  RI, R2, R3 and R represent, independently of each other, a C4C22 alkyl, C7-C9 phenalkyl, C5-C8 cycloalkyl or C1-C4 alkyl, CsC8 cycloalkyl, or RI and R2 and / or R3 and R4 together represent a C1-CD alkylene residue or a group of formula  EMI59.2 21. A phosphite according to claim 20, wherein RI, R2, R3 and R4 or RI + R2 and R3 + R4 are each identical. 22. A phosphite according to claim 20, where n takes a value from 1 to 4. 23. A phosphite according to claim 20, where n is equal to 1. 24. A phosphite according to claim 20, wherein RI, R2, R3 and R are Cg- alkyl  EMI59.3  CI s, or RI and R2 and / or R3 and R together represent a C2-C8 alkylene residue. 25. A composition comprising a synthetic or semi-synthetic organic polymer and at least one phosphite as defined in claim 20. 26. A composition according to claim 25, in which the polymer is a polyolefin, a polyurethane, a polycarbonate, a polyamide or an elastomer. 27. A composition comprising a lubricant, a hydraulic fluid, or a metal shaping fluid and at least one phosphite as defined in claim 20. 28. A composition according to claim 26, further comprising one or more other stabilizers.  <Desc / Clms Page number 60> 29. A composition according to claim 28, further comprising one or more other antioxidants or light stabilizers. 30. A process for stabilizing a synthetic or semisynthetic organic polymer, which comprises incorporating therein at least one phosphite as defined in claim 20. 31. A method for improving the performance properties of lubricants, hydraulic fluids, or metal shaping fluids, which comprises adding thereto at least one phosphite as defined in claim 20. 32. A phosphite of formula 1  EMI60.1  (I)  EMI60.2  where n is a number from 2 to 6,  EMI60.3  R is a divalent bridge having one of the formulas  EMI60.4  CH CHoO CH? CH CH3 CH3 UM3 L; H3 (BRI) or - CH- (H) -CH- (BR5)  EMI60.5  m is a number from 1 to 5, Ri, R2, R3 and Rt represent, independently of each other, a C4C22 alkyl, phenalkyl in Cy-C ?, cycloatkyl in C5-Cg or (C1-C4 alkyl) -cycloalkyl in C5-Cg, OR Ri and R2 and / or R3 and Rt together represent a C2-C9 alkylene residue or a group of formula  EMI60.6 33. A phosphite according to claim 32, in which n takes a value from 2 to 5.  <Desc / Clms Page number 61>   34. A phosphite according to claim 32, in which RI, R2, R3 and R4 represent a C1-C1 alkyl radical or RI and R2 and / or R3 and R4 together represent a C2-C9 alkylene residue. 35. A composition comprising a synthetic or semi-synthetic organic polymer and at least one phosphite as defined in claim 32. 36. A composition according to claim 35, in which the polymer is a polyolefin, a polyurethane, a polycarbonate, a polyamide or an elastomer. 37. A composition comprising a lubricant, a hydraulic fluid, or a metal shaping fluid and at least one phosphite as defined in claim 32. 38. A composition according to claim 35, further comprising one or more other stabilizers. 39. A composition according to claim 38, further comprising one or more other antioxidants or light stabilizers. 40. A process for stabilizing a synthetic or semi-synthetic organic polymer, which comprises incorporating therein at least one phosphite as defined in claim 32. 41. A composition comprising a lubricant, a hydraulic fluid, or a metal shaping fluid and at least one phosphite of formula 1  EMI61.1  where n is a number from 1 to 6, R is a divalent bridge having one of the formulas  EMI61.2    <Desc / Clms Page number 62>    EMI62.1    EMI62.2  - CH2--0-CH2or (BR5) ".  e (BR6) m is a number from 1 to 5, Ri, R2, R3 and R4 represent, independently of each other, a C4C22 alkyl, C7-C9 phenalkyl, Cs-Cg cycloalkyl or (C1-C4 alkyl ) -cyc1oalkyl in Cs-Cs, or RI and R2 and / or R3 and R4 together represent a C2-C9 alkylene residue or a group of formula  EMI62.3  provided that a) the composition does not contain a stabilizer containing Ba, Zn and / or Ca when RI + R2 and R3 + R4 represent a group of formula  EMI62.4  and if R is a BRI or BR2 group, and that  EMI62.5  b) m is different from 2 when RI, R2, R3 and R4 are identical and represent alkyl radicals in Ct2-C22 and R is a BR2 group. 42. A process for improving the performance properties of lubricants, hydraulic fluids, or metal shaping fluids, which comprises the addition of at least one phosphite of formula 1 (I)  <Desc / Clms Page number 63>    EMI63.1  where n is a number from 1 to 6,  EMI63.2  R is a divalent bridge having one of the formulas  EMI63.3    EMI63.4  -CH2-D-CH2or (BR5) 1 (BR6)  EMI63.5  m is a number from 1 to 5, RI, R2, R3 and R4 independently of one another represent a C4-C22 alkyl, C7-C9 phenalkyl, Cs-Cs cycloalkyl or (C1-C4 alkyl) - Cs-Cs cycloalkyl,  or RI and R2 and / or R3 and R together represent a C2-C9 alkylene residue or a group of formula  <Desc / Clms Page number 64>    EMI64.1  provided that a) the composition does not contain a stabilizer containing Ba, Zn and / or Ca when RI + R2 and R3 + R4 represent a group of formula  EMI64.2  and R is a BRI or BR2 group, and that  EMI64.3  b) m is different from 2 when RI, R2, R3 and R4 are identical and represent alkyl residues in CI 2-C22 and that R is a group BR2. 43. A method for improving the performance properties of lubricants, hydraulic fluids, or metal shaping fluids, which comprises adding thereto at least one phosphite as defined in claim 32.