Oligomers or polymers, compositions and uses of said oligomers or polymers

Abstract

The present invention relates to oligomers or polymers that are particularly suitable as stabilizers for organic materials, or compositions containing said oligomers or polymers, and to intermediates for synthesizing said oligomers or polymers.

Description

[Technical field]

[0001] The present invention relates to oligomers or polymers that are particularly suitable as stabilizers for organic materials, or to compositions containing said oligomers or polymers, and also to intermediates for the synthesis of said oligomers or polymers.

[0002] Organic materials such as plastics are subject to ageing processes that ultimately result in the loss of desired properties, such as, for example, mechanical property values. This process is called autoxidation and leads to changes in the polymer chains, such as, for example, molecular weight, or the formation of new chemical groups resulting from the scission of radical chains, by UV irradiation in the presence of oxygen or by mechanochemical processes. Stabilizers are therefore used to prevent or at least slow down said ageing. Important representatives of stabilizers are antioxidants, which interfere with the free radicals generated during autoxidation and hinder the decomposition process. A distinction is usually made between primary antioxidants, which can react directly with oxygen-containing free radicals or C radicals, and secondary antioxidants, which react with the intermediately generated hydroperoxides (see C.Krohnke et al., Antioxidants in Ullmann's encyclopedia of industrial chemistry, Wiley-VCH Verlag, Weinheim 2015). Typical representatives of primary antioxidants are, for example, phenolic antioxidants, amines, but also lactones. Classes of secondary antioxidants are phosphorus compounds, e.g., phosphites and phosphonites, but also organosulfur compounds, e.g., thioethers or disulfides. Usually in practice, primary and secondary antioxidants are often combined, resulting in a synergistic effect.

[0003] Plastics made from fossil raw materials such as crude oil and natural gas are increasingly being supplemented or replaced by plastics based on renewable raw materials available through biotechnological processes, but the primary and secondary antioxidants used for them (and for plastics produced from fossil raw materials) are not yet extensively based on renewable raw materials.

[0004] A further challenge for antioxidants, especially those used in food applications and in plastics at high temperatures, is to keep migration from the plastic and volatility of the product in which they are used as low as possible without adversely affecting efficacy.

[0005] Basically, primary antioxidants made from renewable raw materials are known and are sometimes used in plastics. A typical example is tocopherol (vitamin E). Like common antioxidants, tocopherol has a sterically hindered phenolic structure and can be used alone or in combination with secondary antioxidants (e.g. S. Al Malaika, Macromol. Symp. 2001, 176, 107). For example, tocopherol can be isolated from natural substances such as wheat germ oil, sunflower oil or olive oil. Other well-known phenolic antioxidants from natural substances that have proven antioxidant effects in polymers are, for example, quercetin, hyperin, rutin, dihydromyrecetin, silymarin, curcumin, rosmarinic acid or cardanol.

[0006] Materials with high molecular weight, especially oligomers or polymers, can preferably be used to reduce the migration and volatility of the antioxidant.

[0007] The preparation and effectiveness of such antioxidants are described, for example, in the following patents: EP 2 061 829 (Preparation of liquid polymeric phosphites and phosphonites for use as stabilizers) EP 0 685 519 (Oligomeric HALS-phosphites and HALS-phosphonites as stabilizers)

[0008] However, the known oligomeric and polymeric antioxidants are not based on renewable raw materials and / or do not contain a 6-hydroxychroman core.

[0009] It was therefore an object of the present invention to provide effective oligomeric and polymeric antioxidants which are based partly or largely on renewable raw materials.

[0010] This object is achieved with respect to an oligomer or polymer comprising a phosphorus-containing structural element having the features according to claim 1, with respect to a composition thereof comprising said oligomer or polymer and an organic component to be stabilized having the features according to claim 8, with respect to possible uses of the inventive oligomer or polymer having the features according to claim 13, with respect to moulding compounds or moulded parts having the features according to claim 15 and with respect to intermediates suitable for synthesising the inventive oligomer or polymer having the features according to claim 16. The respective dependent claims represent advantageous developments.

[0011] The present invention therefore relates to oligomers or polymers which comprise a structure according to general formula I as a structural element. [ka] Here, R 1 is defined by the following formula II [ka] where R is the same or different at each occurrence and is selected from the group consisting of hydrogen or a linear or branched alkyl radical having 1 to 36 carbon atoms; and x is 0 or 1.

[0012] For the purposes of the present invention, the terms oligomer or polymer are generally used according to the definition established by IUPAC as defined in Pure Appl. Chem. 2016;88(10-11):1073-1100.

[0013] In particular, oligomers are understood to be molecules having 3 to 10 repeat units, and polymers are understood to be molecules having more than 10 repeat units, which usually results in an average molecular weight (number average) of about 1000 to 4000 for oligomers and more than 4000 for polymers.

[0014] Surprisingly, it has been found that the oligomers or polymers of the invention are highly effective.

[0015] According to a preferred embodiment, R 1 is defined according to formula IIa below: [ka]

[0016] A further preferred embodiment provides that the oligomer or polymer comprises the following repeat unit according to formula III: [ka] where D is the same or different for each occurrence and is functionality derived from a diol.

[0017] Here, the functional group derived from a diol is preferably a functional group derived from an aliphatic, aromatic, or heterocyclic diol.

[0018] According to an exemplary embodiment, the functional groups derived from the diol are as follows: a) functional groups derived from aliphatic diols, preferably functional groups derived from ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,3-cyclohexanediol and / or 1,4-cyclohexanedimethanol, b) Functional groups derived from aromatic diols, preferably those derived from hydroquinone, resorcinol, 1,5-, 2,6- or 2,7-dihydroxynaphthalene, vanillyl alcohol or the following diols: [ka] where, independently of each other, A is a direct bond, -O-, -SO 2 -, -C(O)-, -CH(CH 3 )- or -C(CH 3 ) 2 - means, and R' and R'' are the same or different at each occurrence and are selected from the group consisting of linear or branched alkyl moieties having 1 to 36 carbon atoms; c) a functional group derived from a heterocyclic diol, preferably derived from hydroxyethyl-4-hydroxytetramethylpiperidine, 1,4-dithiane-2,5-diol, or d) Functional groups derived from the following diols: 2,3-Dimethoxy-1,4-butanediol [ka]

[0019] According to a further embodiment of the invention, the oligomer or copolymer is a cooligomer or copolymer, i.e. comprises at least two different repeat units based on a repeat unit according to formula I.

[0020] The embodiment provides, for example, that the oligomer or polymer has the following repeat units according to formula I, which correspond to the following definitions according to formulae III and IIIa: [ka] Here, R 1 , D and x are as defined above, and the definition of D' corresponds to the definition of D, with the proviso that D and D' are derived from different diols.

[0021] For example, the group D derived from a diol as used in formula III above may be selected from one or more diols as described in a) or b) above.

[0022] The group D' derived from a diol can be, for example, a diol selected from the diols as described above under c).

[0023] For example, the molar ratio of repeating units III:IIIa can be from 0.1:99.9 to 50:50, preferably from 0.5:99.5 to 10:90.

[0024] The oligomer or polymer preferably comprises only repeat units according to formula I, where x = 0. Alternatively, the oligomer or polymer can comprise both repeat units of formula I, where x = 0, and repeat units of formula I, where x = 1, where the molar ratio of repeat units of formula I, where x = 0: repeat units of formula I, where x = 1 is from 50:50 to <100:>0, preferably from 90:10 to 99.9:0.1.

[0025] The present invention also relates to a composition comprising at least one organic component to be stabilized and at least one oligomer or polymer according to the invention as described above.

[0026] For example, the composition can be provided to contain at least one oligomer or polymer in a weight ratio of the total composition of 0.01 to 5.0 parts by weight, preferably 0.02 to 2.0 parts by weight, and particularly preferably 0.05 to 1.0 parts by weight.

[0027] A preferred embodiment provides that the at least one organic component to be stabilized is selected from the group consisting of: Plastics (synonymous with "polymers"), in particular thermoplastic, elastomeric or duromeric plastics; at least one oil, fat or wax, in particular a mineral oil, a vegetable fat or oil or an animal fat or oil, such as palm oil, olive oil, rapeseed oil, linseed oil, soybean oil, sunflower oil, castor oil, fish oil or beef tallow, and for example an oil, fat or wax based on synthetic esters, Mineral or synthetic lubricating oils, hydraulic oils, engine oils, turbine oils, gear oils, metalworking oils or lubricating greases, and Polymerizable monomers, in particular radically polymerizable monomers, in particular monomers which can be radically polymerized by an initiator such as a peroxide or oxygen, such as, for example, acrylic esters, methacrylic esters, acrylonitrile, styrene or vinyl chloride.

[0028] Suitable thermoplastic or duromer polymers are in particular: a) polymers from olefins or diolefins, such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, for example natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers and copolymers in the form of random or block structures, such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic acid, for example with 5-ethylidene-2-norbornene as comonomer; Esters such as ethylene-butyl acrylate, ethylene-acrylic acid and its salts (ionomers), and terpolymers such as ethylene-acrylic acid-glycidyl (meth)acrylate, graft polymers such as polypropylene-graft-maleic anhydride, polypropylene-graft-acrylic acid, polyethylene-graft-acrylic acid, polyethylene-polybutyl acrylate-graft-maleic anhydride, and blends such as LDPE / LLDPE or long chain branched polypropylene copolymers prepared with α-olefins as comonomers, such as 1-butene, 1-hexene, 1-octene or 1-octadecene, b) polystyrene, polymethylstyrene, poly-α-methylstyrene, polyvinylnaphthalene, polyvinylbiphenyl, polyvinyltoluene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile (SAN), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including the corresponding graft copolymers, for example styrene on butadiene, maleic anhydride on SBS or SEBS, and methyl methacrylate, graft copolymers of styrene-butadiene and ABS (MABS), and hydrogenated polystyrene derivatives, for example polyvinylcyclohexane, c) halogen-containing polymers, such as polyvinyl chloride (PVC), polychloroprene and polyvinylidene chloride (PVDC), copolymers of vinyl chloride and vinylidene chloride or of vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo- and copolymers, especially those with ethylene oxide (ECO); d) polymers of unsaturated esters, for example polyacrylates and polymethacrylates, such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamide, copolymers, such as polyacrylonitrile-polyalkyl acrylates, e) polymers of unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, f) polyacetals, such as polyoxymethylene (POM) or copolymers, for example with butanal; g) polyphenylene oxide and its blends with polystyrene or polyamides; h) polymers of cyclic ethers, such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, polytetrahydrofuran; i) polyurethanes, in particular linear polyurethanes (TPUs), polyureas, from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, such as, for example, 2,4- or 2,6-tolylene diisocyanate or methylene diphenyl diisocyanate; j) polyamides, for example polyamide 6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides, for example polyphthalamides, for example those made from terephthalic acid and / or isophthalic acid and aliphatic diamines, for example hexamethylenediamine or m-xylylenediamine, or those made from aliphatic dicarboxylic acids, for example adipic acid or sebacic acid, and aromatic diamines, for example 1,4- or 1,3-diaminobenzene, for example blends of different polyamides, such as PA-6 and PA6.6, or blends of polyamides and polyolefins, for example PA / PP, k) polyimides, polyamide-imides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins, l) polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthylate (PEN), poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoic acid, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetramethylene succinate, polycaprolactone; m) Polycarbonates, polyester carbonates and blends such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA, n) cellulose derivatives, such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate; o) epoxy resins consisting of di- or polyfunctional epoxy compounds, for example in combination with hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytic hardeners; p) phenolic resins, such as phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, q) unsaturated polyester resins, alkyd resins from diols and unsaturated dicarboxylic acids, including vinyl compounds, e.g. styrene; r) silicones, for example based on dimethylsiloxane, methylphenylsiloxane or diphenylsiloxane, for example terminated with vinyl groups s) as well as mixtures, combinations or blends of two or more of the foregoing polymers.

[0029] When the polymers identified in a) through r) are copolymers, they may exist in the form of random, block or tapered structures.

[0030] Furthermore, the above-mentioned polymers may exist in the form of linear, branched, star or hyperbranched structures.

[0031] When the polymers identified under a) to r) are stereoregular polymers, they can exist in isotactic, stereotactic form, but also in atactic form or as stereoblock copolymers.

[0032] Furthermore, the polymers identified in a) through r) can have both amorphous and (partially) crystalline morphologies.

[0033] Optionally, the polyolefins according to a) may be crosslinked, for example crosslinked polyethylene is called X-PE.

[0034] Furthermore, the compounds of the present invention can be used for the stabilization of rubber and elastomers. Here, natural rubber (NR) or synthetic rubber materials can be used. Further suitable rubbers and elastomers are, in particular, butadiene rubber (BR), styrene-butadiene rubber (SBR), chlorobutadiene rubber (CR), acrylonitrile-butadiene rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR), ethylene-epichlorohydrin rubber (ECO) or ethylene acrylate rubber (AEM).

[0035] Further particularly preferred are polymers from renewable raw materials, such as polylactic acid (PLA), polyhydroxybutyric acid, polyhydroxyvaleric acid, polybutylene succinate (PBS) or polybutylene succinate-co-adipate (PBSA).

[0036] A further embodiment of the composition according to the invention provides that the composition comprises at least one additive selected from the group consisting of primary antioxidants, secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilic agents, hydrophobic agents, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, foaming agents, prodegradants, defoaming aids, odor scavengers, marking agents, antifog agents, fillers and reinforcing agents.

[0037] In a preferred embodiment, the composition comprises in particular acid scavengers, for example based on salts of long-chain acids such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, calcium lactate, calcium stearoyl-2-lactylate or hydrotalcites, in particular synthetic hydrotalcites based on aluminum, magnesium and zinc, and also hydrocalumites, zeolites, and / or alkaline earth metal oxides, for example calcium oxide and magnesium oxide, and / or alkaline earth metal carbonates, for example calcium carbonate, magnesium carbonate or dolomite, and / or hydroxides such as brucite.

[0038] In a further preferred embodiment, the composition comprises a light stabilizer and / or a dispersant and / or a filler deactivator from the group of the hindered amines (HALS).

[0039] Suitable primary antioxidants (A) are phenolic antioxidants, amines and lactones. Additionally, ascorbic acid is considered a primary antioxidant.

[0040] Preferred synthetic phenolic antioxidantsFor example, Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4 -methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof; Alkylthiomethylphenols, such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol; For example, hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate; Tocopherols, such as α-, β-, γ-, δ-tocopherol and mixtures thereof (vitamin E); For example, hydroxylated thiodiphenyl ethers such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), and 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide; Alkylidenebisphenols, such as, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methyl-phenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-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; O-, N- and S-benzyl compounds such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate; For example, hydroxybenzylated malonic acid esters such as dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonic acid ester, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonic acid ester, didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid ester, and bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid ester; Aromatic hydroxybenzyl compounds, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol; Triazine compounds, such as 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, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate; Benzylphosphonates, such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salts of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid; Acylaminophenols, such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate; Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with, for example, the following monohydric or polyhydric alcohols: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with, for example, the following monohydric or polyhydric alcohols: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) Isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro-[5.5]-undecane; Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with, for example, the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; Esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with, for example, the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as, for example, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard® XL-1, sold by Uniroyal);

[0041] Particularly preferred phenolic antioxidants are: [ka] [ka]

[0042] Suitable amine-based antioxidants For example, N,N'-Diisopropyl-p-phenylenediamine, N,N'-Di-sec-butyl-p-phenylenediamine, N,N'-Bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-Bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-Bis(1-methylheptyl)-p-phenylenediamine, N,N'-Dicyclohexyl-p-phenylenediamine, N,N'-Diphenyl-p-phenylenediamine, N,N'-Bis( 2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)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, octylated diphenylamines such as p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-Octadecanoylamino-phenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines, mixtures of mono- and di-alkylated nonyldiphenylamines, mixtures of mono- and di-alkylated dodecyldiphenylamines, mixtures of mono- and di-alkylated isopropyl / isohexyl-diphenylamines, mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, mixtures of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, and mixtures or combinations thereof.

[0043] Further preferred amine antioxidants are hydroxylamines or N-oxides (nitrones), such as N,N-dialkylhydroxylamines, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α-phenylnitrone, N-octadecyl-α-hexadecylnitrone, and GenoxEP (SI group) according to the following formula: [ka]

[0044] Preferred lactones are benzofuranones and indolinones., for example, 3-(4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-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)benzofuran- 2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, etc.

[0045] Preferred Secondary Antioxidants are phosphorus compounds such as phosphites and phosphonites, and organosulfur compounds such as, for example, sulfides and disulfides.

[0046] Preferred phosphites / phosphonites For example, Triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tri(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, (2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-di Benz[d,g]-1,3,2-dioxaphosphocin, 2,2',2''-nitrilo[triethyltris(3,3'',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl))phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

[0047] Particularly preferred phosphites / phosphonites is as follows: [ka] [ka]

[0048] Suitable Sulfur Compounds are, for example, distearyl thiodipropionate, dilauryl thiodipropionate, ditridecyl dithiopropionate, ditetradecyl thiodipropionate, 3-(dodecylthio)-,1,1'-[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propanediyl]propanoic acid ester.

[0049] Suitable Light Stabilizers are, for example, compounds based on 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acid, acrylates, oxamides, and 2-(2-hydroxyphenyl)-1,3,5 triazines.

[0050] Suitable 2-(2'-hydroxyphenyl)benzotriazoles are, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-( 3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxy-phenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethyl-benzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonyl-ethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl-ethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl-ethyl)phenyl)-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-benzotriazole, '-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-Tetramethylbutyl)-6-benzotriazol-2-ylphenol];Transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300;[R-CH, 2 CH 2 -COO-CH 2 CH 2 -]-2, where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole, 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl]benzotriazole.

[0051] Suitable 2-hydroxybenzophenones are, for example, the 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethyloxy derivatives of 2-hydroxybenzophenone.

[0052] Suitable acrylates are, for example, ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

[0053] Suitable esters of benzoic acid are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0054] Suitable oxamides are, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides, and mixtures of o- and p-ethoxy-disubstituted oxanilides.

[0055] Suitable 2-(2-hydroxyphenyl)-1,3,5-triazines are, for example, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxy-phenyl)-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-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)-phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2 -[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy / tridecyloxy-2-hydroxy-propoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-Dimethylphenyl-1,3,5-triazine.

[0056] Suitable Metal Deactivators are, for example, N,N'-diphenyloxamide, N-salicylar-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxylyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

[0057] Suitable hindered aminesExamples of the bis(1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebazate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazate, and bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl. 4-Hydroxybenzylmalonate, condensation products from 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products from N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)-nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine, and reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane with epichlorohydrin.

[0058] Particularly preferred hindered amines are: [ka] [ka] [ka]

[0059] Preferred oligomeric and polymeric hindered amines have the following structures: [ka] [ka] Here, n is an integer from 3 to 100 in each of the above compounds.

[0060] Suitable Dispersants For example, Polyacrylates, e.g. copolymers with long chain side groups, polyacrylate block copolymers, alkylamides, e.g. N,N'-1,2-ethanediylbisoctadecaneamide sorbitan ester, e.g. monostearyl sorbitan ester, titanates and zirconates, reactive copolymers with functional groups, e.g. polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes, e.g. dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers, e.g. polyethylene block polyethylene oxide, dendrimers, e.g. dendrimers containing hydroxyl groups.

[0061] Suitable Nucleating Agentsare, for example, talc, the alkali metal or alkaline earth metal salts of the following monofunctional and polyfunctional carboxylic acids, for example, benzoic acid, succinic acid, adipic acid, for example, sodium benzoate, zinc glycerolate, aluminum hydroxybis(4-tert-butyl)benzoate, benzylidene sorbitol, for example 1,3:2,4-bis(benzylidene)sorbitol or 1,3:2,4-bis(4-methylbenzylidene)sorbitol, bitol, 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate, and trisamides and diamides, such as trimesic acid tricyclohexylamide, trimesic acid tri(4-methylcyclohexylamide), trimesic acid tri(tert-butylamide), N,N',N''-1,3,5-benzenetriyltris(2,2-dimethylpropanamide) or 2,6-naphthalenedicarboxylic acid dicyclohexylamide.

[0062] Suitable antinucleating agents is an azine dye such as, for example, nigrosine.

[0063] Suitable flame retardants For example, a) For example, Al(OH) 3 , Mg(OH) 2 , AlO(OH), MgCO 3 Inorganic flame retardants such as, for example, sheet silicates such as montmorillonite or sepiolite, for example, Mg-Al silicates, POSS (polyhedral oligomeric silsesquioxane) compounds, unmodified or organically modified double salts such as huntite, hydromagnesite or halloysite, and Sb 2 O 3 , Sb 2 O 5 , MoO 3 , zinc stannate, zinc hydroxide stannate, b) nitrogen-containing flame retardants, such as melamine, melem, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine metal phosphates, such as melamine aluminum phosphate, melamine zinc phosphate, melamine magnesium phosphate, and the corresponding pyrophosphates and polyphosphates, poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide, c) radical formers, such as, for example, alkoxyamines, hydroxylamine esters, azo compounds, dicumyl or polycumyl, hydroxyimides and their derivatives, for example hydroxyimide esters or hydroxyimide ethers, d) phosphorus-containing flame retardants, for example red phosphorus, phosphates, for example resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates, for example salts of hypophosphorous acids and their derivatives, for example alkyl phosphinates, for example diethylaluminium phosphinate or diethylzinc phosphinate or aluminium phosphinate, aluminium phosphites, aluminium phosphonates, phosphonate esters, oligomeric and polymeric derivatives of methanephosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and substituted compounds thereof, e) halogenated flameproofing agents based on chlorine and bromine, such as polybrominated diphenyl oxides, e.g. decabromodiphenyl oxide, tris(3-bromo-2,2-bis(bromomethyl)propyl phosphate, tris(tribromoneopentyl)phosphate, tetrabromophthalic acid, 1,2-bis(tribromophenoxy)ethane, hexabromocyclododecane, brominated diphenylethane, tris-(2,3-dibromopropyl)isocyanurate, ethylene-bis-(tetrabromophthalimide), tetrabromobisphenol A, brominated polystyrene, brominated polybutadiene or polystyrene-brominated polybutadiene copolymers, brominated polyphenylene ethers, brominated epoxy resins, polypentabromobenzyl acrylate, optionally Sb 2 O 3 and / or Sb 2 O 5 Combined with, f) optionally on a support material such as, for example, silica, a borate, such as, for example, zinc borate or calcium borate; g) Sulfur-containing compounds, such as elemental sulfur, disulfides and polysulfides, thiuram sulfides, dithiocarbamates, mercaptobenzothiazoles and sulfenamides; h) anti-drip agents such as, for example, polytetrafluoroethylene; i) silicon-containing compounds, such as, for example, polyphenylsiloxanes; j) carbon modifications, such as, for example, carbon nanotubes (CNTs) or graphene; as well as combinations or mixtures thereof.

[0064] Suitable Fillers and Reinforcing Materialsare, for example, synthetic or natural materials, such as calcium carbonate, silicates, glass fibers, glass beads (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and hydroxides, carbon black, graphite, carbon nanotubes, graphene, wood flour, or fibers of natural origin, such as cellulose or synthetic fibers. Further suitable fillers are hydrotalcites or zeolites or phyllosilicates, such as montmorillonite, bentonite, beidellite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite, etc.

[0065] Suitable pigments can be inorganic or organic in nature. Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, and organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrenes, isoindolinones, azo compounds, perylenes, phthalocyanines or pyranthrones. Further suitable pigments are metal-based effect pigments or metal oxide-based pearlescent pigments.

[0066] For linearly increasing the molecular weight of polycondensation polymers, polyesters or polyamides Suitable Chain Extenders are, for example, diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides. Further suitable chain extenders are polymeric compounds, such as, for example, polystyrene-polyacrylate-polyglycidyl (meth)acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.

[0067] Suitable Optical Brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis(styryl)biphenyls, in particular optical brighteners of the formula: [ka]

[0068] Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxides or polyglycidyl (meth)acrylates and their copolymers, for example with styrene, and epoxides, for example those of the following structure: [ka] [ka]

[0069] Suitable antistatic agents are, for example, ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymers such as polyetheramides.

[0070] Preferred Antiozonants is the above-mentioned amine, for example N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine.

[0071] Polycondensation polymer Additives suitable for increasing molecular weight(Chain extenders) are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides. Further suitable chain extenders are polymeric compounds such as, for example, polystyrene-polyacrylate-polyglycidyl (meth)acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.

[0072] Suitable additives for increasing electrical conductivity are, for example, the antistatic agents mentioned, carbon compounds such as carbon black and carbon nanotubes and graphene, metal powders such as, for example, copper powder, and conductive polymers such as, for example, polypyrrole, polyaniline and polythiophene. Additives suitable for increasing the thermal conductivity are, for example, aluminum nitride and boron nitride.

[0073] Suitable infrared active additives are, for example, aluminum silicates, hydrotalcites, or dyes such as phthalocyanines or anthraquinones.

[0074] Suitable release agent are, for example, silicones, soaps and waxes, such as montan wax.

[0075] Suitable impact modifiers are, for example, ethylene copolymers with acrylates, methacrylates and / or ethylenically unsaturated carboxylic acids, which can be fully or partially neutralized, for example, with zinc, or copolymers of ethylene, propylene and dienes, and core-shell particles, for example, ethylene copolymers with polybutyl acrylate and polymethyl methacrylate.

[0076] Compatibilizercontains, for example, the structural elements of the respective blend components used and mixed in thermodynamically immiscible blends or recycle mixtures. Suitable compatibilizers for polyolefin blends are, for example, olefin block copolymers consisting of ethylene, propylene and an α-olefin, for example 1-octene. Other compatibilizers, in particular for compatibilizing polar polymers such as PET or polyamides and non-polar polymers such as PP or PE, are, for example, polypropylene-g-maleic anhydride, polyethylene-g-maleic anhydride, polypropylene-g-acrylic acid, polyethylene-g-acrylic acid, poly(ethylene-co-maleic anhydride), SBS-g-maleic anhydride or SEBS-g-maleic anhydride.

[0077] Suitable Crosslinking Agents are, for example, peroxides, dialkyl peroxides, alkylaryl peroxides, peroxy esters, peroxy carbonates, diacyl proxides, peroxy ketals, silanes, such as vinyl trimethoxy silane, vinyl triethoxy silane, vinyl triacetoxy silane, vinyl tris (2-methoxy ethoxy) silane, 3-methacryloyloxy propyl trimethoxy silane, vinyl dimethoxy methyl silane or ethylene-vinyl silane copolymers.

[0078] Suitable decomposition agents are additives that specifically promote or control the degradation of polymers in the environment. Examples are transition metal fatty acid esters, e.g., of manganese or iron, that promote the oxidative and / or photooxidative degradation of, e.g., polyolefins, or enzymes that induce the hydrolytic degradation of, e.g., aliphatic polyesters.

[0079] Suitable Chemical Blowing Agentsis, for example, an azo compound such as azodicarboxylic diamide, a sulfonyl semicarbazide such as p-toluenesulfonyl semicarbazide, a tetrazole such as 5-phenyltetrazole, a hydrazide such as p-toluenesulfonyl hydrazide, 4,4'-oxybis(benzenesulfonyl)hydrazide, an N-nitroso compound such as N,N'-dinitrosopentamethylenetetramine, or a carbonate such as sodium bicarbonate or zinc carbonate.

[0080] Suitable slip agents is, for example, an amide wax such as erucamide or oleamide.

[0081] Suitable antiblocking agents are, for example, silica, talc or zeolites.

[0082] Suitable anti-fog additives are, for example, ethoxylated sorbitan esters, ethoxylated fatty acid alcohols or ethoxylated alkylamine esters.

[0083] Suitable Biocides is, for example, a quaternary ammonium salt or silver salt, colloidal silver or silver complex, or a natural product derivative, such as chitosan.

[0084] Suitable aldehyde scavengers are amines, hydroxylamines, polyvinyl alcohols, zeolites or cyclodextrins, suitable formaldehyde scavengers are, for example, melamine derivatives such as benzoguanamine or urea derivatives such as allantoin.

[0085] Suitable odor-binding or odor-suppressing materials is a silicate, such as calcium silicate, a zeolite, or a salt of a hydroxy fatty acid, such as, for example, zinc ricinoleate.

[0086] Suitable markers is, for example, a fluorescent dye or a rare earth.

[0087] Suitable release agentis, for example, montan wax.

[0088] Furthermore, the present invention relates to the use of the oligomers or polymers according to the invention as stabilizers for organic materials.

[0089] In particular, the oligomers or polymers according to the invention can be used as stabilizers for: - To prevent the thermal, actinic or oxidative degradation of plastics or as a flame retardant in plastics thermal, actinic or oxidative decomposition of oils, fats or waxes, in particular mineral oils, vegetable or plant oils or animal fats or tallow, for example palm oil, olive oil, rapeseed oil, linseed oil, soybean oil, sunflower oil, castor oil, fish oil or beef tallow, and oils, fats or waxes, for example based on synthetic esters, Thermal, actinic or oxidative degradation of mineral or synthetic lubricating oils, hydraulic oils, engine oils, turbine oils, gear oils, metalworking oils or lubricating greases; or Against the premature polymerization and / or oxidation of polymerizable monomers, in particular monomers that can be radically polymerized by initiators such as, for example, peroxides or oxygen, such as, for example, acrylic esters, methacrylic esters, acrylonitrile, styrene or vinyl chloride.

[0090] For example, the oligomers or polymers according to the invention are suitable as plastic stabilizers in the form of injection molded parts, foils or films, foams, fibers, cables and pipes, profiles, hollow bodies, ribbons, membranes, such as membranes for example geomembranes, or as adhesives produced by extrusion, injection molding, blow molding, calendering, pressure processes, spinning processes, rotational molding, for example, in the electrical and electronics industries, construction industry, transport industry (automobiles, aircraft, ships, trains), medical applications, household and electrical appliances, vehicle parts, consumer goods, packaging, furniture, for textiles. Further fields of application are lacquers, paints and coatings, and the stabilization of oils, fats and lubricants against thermal, actinic or oxidative degradation, or as flame retardants.

[0091] The invention also relates to intermediates useful for the preparation of the oligomers or polymers according to the invention. This intermediate has the following general formula IV:

Chemical formula

[0092] Stabilization method The additives of the invention can be present as powders, liquids, oils, compressed, on a carrier material, as granules, solutions or flakes, and are preferably mixed with the polymer to be stabilized; the polymer matrix is melted and then cooled. Alternatively, it is also possible to introduce the additive into the molten polymer melt.

[0093] When further components are added to the polymer composition, said components can be added to the polymer separately in the form of liquids, powders, granules or compressed products as described above, or together with the additive composition according to the invention.

[0094] The additive composition and optional additional additives are incorporated into plastics by conventional processing methods, where the polymer is preferably melted and mixed with the additive composition according to the invention and optional additional additives using mixers, kneaders and extruders. Extruders, such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, etc., preferably equipped with vacuum degassing, are preferred as processing machines. Processing can be carried out in air or optionally under inert gas conditions.

[0095] Furthermore, the additive composition according to the invention can be prepared and introduced in the form of so-called masterbatches or concentrates, which contain, for example, 10 to 90% of the composition according to the invention in a polymer.

[0096] The subject matter of the present invention is not limited to the examples, but the invention is explained in detail using the following embodiments.

[0097] Synthesis Example 1: Synthesis of Tocopherol Phosphorus Dichloride 1 ml (11.4 mmol) of phosphorus trichloride, 4.9117 g (11.4 mmol) of α-tocopherol and 40 ml of chloroform are placed in a 250 ml three-neck flask equipped with a reflux condenser and a magnetic stirrer. The reaction mixture is heated at 70 °C for 10 h. The purity and conversion of α-tocopherol phosphorus dichloride are 1 H and 31 The purity of the product is >99% as determined by PNMR spectroscopy. [ka]

[0098] Synthesis Example 2: Synthesis of polymeric phosphite having isosorbide units A structure comparable to that of Example 1 was used. 1.5015 g (10.3 mmol) of isosorbide, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added to the tocopherol phosphorus dichloride. 2 ml (49.3 mmol) of methanol are added after 1 hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is: 1 H and 31 Determined by PNMR spectroscopy. [ka]

[0099] Synthesis Example 3: Synthesis of a copolymer containing isosorbide and piperidine units A similar structure to that of Example 1 was used. To the tocopherol phosphorus dichloride, 0.2063 g (1.0 mmol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-ethanol, 4 ml (28.9 mmol) of triethylamine and 20 ml of chloroform are added. After 1 hour, 1.3467 g (9.2 mmol) of isosorbide, 5.5 ml (39.7 mmol) of triethylamine and 20 ml of acetonitrile are added to the reaction mixture. 2 ml (49.3 mmol) of methanol are added after 1 hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is 1 H and 31 Determined by PNMR spectroscopy. [ka]

[0100] Synthesis Example 4: Synthesis of polymeric phosphite having hydroquinone units A similar structure to that of Example 1 was used. To the tocopherol phosphorus dichloride, 1.1290 g (10.3 mmol) of hydroquinone, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added. 2 ml (49.3 mmol) of methanol are added after 1 hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is 1 H and 31Determined by PNMR spectroscopy. [ka]

[0101] Synthesis Example 5: Synthesis of a copolymer containing hydroquinone and piperidine units A similar structure to that of Example 1 was used. To the tocopherol phosphorus dichloride, 0.2065 g (1.0 mmol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-ethanol, 4 ml (28.9 mmol) of triethylamine and 20 ml of chloroform are added. After 1 hour, 1.0189 g (9.2 mmol) of hydroquinone, 5.5 ml (39.7 mmol) of triethylamine and 20 ml of acetonitrile are added to the reaction mixture. 2 ml (49.3 mmol) of methanol are added after 1 hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is 1 H and 31 Determined by PNMR spectroscopy. [ka]

[0102] Synthesis Example 6: Synthesis of polymeric phosphite having 1,4-cyclohexanediol units A similar structure to that of Example 1 was used. To the tocopherol phosphorus dichloride, 1.1952 g (10.3 mmol) of 1,4-cyclohexanediol, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added. 2 ml (49.3 mmol) of methanol are added after 1 hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is 1 H and 31 Determined by PNMR spectroscopy.

[0103] Synthesis Example 7: Synthesis of polyphosphite having vanillyl alcohol units A similar structure to that of Example 1 was used. 1.5862 g (10.3 mmol) of vanillyl alcohol, 8 ml (36.1 mmol) of triethylamine, and 20 ml of acetonitrile are added to the tocopherol phosphorus dichloride. 2 ml (49.3 mmol) of methanol are added after 1 hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is 1 H and 31 Determined by PNMR spectroscopy.

[0104] Synthesis Example 8: Synthesis of polyphosphite having 1,6-hexanediol units A similar structure to that of Example 1 was used. 1.2158 g (10.3 mmol) of 1,6-hexanediol, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added to the tocopherol phosphorus dichloride. 2 ml (49.3 mmol) of methanol are added after 1 hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is 1 H and 31 Determined by PNMR spectroscopy.

[0105] Synthesis Example 9: Synthesis of polyphosphite having hydroxyethyl-4-hydroxytetramethylpiperidine units A similar structure to that of Example 1 was used. 2.0713 g (10.3 mmol) of hydroxyethyl-4-hydroxytetramethylpiperidine, 8 ml (36.1 mmol) of triethylamine and 20 ml of acetonitrile are added to the tocopherol phosphorus dichloride. 2 ml (49.3 mmol) of methanol are added after 1 hour at room temperature. The product is purified in toluene. The purity of the polyphosphite is 1 H and 31 Determined by PNMR spectroscopy.

[0106] Example 1: Long-term extrusion The compounds of Examples 2, 3, 4, 6, 7, 8 and 9, as well as the commercially available phosphites ADK STAB 2112 (tris(2,4-di-tert-butylphenol)phosphite) and Doverphos S-9228 (bis(2,4-dicumylphenyl)pentaerythritol diphosphite), were incorporated into polypropylene (Moplen HP 500 N) on a Micro Sec Model 2009. The compounds were treated at 200° C. for 30 minutes and the force loss was measured.

[0107] [Table 1] [Table 2]

[0108] The polymer according to the invention has a higher residual strength than the comparative example, resulting in a greater stabilizing effect.

[0109] Example 2: Multiple Extrusions For further testing, the phosphites were treated five times at 230°C with and without a phenolic stabilizer (ADK STAB AO 60, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)) using a Thermo Scientific Process 11. The compounds were analyzed by measuring the MFR (Melt Flow Rate).

[0110] [Table 3]

[0111] [Table 4]

[0112] In the case of multiple extrusions, the lowest MFR values, ie the best stabilizing effect, are obtained with the stabilizing agent according to the invention.

[0113] Example 3: Multiple extrusions at 260°C For further testing, the phosphites were processed five times at 260°C without the phenolic stabilizer using a Thermo Scientific Process 11. The compounds were analyzed by measuring the MFR (Melt Flow Rate). [Table 5]

[0114] In the case of multiple extrusions, the lowest MFR values, ie the best stabilizing effect, are obtained with the stabilizer according to the invention, even at high temperatures (260° C.).

Claims

1. Contains as a structural element a structure according to general formula I, 【Chemistry 1】 where R １ is defined by the following formula: 【Chemistry 2】 where x is 0 or 1; Further comprising the following repeat unit according to formula III: 【Chemistry 4】 where D is the same or different in each occurrence and is a functional group derived from a diol; The oligomer or polymer, wherein the diol-derived functional group is an aliphatic, aromatic, or heterocyclic diol-derived functional group.

2. The functional group derived from the diol is a) a functional group derived from an aliphatic diol; b) a functional group derived from an aromatic diol; c) a functional group derived from a heterocyclic diol, or d) Functional groups derived from the following diols: 2,3-dimethoxy-1,4-butanediol, 【Chemistry 6】 2. The oligomer or polymer according to claim 1, characterized in that it is

3. 3. The oligomer or polymer according to claim 1 or 2, characterized in that the repeating units according to formula I are defined by the following repeating units according to formula III and formula IIIa: 【Chemistry 7】 These are included in oligomers or polymers, where R １ , D and x are as defined above and the definition of D' corresponds to the definition of D, with the proviso that D and D' are derived from different diols.

4. 4. The oligomer or polymer according to claim 3, characterized in that the molar ratio of repeat units III:IIIa is from 0.1:99.9 to 50:

50.

5. 5. The oligomer or polymer according to claim 1, wherein for all repeat units according to formula I, x is 0, or wherein the oligomer or polymer comprises both repeat units according to formula I, where x=0, and repeat units according to formula I, where x=1, and wherein the molar ratio of repeat units according to formula I, where x=0:repeating units according to formula I, where x=1, is from 50:50 to <100:>0.

6. at least one organic component to be stabilized and at least one oligomer or polymer according to any one of claims 1 to 5, A composition wherein the at least one organic component to be stabilized is selected from the group consisting of: · plastic, at least one oil, fat or wax, Mineral or synthetic lubricating oils, hydraulic oils, engine oils, turbine oils, gear oils, metal working oils or lubricating greases, and - Polymerizable monomers.

7. 7. The composition according to claim 6, characterized in that the at least one oligomer or polymer is present in a weight proportion of 0.01 to 5.0 parts by weight, based on the total composition.

8. 8. The composition of claim 6 or 7, comprising at least one additive selected from the group consisting of primary antioxidants, secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilic agents, hydrophobic agents, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, foaming agents, degradation additives, defoamers, odor scavengers, marking agents, antifoam agents, fillers and reinforcing agents.

9. Use of an oligomer or polymer according to any one of claims 1 to 5 as a stabilizer for organic materials, The organic material is selected from the group consisting of: · plastic, at least one oil, fat or wax, Mineral or synthetic lubricating oils, hydraulic oils, engine oils, turbine oils, gear oils, metal working oils or lubricating greases, and - Polymerizable monomers.

10. Use of an oligomer or polymer according to claim 9 as a stabiliser for: - thermal, actinic or oxidative degradation of plastics; - thermal, actinic or oxidative decomposition of lacquers, paints and coatings, Thermal, actinic or oxidative decomposition of oils, fats or waxes; Thermal, actinic or oxidative degradation of mineral or synthetic lubricating oils, hydraulic oils, engine oils, turbine oils, gear oils, metal working oils or lubricating greases; or - Against premature polymerization and / or oxidation of polymerizable monomers.

11. Moulding compounds or moulded parts producible from the plastic composition according to any one of claims 6 to 8 in the form of injection moulded parts, foils, films, foams, fibres, cables, pipes, profiles, hollow bodies, ribbons, membranes and / or adhesives.

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