EP1181330A1

EP1181330A1 - Mixtures containing stabilisers and iminophosphoranes

Info

Publication number: EP1181330A1
Application number: EP00927086A
Authority: EP
Inventors: Sylke Haremza; Martin Klatt; Andreas Koch; Hubert Trauth; Manfred Appel
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1999-05-04
Filing date: 2000-04-27
Publication date: 2002-02-27
Also published as: CA2373013A1; AU4558200A; DE19920590A1; JP2002543262A; BR0010312A; WO2000066661A1

Abstract

The invention relates to mixtures containing the following components: A) stabilisers for protecting organic materials against the harmful effects of light, heat and/or oxidation; B) iminophosphoranes as flameproofing agents for organic materials, C) optionally, other halogen-free flameproofing agents that are different from iminophosphoranes and D) optionally, other additives. The invention also relates to the use of mixtures of this type as combined stabilisers and flameproofing agents for organic materials, especially for plastics, and to organic materials, especially plastics, containing mixtures of this type.

Description

Mixtures containing stabilizers and iminophosphoranes

description

The invention relates to mixtures which are used as a component

A) stabilizers for protecting organic materials against harmful effects of light, heat and / or oxidation,

B) iminophosphoranes as flame retardants for organic materials,

C) optionally further halogen-free and non-iminophosphorane flame retardants for organic materials and

D) optionally contain further additives.

The invention further relates to the use of these mixtures as combined stabilizers and flame retardants for organic materials, in particular for plastics, and also organic materials, in particular plastics, which contain such mixtures.

Stabilizers are usually added to stabilize organic materials and in particular plastics against the harmful effects of light, heat and / or oxidation. If, in addition, such materials are required to have a markedly flame-retardant behavior, this is usually adjusted by adding flame retardants.

Common classes of flame retardants for plastics are listed, for example, in the Römpp Chemical Lexicon Volume 2 (Cm - G), p. 1370, Georg Thieme Verlag Stuttgart - New York, 1990. Iminophosphoranes are also used as flame retardants.

U.S. Patent 3,322,860 is concerned with halogen containing iminophosphoranes, e.g. 2, 5 -Dichlor-3, 6 -bis (triphenylphosphoranylidena ino) -p-benzoquinones, which are obtained by reacting 2,5-dihalogen-3, 6 -diaminobenzoquinones with trisubstituted phosphinium dihalides.

Writings WO 98/24837 and WO 98/24838 describe flame-retardant thermoplastic molding compositions which are halogen-free

Flame retardants, consisting exclusively or essentially of iminophosphoranes. As additives to these Molding compounds are mentioned heat and light stabilizers, otherwise these writings can not be further out about their chemical nature.

It is also known that halogen-containing flame retardants, which are still widely used, often have a negative influence on the effectiveness of added stabilizers. As a result, the stabilized and flame-retardant stabilized organic materials and in particular plastics generally no longer have the desired level of long-term stability.

The object of the present invention was therefore to provide mixtures in which the stabilizers and flame retardants contained therein do not show any negative effects on one another and which can be added as an additive package to organic materials, in particular plastics.

Accordingly, the mixtures described at the outset, containing components A) and B) and, if appropriate, C) and D) were found.

The mixtures according to the invention preferably contain at least one stabilizer selected from the group consisting of as component A)

al) alkylated monophenols, a2) alkylthiomethylphenols, a3) hydroquinones and alkylated hydroquinones, a4) tocopherols, a5) hydroxylated diphenylthioethers, a6) alkylidene bisphenols, a7) O-, N- and S-benzyl compounds, a8) aromatic hydroxybenzyl compounds, a9) alO) benzylphosphonates, all) acylaminophenols, al2) esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, β- (5-tert-butyl -4-hydroxy-3 -methylphenyl) - propionic acid, ß- (3, 5-dicyclohexyl -4-hydroxyphenyl) propionic acid and 3, 5-di-tert. -butyl-4-hydroxyphenylacetic acid, al3) amides of ß- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, al4) ascorbic acid and its derivatives, al5) antioxidants based on amine compounds, alβ) phosphites and phosphonites, al7) 2- (2'-hydroxyphenyl) benzotriazoles, al8) sulfur-containing peroxide scavengers or sulfur-containing

Antioxidants, al9) 2-hydroxybenzophenones, a20) esters of unsubstituted and substituted benzoic acid, a21) acrylates, a22) sterically hindered amines, a23) oxamides and a24) 2- (2-hydroxyphenyl) - 1, 3, 5-triazines .

Group a1) of the alkylated monophenols includes, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl -4, 6-dimethyl-phenol, 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 -Ditert-butyl-4-methoxymethylphenol, nonylphenols, which have a linear or branched side chain, for example 2, 6 -di -nonyl -4 -methylphenol, 2, 4 -dimethyl-6 - (1 '-methylundec- 1' - yl) -phenol, 2, 4 -dimethyl -6 - (1 '-methylheptadec- 1' -yDphenol, 2, 4 -Dimethyl -6 - (1 '-methyltridec- 1' -yDphenol and mixtures of these compounds.

Group a2) of the alkylthiomethylphenols includes, for example

2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4 -dioctylthiomethyl-6-ethylphenol and 2,4-di-dodecylthiomethyl-4-nonylphenol.

Group a3) of the hydroquinones and alkylated hydroquinones include, 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-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-ydroxyphenyl) adipate.

Group a4) of the tocopherols includes, for example, α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures of these compounds, and tocopherol derivatives, such as tocopheryl acetate, succinate, nicotinate and polyoxyethylene succinate ("tocopherol" ").

Group a5) of the hydroxylated diphenylthioethers includes, for example, 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'-thio- bis- (3,6-di-sec-amylphenol) and 4,4'-bis (2,6-dimethyl -4-hydroxyphenyl) disulfide.

Group a6) of the alkylidene bisphenols includes, for example, 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'-methyleneb (4 -methyl-6 -cyclohexyl-phenol), 2,2'-methylenebis (6 -nonyl -4 -methylphenol), 2,2'-methylene bis (4,6-di-tert-butylphenol), 2,2-ethylidene bis (4,6-di-tert-butyl-phenol), 2,2 'ethylidebis (6-tert-butyl-4 -isobutylphenol), 2,2'-methylenebis [6 - (α-methylbenzyl) -4 -nonylphenol], 2,2'-methylenebis [6- (, α-dimethylbenzyl) -4 -nonylphenol], 4,4 '- Methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis - (6-tert-butyl -2-methylphenol), 1,1-bis (5 - tert-butyl-4-hydroxy-2 - methylphenyl) butane, 2,6-bis (3-tert-butyl -5-methyl -2 -hydroxy-benzyl) -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-dodecyl mercapt obutane, 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) ropane, 2,2-bis (5-tert-butyl-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane and 1,1,5,5-tetrakis - (5-tert-butyl-4-hydroxy-2-methylphenyl) entane.

Group a7) of the 0-, N- and S-benzyl compounds includes, for example, 3, 5, 3 ', 5'-tetra-tert-butyl -4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3, 5 -dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3, 5 -di - tert-butylbenzylme captoacetate, tris (3,5 -ditert-butyl-4-hydroxybenzyl) -a in, bis (4 - tert-butyl -3 - hydroxy-2, 6-dimethylbenzyl) dithioterephthalate, bis (3, 5-di-tert-butyl -4-hydroxybenzyl) sulfide and isooctyl - 3, 5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

Group a8) of the aromatic hydroxybenzyl compounds includes, for example, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) 2,4,6-trimethylbenzene, 1,4-bis (3,5 -ditert-butyl -4-hydroxybenzyl) -2, 3, 5, 6 - tetraethylbenzene and 2, 4, 6 -Tris (3, 5 -ditert-butyl-4-hydroxybenzyl) phenol.

Group a9) of the triazine compounds includes, 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, 1,3,5 -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-tri azin, 1, 3, 5 -Tris (3, 5-dicyclohexyl-4-hydroxybenzyl) isocyanurate and 1,3,5 -Tris (2-hydroxyethyl) isocyanurate.

The group alO) of the benzylphosphonates include, for example, dimethyl -2,5 -di-tert-butyl -4 -hydroxybenzylphosphonate, diethyl-3, 5 -di-tert-butyl -4 -hydroxybenzylphosphonate, dioctadecyl -3, 5 -di - tert- butyl-4-hydroxybenzylphosphonate and dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate.

The group all) of the acylaminophenols include, for example, 4-hydroxylauroylanilide, 4-hydroxystearoylanilide and octyl-N- (3,5-di - tert-butyl -4-hydroxyphenyl) carbamate.

The propionic and acetic acid esters of group al2) are based on mono- or polyhydric alcohols such as, for example, 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 and 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

The propionic acid amides from group al3) are based on amine derivatives such as, for example, N, N 'bis (3,5-di-tert-butyl -4-hydroxyphenylpropionyl) hexamethylene diamine, N, N' bis (3,5-di - tert -butyl-4-hydroxyphenylpropionyl) trimethylene diamine and N, N 'bis (3, 5 - di - tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

In addition to ascorbic acid (vitamin C), group al4) also includes ascorbic acid derivatives such as, for example, ascorbyl palmitate, laurate and stearate, and ascorbyl sulfate and phosphate.

Group al5) of the antioxidants based on amine compounds include, for example, N, N'-di-isopropyl-p-phenylenediamine, N, N '-di-sec-butyl-p-phenylenediamine, N, N' - bis (1, 4 -dimethylpentyl) - p-phenylenediamine, N, N 'bis (l-ethyl-3-methylpentyl) -p-phenylenediamine, N, N' bis (1-methylheptyl) -p-phenylenediamine, N, N '-dicyclo - hexyl-p-phenylenediamine, N, N '-diphenyl -p-phenylenediamine, N, N' -Bis- (2-naphthy1) -p-pheny1endiamine, - 1sopropy1 -N '-pheny1 -p-pheny1en- dia in, 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, octyl-substituted diphenylamine, such as, for example, 5, p, p'-di-tert-octyldiphenylamine, 4 -n-butylaminophenol,

4-butyrylaminophenol, 4 -nonanoylaminophenol, 4 -dodecanoylamino-phenol, 4 -octadecanoylaminophenol, bis [4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4-diaminodiphenylmethane 4'-diaminodiphenylmethane, N, N, N ', N' -tetramethyl -

10 4,4'-di-aminidiphenylmethane, 1, 2-bis [(2-methylphenyl) amino] ethane, 1, 2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4 - (1 ', 3'-di-methylbutyl) phenyl] amine, tert-octyl substituted N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamine, a mixture of mono- and

15 dialkylated nonyldiphenylamine, a mixture of mono- and dialkylated dodecyldiphenylamine, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamine, a mixture of mono- and dialkylated tert-butyldiphenyla in, 2, 3 -dihydro-3, 3-dimethyl -4H- 1, 4 -benzothiazine, phenothiazine, a mixture of

20 mono- and dialkylated tert-butyl / tert-octylphenothiazine, a mixture of mono- and dialkylated tert-octylphenothiazine, N-allylphenothiazine, N, N, N ', N' -tetraphenyl - 1, 4 -diaminobut-2 -en, N, N-bis (2,2,6,6-tetramethyl-piperidin-4-yl) -hexamethylene diamine, bis (2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, 2,2,6,6 - Tetra -

25 methylpiperidin-4-one and 2, 2, 6, 6-tetramethylpiperidin-4 -ol.

The group al6) of the phosphites and phosphonites include, for example, triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilaurylphosph.it, triocta-

30 decylphosphite, distearylphentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methyl) ) -pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2, 4 -di - tert-butyl -6 -

35 methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris - (tert-butylphenyl)) pentaerythritol diphosphite, tristearylsorbitol tri-phosphi, tetrakis (2,4-di - tert-butylphenyl) -4,4'-biphenylenedi-phosphonite, 6 -Isooctyloxy-2, 4,8,10 - tetra-tert-butyl - 12H-dibenz - [d, g] -1,3,2 -dioxaphosphocin, 6 -Fluoro-2, 4, 8, 10 - tetra-tert -butyl -

40 12 -methyl-dibenz [d, g] -1,3,2-dioxaphosphocin, bis (2,4-di - tert-butyl -6-methylphenyl) methylphosphite and bis (2,4-di-tert -butyl - 6-methylphenyl) ethyl phosphite.

Group al7) of the 2 - (2 '-hydroxyphenyl) benzotriazoles includes 45 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-chloro-benzotriazole, 2- (3 'tert-butyl-2' - hydroxy-5 ' -methylphenyl) -5-chloro-benzotriazole, 2- (3 '-sec-butyl- 5' -tert-butyl-2 '-hydroxyphenyl) -benzotriazole, 2- (2' -hydroxy-4 '- octyloxyphenyl) -benzotriazole , 2- (3 ', 5' -Ditert-amyl -2 '-hydroxyphenyl) benzotriazole, 2- (3', 5 '-Bis (α, α-dimethylbenzyl) -2' - hydroxyphenyl) benzotriazole , a mixture of 2 - (3 'tert-butyl - 2' -hydroxy-5 '- (2 -octyloxycarbonylethyl) phenyl) - 5 -chloro-benzotriazole, 2- (3' tert-butyl-5 '- [ 2- (2-ethylhexyloxy) carbonylethyl] - 2'-hydroxyphenyl) -5-chlorobenzotriazole, 2 - (3 'tert-butyl-2' - hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5 -chloro-benzotriazole, 2- (3 'tert-butyl-2' -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -benzotriazole, 2- (3' tert-butyl-2 '-hydroxy-5' - (2-Octyloxycarbonyl - ethyDphenyl) benzotriazole, 2- (3 'tert-butyl-5' - [2- (2-ethylhexyl - oxy) approx rbonylethyl] -2 '-hydroxyphenyl) benzotriazole, 2- (3' -dodecyl - 2 '-hydroxy-5' -methylphenyl) -benzotriazole and 2- (3 'tert -butyl-2' - hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2 '-methylene-bis [4 - (1,1,3,3-tetramethylbutyl) -6 -benzotriazole - 2 -ylphenol]; the product of the complete esterification of 2- [3 'tert -butyl -5' - (2-methoxycarbonylethyl) -2 '-hydroxyphenyl] - 2H-benzotriazole with polyethylene glycol 300; [R-CHCH -COO (CH ₂ ) ₃ ^ - ₂ , with R = 3 'tert-butyl-4' -hydroxy-5 '-2H-benzotriazole -2 -ylphenyl].

Group al8) of the sulfur-containing peroxide scavenger or sulfur-containing antioxidants includes, for example Esters of 3, 3 '- hiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldi - sulfide and pentaerythritol dodecisate (dodecyl ether).

Group al9) of the 2-hydroxybenzophenones includes, for example, the 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4 -decycloxy-, 4 -dodecyl-oxy-, 4-benzyloxy-, 4, 2 ', 4' -Trihydroxy- and 2 '-Hydroxy-4, 4' -dimethoxy derivatives.

Group a20) of the esters of unsubstituted and substituted benzoic acid includes, for example, 4-tert-butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-3-tert-butyl di-tert-butyl -4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl -4,6 -di-tert-butylphenyl -3,5-di-tert-butyl-4-hydroxybenzoate.

Group a21) of the acrylates includes, for example, ethyl -α-cyano-β, β-diphenyl acrylate, isooctyl-α-cyano-β, β-diphenyl acrylate, methyl - α-methoxycarbony1cinnamate, methyl1 -α-cyano -ß-methyl -p - methoxy cinnamate, butyl -α-cyano -ß-methyl -p-methoxy-cinnamate and methyl-α-methoxycarbonyl -p-methoxycinnamate.

Group a22) of the sterically hindered amines includes, for example, bis (2, 2, 6, 6 - tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis ( 1,2,2,6,6-pentamethylpi-peridin-4-yl) sebacate, N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N '-bisformyl-1 , 6 -diaminohexane, bis (1 -octyloxy-2, 2, 6, 6 - tetramethylpiperidin-4 -yl) sebacate, bis (1,2,2,6, 6 -pentamethylpi - peridin-4 -yl) - n-butyl-3, 5-di - tert-butyl-4-hydroxybenzylmalonate, the condensation product from 1- (2-hydroxyethyl) -2, 2, 6, 6 - tetra-methyl-4-hydroxypiperidine and succinic acid, the condensation - Product of N, N 'bis (2, 2, 6, 6 - tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2, 6 -dichloro-1, 3, 5-triazine, tris (2nd , 2,6, 6 - tetramethylpiperidin-4 -yl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethylpiperidin-4 -yl) -1,2,3,4 -butanetetracarboxylate, 1,1 ' - (1,2-ethylene) -bis (3,3,5,5-tetramethylpiperazinone), 4 -Benzoyl-2, 2,6,6 - tetramethylpiperidine, 4 - stearyloxy-2, 2, 6, 6 - tetramethylpiperidine, bis (l, 2,2,6,6 -pentarnethylpiperidin-4 -yl) -2 - n-butyl-2- (2-hydroxy-3, 5-di-tert-butylbenzyl) alonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane -2, 4-dione, bis (l-octyloxy-2, 2,6,6 - tetramethylpiperidin-4-yl) succinate, the condensation product of N, N 'bis - (2, 2, 6, 6 - tetramethylpiperidine- 4 -yl) hexamethylenediamine and 4-morpholino-2, 6 -dichloro-1, 3, 5-triazine, the condensation product of 2-chloro-4, 6-bis (4-n-butylamino-2, 2,6,6 tetramethylpiperidin-4-yl) 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 -pentamethylpiperid-4-yl) -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] decan-2,4-dione, 3 -dodecyl -1- (2,2,6,6 -tetramethylpiperi din-4-yl) pyrrolidin-2, 5-dione, 3 -dodecyl- 1- (1,2,2,6, 6 -pentamethyl-piperidin-4 -yl) pyrrolidin-2, 5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2, 2, 6, 6 - tetramethylpiperidine, the condensation product from N, N 'bis - (2, 2, 6, 6 - tetramethylpiperidin-4-yl) -hexamethylene diamine and 4-cyclohexylamino-2, 6 -dichloro-1, 3, 5-triazine, the condensation product of 1, 2-bis (3-aminopropylamino) -ethane and 2, 4, 6 -trichloro-1, 3, 5-triazine , 4-butylamino-2, 2,6,6-tetramethylpiperidine, N- (2,2,6,6-tetramethyl-piperidin-4 -yl) -n-dodecylsuccinimide, N- (1, 2, 2, 6, 6 -pentamethyl-piperidin-4-yl) -n-dodecylsuccinimide, 2 -ndecyl-7, 7, 9, 9 - tetramethyl-1-oxa- 3, 8 -diaza-4 -oxo-spiro [4.5] - decane, the condensation product of 7, 7, 9, 9 -tetramethyl -2-cycloundecyl-l-oxa-3, 8 -diaza- 4 -oxospiro- [4.5] decane and epichlorohydrin, the condensation products of 4-amino -2, 2, 6, 6- tetramethylpiperidine with tetramethylol cetylene diureas, poly (methoxypropyl-3-oxy) - [4 (2,2,6,6-tetramethyl) piperidinyl] siloxane and the oligomeric amine of the formula with a molecular weight of approx. 3500 g / mol.

Group a23) of the oxamides include, for example, 4,4'-dioctyl-oxyoxanilide, 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 its mixture with 2-ethoxy-2'-ethyl-5, 4'-di-tert-butoxanilide and mixtures of ortho-, para-methoxy-disubstituted oxanilides and mixtures of ortho- and para-ethoxy disubstituted oxanilides.

Group a24) of the 2 - (2-hydroxyphenyl) - 1, 3, 5 - triazines includes, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-tri-azine, 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 (2nd , 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-butyloxy-propoxy) - phenyl] -4, 6 -bis (2, 4 -dimethyl) - 1, 3, 5 - triazine, 2- [2 -hydroxy- 4 - (2-hydroxy-3-octyloxypropoxy) phenyl] -4, 6 -bis (2,4, dimethyl) - 1,3,5 - triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) - 2-hydroxy-pheny1] -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-hexyloxyphenyl) -4,6 -diphenyl -1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6 -diphenyl -1,3 5- triazine, 2,4,6-tris [2-hydroxy-4 - (3-butoxy-2-hydroxy-propoxy) phenyl] -1, 3,5-triazine and 2 - (2-hydroxyphenyl) -4 - (4-methoxyphenyl) -6-phenyl -1, 3,5-triazine.

The mixtures according to the invention preferably contain as component B) at least one iminophosphorane of the formula ZX (I) or of the formula Y (-Z) _n (II), in which

Z is a radical R ¹ R ² R ³ P = N-, R ¹ , R ² and R ³ independently of one another C ₁ -C ₂ n-alkyl, Cg-C ₂ o-aryl or ^c ₃ ^_ C ₂ o ~ heteroaryl,

X hydrogen f, -CC ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₃ -C ₂ o-heteroaryl, RS0 ₂ -, P (0) R ₂ -, P (S) R ₂ -, cyano, Amino or tri (-C ₆ - al - kyl) - silyl,

R Cι-Cι ₂ -alkyl, Cι ₂ -alkoxy, C ₁₂ alkylthio, C ₆ -C ₂₀ aryl, C ₆ ^_ C o-aryloxy, or C ₆ -C ₀ arylthio,

Y is an n-valent organic radical selected from the group consisting of C ₂ -C ₂ o -alkylenes and C -C ₂ o -cycloalkylenes, in which one or more non-adjacent CH ₂ groups by oxygen, sulfur, -N (R ') -, -CO-, -S0 -, optionally alkyl-substituted arylene and / or optionally alkyl-substituted heteroarylene and / or which can be substituted with cyano or isocyanate groups, arylenes, heteroarylenes, C ₆ -C ₂₀ aryl (S0 ₂ -) _n , HP (0) =, P (0) ≡, P (S) ≡, -Cι-Cι ₂ - alkyl-P (0) =, C ₆ -C ₂ o-aryl-P (0 ) =, -CC ₂ -alkyl - P (S) = and C ₆ -C ₂₀ - aryl-P (S) =,

R 'is hydrogen or Cχ-Cι ₂ alkyl and

n is an integer value of 2, 3, 4, 5, 6, 7, 8, 9 or 10.

Iminophosphoranes of the formulas (I) and (II) can each be present individually or in combination in component B) of the mixtures according to the invention, in which case the Z radicals of (I) and (II) do not have to match.

C ₁ -C ₂ -alkyl radicals for X, R ¹ , R ² and R ³ are branched or unbranched alkyl chains, such as, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl , tert -Butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2 -dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2 -dimethylpropyl, 1-methylpentyl , 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1, 1-Dirnethylbutyl, 1, 2 -Dirnethylbutyl, 1, 3 -Dirnethylbutyl, 2,2-Dimethylbutyl, 2, 3 -Dimethylbutyl, 3, 3 -Dimethylbutyl, 1 -Ethyl-butyl, 2-ethylbutyl, 1, 1, 2 -trimethylpropyl, 1, 2, 2 -trimethylpropyl, 1 -ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n -Octyl, 2 -ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hep-tadecyl, n-octadecyl , called n-nonadecyl or n-eicosyl.

C 1 -C ₂ -alkyl radicals for R and R 'have already been listed under the above-mentioned C ₁ -C ₂ -alkyl radicals. The C 1 -C ₂ -alkoxy and C 1 -C ₂ -alkylthio radicals for R are derived analogously from the corresponding C 1 -C ₂ -alkyl radicals already mentioned by way of example in the C ₁ -C -alkyl radicals.

C ₆ -C ₂ o-ryl for X, R, R ¹ , R ² and R ³ includes, for example, phenyl and naphthyl, which, if appropriate, are selected from the group consisting of C ₁ -C ₁ -alkyl, C ¹ with one or more substituents -C ₂ alkoxy, C 1 -C ₂ alkylthio, mono- and di (C 1 -C ₂ -al - kyl) amino, mono- and diphenylamino, C 1 -C ₂ alkylcarbonyl, C 1 -C 4 -alkylcarbonyloxy, Cι-Cι ₂ -Alkyloxycarbonyl, -COOH, -CN, -NCO, -N0 ₂ , Hydroxy1amino, 0- (-Cι-Cι ₂ -alkyl) -hydroxy1amino and 0- Phenylhydro- xyla ino, -S0 ₃ H, W ¹ W ² N- S0 ₂ -, WW ² NN (W ³ ) - S0 ₂ -, where W ¹ , W ² and W ^{3 are} independently C] _. -Cι ₂ alkyl or phenyl, and OM, where M is hydrogen, an equivalent of a mono- or divalent metal from the group of alkali or alkaline earth metals, preferably sodium or potassium or magnesium, calcium or strontium, or an equivalent of a metal selected from the group consisting of iron, cobalt, nickel, copper, zinc and titanium. Corresponding C 1 -C ₂ -alkyl radicals contained as substituents or contained in the substituents have already been listed as examples above under the C ₁ -C ₂ o -alkyl radicals.

Next come as C ₆ -C o-aryl for X, R, R ¹ , R ² and R ³ with an aromatic C ₆ -Cιo radical substituted Cg-cin-aryl, such as biphenyl, or alkyl aromatic substituted Cε- Cio-aryl, such as Ci-Cg-alkyl or di (-CC-alkyl) -substituted biphenyl in question. Given appropriate as a substituent Ci-Cs-alkyl or Cι ~ C alkyl groups have also been listed above under ^c ι ^_C2o ~ alkyl radicals with exemplary.

Suitable C ₆ -C ₂ o ~ aryloxy or C ₆ -C ₂ o ~ arylthio for R are those radicals which are correspondingly derived from the C ₆ ^_ C ₂ o ^_ ryl radicals described above.

As C -C ₂ o heteroaryl for X, R ¹ , R ² and R ³ are preferably radicals which contain 1 to 3 nitrogen atoms and optionally other heteroatoms such as oxygen and / or sulfur. This heteroaryl can also carry one or more of the substituents listed above for the C ₆ -C ₂ o-aryl radicals. Furthermore, these heteroaryl radicals can also be alkylaromatic substituted, preferably a phenyl radical with a methyl group in the 2-, 3- or 4-position or a phenyl radical with two methyl groups in 2,6-, 2,5-, 2,4-, 2,3-, 3,5- or 3,4-position is used. Heteroaromatic radicals for X, R ¹ , R ² and R ^{3 are} derived, for example, from pyrrole, pyrazole, isoxazole, isothiazole, imidazole, 1H-1,2, 3-triazole, 1H-1, 2, 4-triazole, pyridine, Pyrazine, pyridazine, 1H-azepine, 2H-azepine, oxazole, thiazole, 1,2,3-, 1,2,4- or 1,3,4-oxadiazole, 1,2,3-, 1,2,4 - or 1, 3, 4-thiadiazole and the optionally benzo- or dibenzo-fused rings, such as quinoline, isoquinoline, indole, carbazole, 1H-indazole, indoxazole, benzo [d] isothiazole, anthranil, benzimidazole, benzoxazole, benzothiazole, Cinnoline, phthalazine, quinazoline, quinoxaline or phenazine.

The attachment of the radical Z to the heteroaromatic compounds is usually via a carbon atom. However, if the underlying heteroaromatic is in an H-N form or has such a tautomeric form, the radical Z can also be bound via the corresponding nitrogen atom (replacing the hydrogen atom). The same applies mutatis mutandis to one or more substituents on the heteroaromatic radical which are present and which are mentioned above.

If X is a group P (0) R ₂ - or P (S) R ₂ -, the radicals R can be different or the same. However, they are preferably the same.

If X is a tri (Ci-Cg-alkyl) silyl group, the alkyl radicals contained therein can be different from one another or also partially or completely identical. The latter is preferably the case. For example, the trimethylsilyl group may be mentioned here. Corresponding Ci-Cg-alkyl groups _were> alkyl radicals listed examples already among the Cι-C ₂ c with.

The n-valent organic radicals Y in formula (II) which can be used are C ₂ -C 1 -oo-kylenes in which one or more non-adjacent CH groups are formed by oxygen, sulfur, -N (R ') -, -CO- , -S0 -, optionally alkyl-substituted arylene and / or optionally alkyl-substituted heteroarylene and / or which can be substituted with cyano or isocyanate groups.

Divalent C ₂ -Cιoo alkylenes correspond, for example, to the form (-CH ₂ -CH ₂ ) _v -, (-CH ₂ -CH (CH ₃ )) _W -CH ₂ -CH (CH ₃ ) -,

(-CH ₂ -CH ₂ -N (R ')) _W -CH ₂ -CH ₂ -, (-CH ₂ -CH ₂ -0) _W "CH ₂ -CH ₂ - and (-CH ₂ -CH (CH ₃ ) -0) _t -CH ₂ -CH (CH ₃ ) -, in which the variables v, w and t assume integer values from 1 to 50, 1 to 32 and 1 to 24, respectively, and in which R 'of those already given Definition corresponds. Further n-valent C ₂ -C alkoxides correspond, for example, to the formulas

A- (-CH ₂ -CH) _V -Ω, A- (-CH ₂ -CH) _r -Ω, A- (-CH ₂ -CH) _r -Ω

I I I

CH ₂ C = 0

II or A- (-CH ₂ -CH) _r -Ω, I

S0 ₂

I in which the variables v and r assume integer values between 2 and 50 (ie 2 <n = v <50) or 2 and 33 (ie 2 <n = r <33) and A and Ω are the usual starting (A ) and terminating (Ω) fragments denote which result from the production of the polymers on which these residues are based from the corresponding monomer units.

Preferred n-valent organic radicals Y in formula (II) are C ₂ -C ₂ o -alkylenes or C ₃ -C ₂ o -cycloalkylenes in which one or more non-adjacent CH ₂ groups are formed by oxygen, sulfur, -N (R ') -, -CO-, -S0 ₂ -, optionally alkyl-substituted arylene and / or optionally alkyl-substituted heteroarylene and / or which can be substituted with cyano or isocyanate groups.

The divalent C ₂ -C ₂ o-alkylene radicals here are in particular the radicals (-CH ₂ -CH ₂ ) _v -, (-CH ₂ -CH (CH ₃ )) _W -CH ₂ -CH (CH ₃ ) -, ( -CH ₂ -CH ₂ -N (R ')) _w - -CH ₂ -CH ₂ -, (-CH ₂ -CH ₂ -0) _w - -CH ₂ -CH ₂ - and

(-CH ₂ -CH (CH ₃ ) -0) -CH ₂ -CH (CH ₃ ) - into consideration, in which the variables v, w, w 'and t are integer values between 1 and 10, 1 and 6, 1 and accept 5 or 1 and 4.

In particular, radicals such as, for example, come as n-valent C ₂ -C ₂ alkylene radicals

A- (-CH ₂ -CH) _V -Ω, A- (-CH ₂ -CH) _r -Ω, A- (-CH ₂ -CH) _r -Ω I 1 I

CH ₂ C = 0

II or A- (-CH ₂ -CH) _r -Ω,

T ° ² in which the variables v and r take integer values from 2 to 10 (ie 2 <n = v <10) and 2 to 6 (ie 2 <n = r <6).

Among C ₃ -C o-cycloalkylenes in which one or more non-adjacent CH ₂ groups by oxygen, sulfur, -N (R ') -, -CO-, -S0 ₂ -, optionally alkyl-substituted arylene and / or optionally alkyl-substituted The residues are, for example, substituted heteroarylene and / or which can be substituted with cyano or isocyanate groups

to call.

Furthermore, arylene and heteroarylenes are suitable as n-valent organic radicals Y in formula (II). Here are, for example, the divalent 1,2-, 1,3- and 1,4-phenylene and 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1 , 7-, 1,8-, 2,3-, 2,4-, 2,5-, 2,6-, 2,7- and 2,8-naphthylene residues as well as the divalent 2,3- and 2 , 4-pyridine and 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 3,4-, 3,5-, 3,6-, 3.7-, 3.8-, 4.5-, 4.6-, 4.7-, 4.8-, 5.6-, 5.7-, 5.8-, 6.7-, 6,8- and 7, 8-quinoline residues. In addition, the arylenes and heteroarylenes are also to be understood as meaning higher-valent radicals, such as the 1, 3, 5-phenyl or 1, 2, 4-naphthyl radical. These radicals are preferably derived from the C ₆ -C ₂ o ~ ryl and C ₃ -C ₂ o ~ heteroaryl radicals already described above. Further n-valent organic radicals Y in formula (II) are those of the formula C ₆ -C ₂ o ~ ryl (S0 ₂ -) _n . These are preferably also residues which are derived from the C ₆ -C ₂ o-aryl and C ₃ -C ₂ o heteroaryl radicals already described above. The C ₆ -C ₂₀ aryl radicals are, in particular, phenyl or naphthyl, which may optionally carry said one or more substituents. The number of S0 ₂ units (and thus the value of n) for unsubstituted phenyl or naphthyl is 2 to 6 or 2 to 8, the maximum value for n correspondingly decreasing in accordance with the additional substituents present.

It should be noted here that, for production reasons, not only an aromatic disulfonic acid (corresponding to a divalent radical Cg-C ₂ o-aryl (S0 ₂ -) ₂ ), but also to a certain extent also higher sulfonated products (corresponding to the trivalent or tetravalent radicals, for example) C ₆ -C ₂ o ^_ aryl (S0 ₂ -) ₃ or C ₆ -C o ~ aryl (S0 ₂ -) ₄ ) can be obtained. Component B) can therefore either be a mixture of the (defined) iminophosphoranes C ₅ -C ₂₀ aryl (S0 ₂ -Z) ₂ . C ₆ -C ₂ o-aryl (S0 ₂ -Z) ₃ and C ₆ -C ₂ o-aryl (S0 ₂ -Z) ₄ ) or as iminophosphorane the C ₆ -C ₂ o ~ aryl (S0 ₂ -Z) _{u are} considered, in which u, according to the molar distribution of the various compounds, assumes a fractional average between 2 and 4.

This alternative approach, explained by way of example, is to be included in the context of the present invention for analogous cases in which one finds a distribution of the products corresponding to the n -valent radicals Y, without explicitly going into further details.

As preferred divalent (n = 2) organic radicals Y in formula (II) come into consideration HP (0) =, -C-C ₁₂ -alkyl-P (0) =, -C-C ₁₂ -alkyl-P (S ) =, C ₆ -C ₂ o-aryl-P (0) = and C ₅ -C ₂₀ aryl -P (S) =, as preferred trivalent (n = 3) organic radicals P (0) ≡ and P ( S) ≡, where the radicals Z in the resulting amide derivatives of monoalkyl and monoarylphosphonic, monoalkyl and monoarylthiophosphonic acids and in the resulting amide derivatives of phosphoric and thiophosphoric acid can be identical or different.

Component B) can also be derived from carboxamides iminophosphoranes of the general formula (III)

included, where Z, Y and n correspond to the definitions given above.

A large number of 5 established synthetic possibilities can be used for the production of iminophosphoranes. In addition to the Staudinger method - the reaction of triphenylphosphine with an azide (YG Gololobov et al., Tetrahedron 1981, 37, p. 437) - iminophosphoranes are based on amines (TW Rave et al., J.Org.Chem. 1966, 31, p. 2894), amides (using 10 diethyl azodicarboxylate for activation and coupling with

Triphenylphosphine; s. S. Bittner, J.Org.Chem. 1985, 50 p. 1712) and isoxazoles (e.g. from T.L. Lemke et al., J. Heterocycl. Chem. 1983, 20, p. 899).

15 For α-amino heteroaromatics, direct coupling with triphenylphosphine is possible if, for example, carbon tetrachloride (J. Boedeker, P. Köckritz, J. Prakt. Chem. 1978, 320, 1043-1046) or hexachloroethane (T. Okawa, S Eguchi, Synlett 1994, 555-556).

20th

Iminophosphoranes can also be prepared using phosphorus dihalides, such as triphenylphosphine dibromide or triphenylphosphine dichloride, if appropriate in the presence of auxiliary bases (cf. Molina et al. Heterocycles 1994, 37,

25 997-1018).

The synthesis of iminophosphoranes from primary amines using trisubstituted phosphine and chlorine or bromine is described in DE-A 167 02 96. Another approach was developed by Katritzky et al. created by base treatment of 1- [α- (phosphoranylideneamino) alkyl] benzotriazoles (J.Org.Chem. 1994, 59, p. 2740).

Iminophosphoranes are usually very reactive and therefore react with most of the reactants under very mild conditions. also explains the sensitivity to moisture.

With the exception of the compounds of the general formula (III), the iminophosphoranes listed here are distinguished in that they are usually not sensitive to moisture or aqueous media or to heat, so that they usually occur when they are incorporated into polymeric molding compositions As a rule, survive thermal stress without damage. 5 If desired, further halogen-free flame retardants for organic materials different from the iminophosphoranes of component B) can be added as component C) to the mixtures according to the invention. Such further flame retardants are, for example, the phosphorus compounds disclosed in German Offenlegungsschπft 196 326 75 under component E). In addition, there are inorganic flame retardants based on hydroxides or carbonates, in particular magnesium, inorganic and organic boron compounds, such as boric acid, sodium borate, boron oxide, sodium tetraphenyl borate and t-benzyl borate, and nitrogen-containing flame retardants, such as melamine cyanurate and ammonium polyphosphate.

The mixtures according to the invention can contain further additives, such as e.g. Contain lubricants and mold release agents, colorants such as dyes and pigments, lubricants such as polyethylene waxes and / or fillers.

Pigments include A wide variety of carbon blacks are suitable here. Oven blacks, acetylene blacks, gas blacks and thermal blacks obtainable by thermal production, or titanium dioxide, rutile and anatase are suitable here, which may be coated with metal oxides, such as e.g. Aluminum oxides, silicon oxides, oxides of Zn, or coated with siloxanes are considered.

The proportion of component B) or, in the given case, of components B) and C) in the mixtures according to the invention is generally from 50 to 99% by weight, preferably from 60 to 90% by weight and particularly preferably from 65 to 85% by weight, based on the total amount of components A), B) and optionally C). In addition to 100% by weight, based on the total amount of components A), B) and optionally C), the proportion of component A) is accordingly generally 1 to 50% by weight, preferably 10 to 40% by weight and particularly preferably 15 to 35% by weight.

If component C) is present, its proportion is generally 1 to 40% by weight, preferably 2 to 25% by weight and particularly preferably 3 to 15% by weight, based on the total amount of components B. ) and C). In addition to 100% by weight, based on the total amount of components B) and C), the proportion of component B) is accordingly generally 60 to 99% by weight, preferably 75 to 98% by weight and particularly preferably 85 up to 97 wt.

If component D) is present, its proportion is generally 1 to 40% by weight, preferably 2 to 25% by weight and particularly preferably 3 to 15% by weight, based on the total amount of the mixtures according to the invention. In addition to 100% by weight, based on the total amount of the mixtures according to the invention, the proportion of the components other than D) is accordingly generally 60 to 99% by weight, preferably 75 to 98% by weight and particularly preferably 85 up to 97% by weight.

The mixtures according to the invention are expediently prepared by intensive mixing of the components at temperatures in the range from 20 ° C. to 300 ° C. This is done using conventional mixing devices, e.g. Kneaders, mixers or screw extruders.

The order of mixing the components can be varied. For example, two or possibly more of the components can be premixed or all components can be mixed together.

The mixtures according to the invention can be used quite generally for the simultaneous stabilization and flame-retardant finishing of organic material.

The mixtures according to the invention and their preferred embodiments are preferably used as combined stabilizers and flame retardants for plastics.

As such, for example

Polyolefins, especially polymers of mono- and diolefins, e.g. Polyethylene, polypropylene, linear polybutene-1, polyisoprene, polybutadiene and copolymers of mono- or diolefins or mixtures of the polymers mentioned,

Copolymers of mono- or diolefins with other vinyl monomers, such as e.g. Ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers,

Polystyrene and copolymers of styrene or α-methylstyrene with dienes and / or acrylic derivatives, such as e.g. Styrene-butadiene, styrene-acrylonitrile (SAN), styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile-methacrylate, acrylonitrile-butadiene-styrene (ABS) or methyl methacrylate-butadiene-styrene (MBS),

Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates, polymethacrylates, polyacrylamides and polyacrylonitriles, Polymers derived from unsaturated alcohols and amines or from their acrylic derivatives or acetals, for example polyvinyl alcohol and polyvinyl acetate and

Polyurethanes, polyamides, polyureas, polyphenylene ethers, polyesters, polycarbonates, polysulfones, polyether sulfones and polyether ketones.

The mixtures according to the invention are particularly suitable for the first-mentioned group of polyolefins.

The present invention furthermore relates to organic materials which contain mixtures according to the invention and their preferred embodiments.

In addition, plastics are claimed in the context of the present invention which contain such mixtures according to the invention and their preferred embodiments.

In particular, polyolefins are claimed which are stabilized with such mixtures according to the invention and their preferred embodiments and are made flame-resistant.

Examples:

I) Preparation of Various Iminophosphoranes (Component B)

example 1

Synthesis of N-α-pyridyliminotriphenylphosphorane

188.6 g (0.72 mol) of triphenylphosphine, 56.4 g (0.6 mol) of 2-aminopyridine, 600 ml of acetonitrile and 180 were placed in a 2 1 four-necked flask equipped with KPG stirrer, internal thermometer, reflux condenser and dropping funnel ml of triethylamine submitted. The

The mixture was preheated to an internal temperature of 45 ° C with stirring before the dropping of 92.4 g (0.6 mol) of carbon tetrachloride was started, the rate of addition being controlled so that the temperature did not rise above 55 ° C. After the addition had ended, stirring was continued for at least two hours. The salt which separated out from the cooled reaction mixture was filtered off with suction and washed with acetonitrile. The residue resulting from the concentrated filtrate was dissolved in isopropanol and the product was precipitated again by adding water. A total of 167 g of the desired product with a melting point of 145-146 ° C. were obtained. MS (CD: 355 (M ⁺ +1).

Example 2

5

Reaction of triphenylphosphine with 2,6-diaminopyridine

If the reaction was carried out as described in Example 1, but 32.7 g of 2,6-diaminopyridine were used instead of 56.4 g of 10 2 -amopyride, 146 g of the bisiminophosphorane with a melting point of 177-178 ° C. were obtained. MS (ESI): 630 (M ⁺ +1); ³¹ P NMR (CDC1 ₃ ): 6.0 ppm.

15 Example 3

Implementation of triphenylphosphine with acetoguanamine

a) If the procedure was as in Example 2, but 37.5 g of 20 acetoguanamine were used, 162 g of a white powder were obtained.

b) In a 250 ml four-necked flask equipped with a blade stirrer, reflux condenser and internal temperature measurement, 126 g (0.053 mol) of 14% triphenylphosphine dichloride solution (in

25 chlorobenzene) and 3 g (0.024 mol) acetoguanamine

(2, 4 -Diamino-6-methyl-s-triazine) submitted. The reaction mixture was kept under reflux for 25 min, the salt which precipitated on cooling to room temperature was filtered off with suction, washed with 15 ml of chlorobenzene and 50 ml of toluene and in air

30 dried. The dry product was introduced into a 500 ml four-necked flask equipped with a blade stirrer, reflux condenser and internal temperature measurement, in 100 ml of isobutanol and 100 ml of water. 3.8 g of a 50% aqueous sodium hydroxide solution (0.048 mol) were added to the suspension. That in the

The target product present in the isobutanol fraction was obtained by removing the isobutanol by means of steam distillation. The resulting solid was filtered off, washed with 50 ml of water and dried at 60 ° C in a vacuum. 13.4 g of the desired product were obtained.

40

Melting point 239 to 243 ° C;

MS (FAB): 646 (M ⁺ +1);

"C NMR (CDCI3): 173.8, 171.3, 133.4, 131.6, 130.0, 128.9, 128.2,

25th 3 ppm;

45 ¹³ P NMR (CDCI3): 17. 5 ppm. Example 4

Reaction of triphenylphosphine with p-toluenesulfonic acid amide

5 a) 65.5 g (0.125) mol triphenylphosphine, 42.8 g (0.25 mol) p-toluenesulfonamide and 250 were in a 500 ml four-necked flask equipped with KPG stirrer, internal thermometer, dropping funnel and reflux condenser ml of tetrahydrofuran submitted. While cooling with a dry ice bath to -10 ° C was inside

A solution of 43.4 g (0.25 mol) of diethyl azodicarboxylate in 50 ml of THF was added dropwise for 10 90 minutes. After stirring for 1 h at 0 ° C and a further 4 h at 20 ° C, the mixture was worked up by suction and concentration in vacuo. Recrystallization from ethanol gave 81.1 g of the colorless product.

15 b) 1164 g (0.49 mol) of 14% triphenylphosphine dichloride solution (in chlorobenzene) and 82 g (0.48 mol) of p-toluenesulfonamide were prepared in a 2 1 four-necked flask equipped with a blade stirrer, reflux condenser and internal temperature measurement.

20 laid. The reaction mixture was heated to reflux temperature (125 to 130 ° C.) within 1 h and kept at this temperature for 2 h. After cooling to 75 ° C, 500 ml of water were added. Concentration using steam distillation led to the crystalline product, which after filtration

25 tration, washing with 2500 ml of water and drying for 16 h in vacuo at 75 ° C in an amount of 205.8 g was obtained. For cleaning, the residue was stirred at 35 ° C. with 350 ml of ethanol, filtered and washed in portions with 200 ml of ethanol. 199.5 g of a crystalline product were obtained.

30 products.

Melting point 190 to 191 ° C; MS (EI): 430 (M ⁺ );

¹³ C NMR (CDC1 ₃ ). 143.6 (s), 140.4 (s), 133.1 (d), 132.8 (d), 35 128.7 (s), 128.6 (d), 127.3 (s), 125.7 (d), 21.2 (q) ppm; ³¹ P NMR (CDCI3): 14.8 ppm.

Example 5

40 Production of t-butyliminophosphorane

1118.4 g (0.47 mol) of 14% tri-5-phenylphosphine dichloride solution (in chlorobenzene) were placed in a 2 1 double-jacketed vessel provided with a Teflon-coated metal stirrer, reflux condenser, thermal sensor for measuring the internal temperature and dropping funnel. For this purpose, a mixture of 34.3 g (0.47 ml) of t-butylamine and 47.5 g was added at an internal temperature of 2 to 8 ° C. within 77 minutes (0.47 mol) triethylamine. The mixture was stirred with cooling for a further 10 min after the end of the feed, the bath temperature was then raised gradually to 25 ° C. and the mixture was stirred at this temperature for 2 hours. The salt-like product was obtained as a residue insoluble in chlorobenzene and was isolated by filtration and washed with 200 ml of chlorobenzene and in portions with a total of 1 liter of petroleum ether. 231 g (0.46 mol) of the dry product were dissolved in a 2 1 double-jacketed vessel provided with a glass stirrer, reflux condenser, thermocouple for internal temperature measurement and dropping funnel in 1.1 1 methanol and within 10 min with 164 g (0, 91 mol) of a 30% sodium methylate solution in methanol. After stirring for 30 minutes, the solution, likewise with stirring, was added to 5.5 l of water (10 l beaker). The mixture was stirred for 10 min, the precipitate was filtered off, washed with water and dried in vacuo. 142.1 g of a colorless powder were obtained.

Melting point 145 to 147 ° C.

Example 6

Manufacture of phenyl iminophosphorane

1407 g (0.54 mol) of 14% tri-phenylphosphine dichloride solution (in chlorobenzene) were placed in a 2 1 double-jacketed vessel equipped with a Teflon-coated metal stirrer, reflux condenser, thermal sensor for internal temperature measurement and dropping funnel. For this purpose, a mixture of 49 g (0.53 ml) of aniline and 54 g (0.54 mol) of triethylamine was added at an internal temperature of 1 to 9 ° C. within 60 min. The mixture was stirred with cooling for a further 10 min after the end of the feed, the bath temperature was then raised gradually to 25 ° C. and the mixture was stirred at this temperature for 3 hours. The salt-like product was obtained as a residue insoluble in chlorobenzene and was isolated by filtration and washed with 200 ml of chlorobenzene and in portions with a total of 1 liter of petroleum ether. 280 g of dry product were dissolved in 11 ml of methanol in a 2 1 double-jacketed vessel provided with a glass stirrer, reflux condenser, thermal sensor and dropping funnel, and 180 g (1 mol) of a 30% strength sodium methylate solution in methanol were added within 10 minutes. After stirring for 30 minutes, the solution, likewise with stirring, was added to 5 l of water (10 l beaker). The mixture was stirred for 10 min, the precipitate was filtered off, washed with water and dried in vacuo. 181.4 g (97% of theory) of a colorless powder were obtained. Melting point 132 to 133 ° C.

Example 7

Synthesis of N-α-pyrazidyliminotriphenylphosphorane

33.1 g (0.126 mol) of triphenylphosphine, 10 g (0.105 mol) of 2-aminopyrazine, 100 ml of acetonitrile and 30 ml of triethylamine were placed in a 250 ml four-necked flask equipped with a KPG stirrer, internal thermometer, reflux condenser and dropping funnel. The mixture was preheated to an internal temperature of 45 ° C. with stirring. The dropwise addition of 16.2 g (0.105 mol) of carbon tetrachloride was then started. The rate of addition was controlled so that the temperature did not rise above 55 ° C. After the addition had ended, stirring was continued for at least two hours. The salt which separated out from the cooled reaction mixture was filtered off with suction and washed with acetonitrile. The residue resulting from the concentrated filtrate was dissolved in isopropanol and the product was precipitated by adding water.

A total of 29.1 g of the desired product with a melting point of 176-177 ° C. was obtained. MS (CI): 356 (M ⁺ +1).

Example 8

Synthesis of N-α-pyrimidyliminotriphenylphosphorane

If the procedure was as in Example 1, but using 57.0 g (0.6 mol) of 2-aminopyrimidine instead of 2-aminopyridine, 175.7 g of the target compound of melting point 153-155 ° C. were obtained. MS (CI): 356 (M ⁺ +1); ³¹ P NMR (CDC1 ₃ ): 15.7 ppm.

Example 9

Implementation of triphenylphosphine with benzoguanamine

If the procedure was as in Example 2, but using 56.1 g of benzoguanamine, 150 g of a white powder with a melting point of 256-257 ° C. were obtained. MS (EI): 706 (M ⁺ - 1); ³¹ P NMR (CDC1 ₃ ): 17.2 ppm. Example 10

Synthesis of N-cyano-iminotriphenylphosphorane

331 g (1.26 mol) triphenylphosphine, 88.2 g (1.05 mol) cyanguanidine [alternatively, urea can also be used], 1 were placed in a 2 1 four-necked flask equipped with a KPG stirrer, internal thermometer, reflux condenser and dropping funnel 1 acetonitrile and 300 ml of triethylamine. The mixture was preheated to an internal temperature of 45 ° C. with stirring before 102 g (1.05 mol) of carbon tetrachloride were added dropwise. The rate of addition was controlled so that the temperature did not rise above 55 ° C. After the addition had ended, stirring was continued for at least two hours. The salt which separated out from the cooled reaction mixture was filtered off with suction and washed with a little acetonitrile. The residue was stirred with water, then suction filtered and dissolved in warm isopropanol. The product precipitated again when water was added. 119 g of the product with a melting point of 195-196 ° C. were obtained. MS (FAB): 303 (M ⁺ +1);

¹³ C-NMR (CDC1 ₃ ): 133.4, 132.5, 132.4, 129.3, 129.1, 127.3, 126.2, 118.7ppm. ³¹ P NMR (CDCI ₃ ): 25.1 ppm;

Analysis for CιgHι ₅ N ₂ P: calc. C 75.49, H 5.00, N 9.27; found C 75.2, H 5.1, N 9.3.

Example 11

Preparation of the bis-iminophosphorane from 1,8-diaminomentane

The procedure was analogous to Example 5, using triethylamine as the auxiliary base. The residue isolated from chlorobenzene was treated with a strong base.

Melting point 200-205 ° C

Example 12

Production of the iminophosphorane from 2-amino-3-cyano-4-oxo-tetra-hydrothiophene

The procedure was analogous to Example 6

Melting point 168 ° C II) Test in polypropylene

The stabilizers and flame retardants given in Table 1 below (the percentages are% by weight in the total mixture of stabilizers, flame retardants and polypropylene; the proportion of the latter is 100% in addition) were used together with the polypropylene (Novolen ^® 1102 H, From BASF) premixed on a high-speed mixer and then homogenized and granulated using a screw-in laboratory extruder (from Weber) at a melt temperature of 240 ° C.

Test pieces in the format (65x45x2) mm were produced from the present granulate on an injection molding machine and these were weathered in a rapid weathering device of the Xenotest 1200 type in accordance with DIN 53 387. Crack formation was assessed after 600 hours.

Designate in Table 1:

Uvinul ^® 4050 H (from BASF) a monomeric, sterically hindered amine (N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-bisformyl-1,6-diaminohexane) ,

Uvinul 5050 H (BASF) an oligomeric sterically hindered amine of the formula

and a molecular weight of approx. 3500 g / mol (ie n is approx. 6 to 7),

FR 7053 PP (from Constab) a conventional halogen-containing flame retardant based on decabromodiphenylethane / antimony trioxide,

Melapur ^® MC 25 (from Chemie Linz) a halogen-free flame retardant based on melamine cyanurate and

IP 6 is the iminophosphorane (aniliniminophosphorane) produced in Example 6. For the purposes of the present invention, Uvinul ^υ 4050 H and / or Uvinul ^® 5050 H as component A (group a22)), IP 6 (aniliniminophosphorane) as component B and Melapur ^® MC 25 as (optional) further component C are to be addressed.

Table 1

* Comparative examples

A comparison of Examples 16 * to 18 * with the corresponding Examples 20 to 21 shows that when a conventional halogen-containing FSM is used, the effectiveness of the stabilizers against exposure to the polymer is negatively influenced to a large extent.

In addition, the comparison of Examples 13 * (unstabilized polymer) and 15 * with Example 19 * shows that the mixture of FSMn used in the latter already has a certain stabilizing effect compared to the conventional halogen-containing FSM.

Claims

claims

1. Mixtures containing as a component

A) stabilizers for protecting organic materials against the harmful effects of light, heat and / or oxidation,

B) iminophosphoranes as flame retardants for organic materials,

D) if necessary, further additives.

2. Mixtures according to claim 1 containing as component A) at least one stabilizer selected from the group consisting of

al) alkylated monophenols, a2) alkylthiomethylphenols, a3) hydroquinones and alkylated hydroquinones, a4) tocopherols, a5) hydroxylated diphenylthioethers, a6) alkylidene bisphenols, a7) 0-, N- and S-benzyl compounds, a8) aromatic hydroxybenzyl compounds, a9 alO) benzylphosphonates, all) acylaminophenols, al2) esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, β- (5-tert-butyl-4-hydroxy-3) -methylphenyl) - propionic acid, ß- (3, 5 -dicyclohexyl -4 -hydroxyphenyl) -propionic acid and 3, 5 -Di - tert. -butyl -4-hydroxyphenylacetic acid, al3) amides of ß- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, al4) ascorbic acid and its derivatives, al5) antioxidants based on amine compounds , al6) phosphites and phosphonites, al7) 2- (2'-hydroxyphenyl) benzotriazoles, al8) sulfur-containing peroxide scavengers or sulfur-containing antioxidants al9) 2 -hydroxybenzophenones, a20) esters of unsubstituted and substituted benzoic acid, a21) acrylates, a22) sterically hindered amines, a23) oxamides and a24) 2- (2-hydroxyphenyl) - 1, 3, 5 - triazines.

3. Mixtures according to claim 1 or 2 containing as component B) at least one iminophosphorane of the formula ZX (I) or of the formula Y (-Z) _n (II), in which

Z is a radical R ¹ R ² R ³ P = N-,

R ¹ , R ² and R ³ independently of one another are C ₁ -C ₄ alkyl, C ₆ -C ₂ o ^_ aryl or C -C ₂ o heteroaryl,

X is hydrogen, -CC ₂ o-alkyl, C ₆ -C ₂ o-aryl, C ₃ -C ₂ o-heteroaryl, RS0 ₂ -, P (0) R ₂ -, P (S) R ₂ -, cyano , Amino or tri (-CC ₆ -alkyl) -silyl,

R Cι-Cι ₂ -alkyl, Cι ₂ -alkoxy, Cι ₂ alkylthio, C ₆ -C ₂ o-aryl, C ₆ -C ₂ o ~ aryloxy or C ₆ -C ₂ o ~ arylthio,

Y is an n-valent organic radical selected from the group consisting of C ₂ -C ₂ o-alkylenes and C ₃ -C o-cycloalkylenes in which one or more non-adjacent CH ₂ groups are replaced by oxygen, sulfur, -N (R ') -, -CO-, -S0 ₂ -, optionally alkyl-substituted arylene and / or optionally alkyl-substituted heteroarylene and / or which can be substituted with cyano or isocyanate groups, arylenes, heteroarylenes, C ₆ -C ₂ o ~ aryl (S0 ₂ -) _n , HP (0) =, P (0) s. P (S) s, C ₁ -C ₂ -Al yl-P (0) =, C ₆ -C ₂₀ aryl P (0) =, C ₁ -C ₂ -alkyl-P (S) = and C ₆ - C ₂₀ aryl -P (S) =,

R 'is hydrogen or -CC ₁₂ alkyl and

n is an integer value of 2, 3, 4, 5, 6, 7, 8, 9 or 10.

4. Use of mixtures according to claims 1 to 3 as combined stabilizers and flame retardants for organic materials.

5. Use of mixtures according to claims 1 to 3 as combined stabilizers and flame retardants for plastics.

6. Organic materials containing mixtures according to claims 1 to 3.

7. plastics containing mixtures according to claims 1 to 3.