EP0000352A1 - Cyclic aromatic diesters of phosphonous acid and the organic materials stabilized by them - Google Patents

Cyclic aromatic diesters of phosphonous acid and the organic materials stabilized by them Download PDF

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Publication number
EP0000352A1
EP0000352A1 EP78100271A EP78100271A EP0000352A1 EP 0000352 A1 EP0000352 A1 EP 0000352A1 EP 78100271 A EP78100271 A EP 78100271A EP 78100271 A EP78100271 A EP 78100271A EP 0000352 A1 EP0000352 A1 EP 0000352A1
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Prior art keywords
tert
butyl
dibenz
methyl
phenoxy
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EP78100271A
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German (de)
French (fr)
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EP0000352B1 (en
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Michael Dr. Rasberger
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/65719—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonous acid derivative
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2

Definitions

  • the invention relates to new phosphonites, their production, use as stabilizers for plastics and elastomers, and the polymers stabilized therewith.
  • Phosphonites are known as stabilizers, in particular 6-phenoxy-dibenz [c, e] - [1,2] -oxaphosphorine and 6- (2,6-di-tert-butyl-4-methyl-phenoxy) -dibenz - (c, e) - [1,2] -oxaphosphorin (Examples 9 and 10 of DT-OS 2.034.887).
  • stabilizers in particular 6-phenoxy-dibenz [c, e] - [1,2] -oxaphosphorine and 6- (2,6-di-tert-butyl-4-methyl-phenoxy) -dibenz - (c, e) - [1,2] -oxaphosphorin.
  • these phosphonites do not meet the high requirements that a stabilizer should meet in every respect, in particular with regard to storage stability, water absorption, sensitivity to hydrolysis, processing stabilization, color improvement, volatility, compatibility and improvement in light protection.
  • the object of the invention was to provide stabilizers which do not have these disadvantages or only have them to a lesser extent.
  • R 1 and R 2 are in particular those with 1-8 C atoms, such as straight-chain or branched alkyl with 1-8 C atoms, for example methyl, i-propyl or tert-butyl, and in particular as halogen Chlorine.
  • R 3 and R 5 are in particular those with 1-25 C atoms, such as C 1 -C 12 , especially C 1 -C 8 alkyl, for example methyl, ethyl, i-propyl, tert-butyl , tert-pentyl or tert-octyl, C 3 -C 4 alkenyl, e.g. allyl or methallyl, C3-C4 alkynyl, e.g. propargyl, C 5 -C 12 cycloalkyl, e.g.
  • cyclohexyl (C 1 -C 8 alkyl) - C 5 -C 8 cycloalkyl, for example a-methylcyclohexyl, C 7 -C 14 aralkyl, for example benzyl, a-methylbenzyl or a, a-dimethylbenzyl, C 6 -C 14 aryl, for example phenyl, C 7 -C 14 alkaryl, such as (C 1 -C 8 alkyl) phenyl, for example tolyl.
  • R 3 and R 5 can also be substituted alkyl, in particular with a total of 1-25 C atoms, such as - (C 1 -C 8 ) -alkyl-CO-XR 6 , in which X and R 6 are the above and are given below as preferred
  • X and R 6 are the above and are given below as preferred
  • Have importance such as 1,1-dimethyl-4-ethoxycarbonyl-butyl, or di- (C 1 -C 8 alkyl) -phosphonomethyl, for example diethylphosphonomethyl, or C 1 -C 36 aminoalkyl, especially aminomethyl, such as (C 1 -C 18 alkyl) aminomethyl or di (C 1 -C 18 alkyl) aminomethyl, for example dimethylaminomethyl or di-n-butylaminomethyl, or (C 1 -C 18 acyloxy) methyl or (C 1 -C 18 acylthio) methyl , such as (C 1 -C 18 alkan
  • R 5 can also be: C 1 -C 18 alkoxycarbonylmethyl, for example methoxycarbonylmethyl or n-octadecyloxycarbonylmethyl, or 2- (C 1 -C 18 alkoxycarbonyl) ethyl, such as 2- (methoxycarbonyl) ethyl, or cyanomethyl.
  • R 4 is as optionally substitutierter hydrocarbon radical, in particular the meanings given in general for R 3 / R S and, as preferred, and as -CO-XR 6 in particular (C 1 -C 18 alkoxy) carbonyl, for example methoxycarbonyl or n-octadecyloxycarbonyl, (C 6 -C 14 aryloxy) carbonyl, such as phenoxycarbonyl, or (C 1 -C 18 alkyl) phenoxycarbonyl, for example 2,4-di-tert-butylphenoxycarbonyl, or (C S -C 7 cycloalkoxy) - carbonyl, e.g. cyclohexyloxycarbonyl.
  • R 4 as -PO- (OR 8 ) 2 is especially one in which R 8 is C 1 -C 18 alkyl, such as diethylphosphono, di-n-butylphosphono or di-n-octylphosphono.
  • the phosphonites of the formulas I and II can be prepared by methods known per se, in particular by esterification or transesterification reactions, for example by using a phosphonite of the formulas wherein R 10 is a reactive group and R 1 , R 2 , x and y have the meaning given above, with a phenol of the formula where R 3 , R 4 , R 5 and R 9 have the meaning given above.
  • a reactive group R 10 is, for example, halogen, especially chlorine; Alkoxy or optionally substituted phenoxy.
  • the reaction can be carried out in a manner known per se, for example by heating, preferably to above about 80 ° C., in particular above 150 ° C., such as 150-240 °, for example 220 °, HR 10 being split off, R 10 being the above Has meaning; or in the presence of bases, such as amines, for example triethylamine, pyridine, N, N-dimethylaniline or sodium carbonate, preferably in an inert solvent, such as aprotic solvents, for example ligroin, toluene, dimethylformamide, dimethylacetamide, sulfolane, methyl ethyl ketone, acetonitrile or ethyl acetate, but it is also possible to use excess amine bases and serve as solvents (cf. also DT-OS 2,034,887).
  • bases such as amines, for example triethylamine, pyridine, N, N-dimethylaniline or sodium carbonate
  • the starting materials are known or, if they are new, can be prepared analogously to known ones.
  • P-Cl phosphonites are e.g. known from DT-OS 2.034.887, while the starting phenols are long-known compounds and are often commercially available.
  • the compounds of the formula I / II can be used as stabilizers for plastics and elastomers against their damage by the action of oxygen, light and heat.
  • plastics are the polymers listed in DT-OS 2,456,864 on pages 12-14.
  • Another object of the present invention is a method for stabilizing polymers against thermo-oxidative degradation during manufacture, insulation, processing and use, which is characterized in that that at least one compound of the formula I / II is added to the polymer.
  • the compounds of the formula I / II are incorporated into the substrates in a concentration of 0.005 to 5% by weight, calculated on the material to be stabilized.
  • 0.01 to 1.0, particularly preferably 0.02 to 0.5% by weight of the compounds, calculated on the material to be stabilized, are preferably incorporated into the latter.
  • the incorporation can be carried out, for example, by mixing in at least one of the compounds of the formula I / II and, if appropriate, further additives by the methods customary in industry, before or during shaping, or by applying the dissolved or dispersed compounds to the polymer, optionally with subsequent evaporation of the solvent.
  • the new compounds can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example in a concentration of 2.5 to 25% by weight.
  • the compounds are added before cross-linking.
  • the invention therefore also relates to the plastics stabilized by the addition of 0.01 to 5% by weight of a compound of the formula I / II, which may also contain other additives.
  • the plastics stabilized in this way can be used in various forms, e.g. as foils, fibers, tapes, profiles or as binders for paints, adhesives or putties.
  • antioxidants such as 2- (2'-hydroxyphenyl) benzotriazoles, 2,4-bis (2'-hydroxyphenyl) -6-alkyl-s-triazines, 2-hydroxybenzophenones, 1,3-bis (2'-hydroxybenzoyl) benzenes, esters of optionally substituted benzoic acids, acrylates, further nickel compounds, sterically hindered amines, oxalic acid diamides, metal deactivators, phosphites, peroxide-destroying compounds, polyamide stabilizers, basic co-stabilizers, nucleating agents or other additives such as Plasticizers, lubricants, emulsifiers, fillers, carbon black, asbestos, kaolin, talc, glass fibers, pigments, optical brighteners, flame retardants, antistatic agents.
  • UV absorbers and light stabilizers such as 2- (2'-hydroxyphenyl) benzotriazoles, 2,4-bis (2'-hydroxyphenyl) -6-alkyl-s-tri
  • the mixture obtained is extruded in a laboratory single-screw extruder at a die temperature of 280 ° C. and then granulated.
  • the granules without additives required for comparison purposes are produced in an analogous manner.
  • the granules are dried in a vacuum oven at 120 ° C for 12 hours.
  • the effectiveness of the stabilizer against yellowing of the material is tested in a laboratory injection molding machine at a maximum of 310 ° C.
  • the yellowing of the 2 mm thick die cast plates is assessed by measuring the Yellowness Index according to ASTM 1925-63.
  • melt index of the polymer is measured in each case after the 1st, 3rd and 5th, or after the 1st and 3rd extrusion, the load being 2160 g, the temperature 230 ° C. and the measurement variable g / 10 min.
  • the degradation of the polymer manifests itself in an increase in the melt index.
  • Example 20 The procedure was as in Example 20, but using a different polypropylene powder (Shell Carlona HY 61 / 1090/1324) of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate ] 0.07 parts were used.
  • a different polypropylene powder Shell Carlona HY 61 / 1090/1324
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate ] 0.07 parts were used.
  • the oil to be tested is placed in a glass vessel together with water and a copper spiral as a catalyst and the glass vessel is placed in a pressure vessel provided with a pressure registering device. After the pressure vessel has been flushed with oxygen and set to 6.25 bar (90 psi), it is rotated axially in a bath at a constant temperature (150 ° C). The time until a pressure drop of 1.7 bar (25 psi) occurs is determined.

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Abstract

Aromatische cyclische Phosphonigsäure-diester der Formeln <IMAGE> eignen sich als Stabilisatoren für organisches Material.Aromatic cyclic phosphonous acid diesters of the formulas <IMAGE> are suitable as stabilizers for organic material.

Description

Die Erfindung betrifft neue Phosphonite, ihre Herstellung, Verwendung als Stabilisatoren für Kunststoffe und Elastomere, sowie die damit stabilisierten Polymeren.The invention relates to new phosphonites, their production, use as stabilizers for plastics and elastomers, and the polymers stabilized therewith.

Phosphonite sind als Stabilisatoren bekannt, insbesondere das 6-Phenoxy-dibenz[c,e]-[1,2]-oxaphosphorin und das 6-(2,6-Di-tert.-butyl-4-methyl-phenoxy)-dibenz-(c,e)-[1,2]-oxaphosphorin (Beispiele 9 und 10 der DT-OS 2.034.887). Diese Phosphonite genügen jedoch nicht in jeder Hinsicht den hohen Anforderungen, denen ein Stabilisator genügen soll, insbesondere hinsichtlich Lagerstabilität, Wasseraufnahme, Hydrolyseempfindlichkeit, Verarbeitungsstabilisierung, Farbverbesserung, Flüchtigkeit, Verträglichkeit und Lichtschutzverbesserung.Phosphonites are known as stabilizers, in particular 6-phenoxy-dibenz [c, e] - [1,2] -oxaphosphorine and 6- (2,6-di-tert-butyl-4-methyl-phenoxy) -dibenz - (c, e) - [1,2] -oxaphosphorin (Examples 9 and 10 of DT-OS 2.034.887). However, these phosphonites do not meet the high requirements that a stabilizer should meet in every respect, in particular with regard to storage stability, water absorption, sensitivity to hydrolysis, processing stabilization, color improvement, volatility, compatibility and improvement in light protection.

Aufgabe der Erfindung war es, Stabilisatoren zu schaffen, die diese Nachteile nicht oder nur in schwächerem Mass aufweisen.The object of the invention was to provide stabilizers which do not have these disadvantages or only have them to a lesser extent.

Demgemäss betrifft die Erfindung Phosphonite der Formeln I und II

Figure imgb0001
worin

  • R1 und R2 unabhängig voneinander ein gegebenenfalls substituierter Kohlenwasserstoffrest oder Halogen sind,
  • x und y unabhängig voneinander 0, 1,2 oder 3 sind,
  • R3 und R5 unabhängig voneinander Wasserstoff oder ein gegebenenfalls substituierter Kohlenwasserstoffrest sind, und
  • R4 Wasserstoff, ein gegebenenfalls substituierter Kohlenwasserstoffrest, -CO-X-R6, -PO-(OR8)2 oder -OR8 ist, worin
  • X -0- oder -NR7- ist,
  • R6 und R7 unabhängig voneinander Wasserstoff oder ein gegebenenfalls substituierter Kohlenwasserstoffrest sind, und
  • R8 ein gegebenenfalls substituierter Kohlenwasserstoffrest ist,
  • wobei nicht alle drei Reste R3, R4 und R5 zugleich Wasserstoff sind, und
  • wobei im Fall von R3 und R5 gleich tert.-Butyl R4 nicht Methyl ist, und
  • R9 Wasserstoff, und falls R3 Wasserstoff ist, auch Methyl bedeutet.
Accordingly, the invention relates to phosphonites of the formulas I and II
Figure imgb0001
 wherein
  • R1 and R 2 are, independently of one another, an optionally substituted hydrocarbon radical or halogen,
  • x and y are independently 0, 1, 2 or 3,
  • R 3 and R 5 are independently hydrogen or an optionally substituted hydrocarbon radical, and
  • R 4 is hydrogen, an optionally substituted hydrocarbon radical, -CO-XR 6 , -PO- (OR 8 ) 2 or -OR 8 , wherein
  • X is -0- or -NR 7 -,
  • R 6 and R 7 are independently hydrogen or an optionally substituted hydrocarbon radical, and
  • R 8 is an optionally substituted hydrocarbon radical,
  • where not all three radicals R3, R 4 and R 5 are simultaneously hydrogen, and
  • where in the case of R 3 and R 5 is tert-butyl R 4 is not methyl, and
  • R 9 is hydrogen, and if R 3 is hydrogen, also means methyl.

R1 und R2 sind als gegebenenfalls substituierter Kohlenwasserstoffrest insbesondere ein solcher mit 1-8 C-Atomen, wie geradkettiges oder verzweigtes Alkyl mit 1-8 C-Atomen, z.B. Methyl, i-Propyl oder tert.-Butyl, und als Halogen insbesondere Chlor.As optionally substituted hydrocarbon radicals, R 1 and R 2 are in particular those with 1-8 C atoms, such as straight-chain or branched alkyl with 1-8 C atoms, for example methyl, i-propyl or tert-butyl, and in particular as halogen Chlorine.

R3 und R5 sind als gegebenenfalls substituierter Kohlenwasserstoffrest insbesondere ein solcher mit 1-25 C-Atomen, wie C1-C12, vor allem C1-C8 Alkyl, z.B. Methyl, Aethyl, i-Propyl, tert.-Butyl, tert.-Pentyl oder tert.-Octyl, C3-C4 Alkenyl, z.B. Allyl oder Methallyl, C3-C4 Alkinyl, z.B. Propargyl, C5-C12 Cycloalkyl, z.B. Cyclohexyl, (C1-C8 Alkyl)-C5-C8 Cycloalkyl, z.B. a-Methylcyclohexyl, C7-C14 Aralkyl, z.B. Benzyl, a-Methylbenzyl oder a,a-Dimethylbenzyl, C6-C14 Aryl, z.B. Phenyl, C7-C14 Alkaryl, wie (C1-C8 Alkyl)-phenyl, z.B. Tolyl. R3 und R5 kann auch substituiertes Alkyl sein, insbesondere mit insgesamt 1-25 C-Atomen, wie -(C1-C8)-Alkyl-CO-X-R6, worin X und R6 obige und im folgenden als bevorzugt angegebene Bedeutung haben, wie 1,1-Dimethyl-4-äthoxycarbonyl-butyl, oder Di-(C1-C8 Alkyl)-phosphonomethyl, z.B. Diäthylphosphonomethyl, oder C1-C36 Aminoalkyl, insbesondere Aminomethyl, wie (C1-C18 Alkyl)-aminomethyl oder Di-(C1-C18 Alkyl)-aminomethyl, z.B. Dimethylaminomethyl oder Di-n-butylaminomethyl, oder (C1-C18 Acyloxy)-methyl oder (C1-C18 Acylthio)-methyl, wie (C1-C18 Alkanoyloxy)-methyl, oder, (C1-C18 Alkanoylthio)-methyl, N-alkyliertes (C1-C18 Carbamoyloxy)-methyl, n-alkyliertes (C1-C18 Carbamoylthio)-methyl oder N-alkyliertes (C1-C18 Thiocarbamoylthio)-methyl, z.B. Acetoxymethyl, Propionylthiomethyl, N,N-Di-n-butyl-carbamoyloxy-methyl, N,N-Di-n-butyl-carbamoylthio-methyl, N,N-Di-n-butyl-thio- carbamoylthio-methyl oder N,N-Di-n-octyl-thiocarbamoylthio- methyl. R5 kann zudem auch sein: C1-C18 Alkoxycarbonylmethyl, z.B. Methoxycarbonylmethyl oder n-Octadecyloxycarbonylmethyl, oder 2-(C1-C18 Alkoxycarbonyl)-äthyl, wie 2-(Methoxycarbonyl)-äthyl, oder Cyanomethyl.As optionally substituted hydrocarbon radicals, R 3 and R 5 are in particular those with 1-25 C atoms, such as C 1 -C 12 , especially C 1 -C 8 alkyl, for example methyl, ethyl, i-propyl, tert-butyl , tert-pentyl or tert-octyl, C 3 -C 4 alkenyl, e.g. allyl or methallyl, C3-C4 alkynyl, e.g. propargyl, C 5 -C 12 cycloalkyl, e.g. cyclohexyl, (C 1 -C 8 alkyl) - C 5 -C 8 cycloalkyl, for example a-methylcyclohexyl, C 7 -C 14 aralkyl, for example benzyl, a-methylbenzyl or a, a-dimethylbenzyl, C 6 -C 14 aryl, for example phenyl, C 7 -C 14 alkaryl, such as (C 1 -C 8 alkyl) phenyl, for example tolyl. R 3 and R 5 can also be substituted alkyl, in particular with a total of 1-25 C atoms, such as - (C 1 -C 8 ) -alkyl-CO-XR 6 , in which X and R 6 are the above and are given below as preferred Have importance, such as 1,1-dimethyl-4-ethoxycarbonyl-butyl, or di- (C 1 -C 8 alkyl) -phosphonomethyl, for example diethylphosphonomethyl, or C 1 -C 36 aminoalkyl, especially aminomethyl, such as (C 1 -C 18 alkyl) aminomethyl or di (C 1 -C 18 alkyl) aminomethyl, for example dimethylaminomethyl or di-n-butylaminomethyl, or (C 1 -C 18 acyloxy) methyl or (C 1 -C 18 acylthio) methyl , such as (C 1 -C 18 alkanoyloxy) methyl, or, (C 1 -C 18 alkanoylthio) - methyl, N-alkylated (C 1 -C 18 carbamoyloxy) methyl, n-alkylated (C 1 -C 18 carbamoylthio) methyl or N-alkylated (C 1 -C 18 thiocarbamoylthio) methyl, e.g. acetoxymethyl, propionylthiomethyl, N , N-Di-n-butyl-carbamoyloxy-methyl, N, N-Di-n-butyl-carbamoylthio-methyl, N, N-Di-n-butyl-thio-carbamoylthio-methyl or N, N-Di-n -octyl-thiocarbamoylthio-methyl. R 5 can also be: C 1 -C 18 alkoxycarbonylmethyl, for example methoxycarbonylmethyl or n-octadecyloxycarbonylmethyl, or 2- (C 1 -C 18 alkoxycarbonyl) ethyl, such as 2- (methoxycarbonyl) ethyl, or cyanomethyl.

R4 hat als gegebenenfalls substitutierter Kohlenwasserstoffrest insbesondere die für R3/RS allgemein und als bevorzugt angegebene Bedeutung und ist als -CO-X-R6 insbesondere (C1-C18 Alkoxy)-carbonyl, z.B. Methoxycarbonyl oder n-Octadecyloxycarbonyl, (C6-C14 Aryloxy)-carbonyl, wie Phenoxycarbonyl,oder (C1-C18 Alkyl)-phenoxycarbonyl, z.B. 2,4-Di-tert.-butyl-phenoxycarbonyl, oder (CS-C7 Cyclo- alkoxy)-carbonyl, z.B. Cyclohexyloxycarbonyl. R4 ist als -PO-(OR8)2 insbesondere solches, worin R8 C1-C18 Alkyl ist, wie Diäthylphosphono, Di-n-butylphosphono oder Di-n-octylphosphono.R 4 is as optionally substitutierter hydrocarbon radical, in particular the meanings given in general for R 3 / R S and, as preferred, and as -CO-XR 6 in particular (C 1 -C 18 alkoxy) carbonyl, for example methoxycarbonyl or n-octadecyloxycarbonyl, (C 6 -C 14 aryloxy) carbonyl, such as phenoxycarbonyl, or (C 1 -C 18 alkyl) phenoxycarbonyl, for example 2,4-di-tert-butylphenoxycarbonyl, or (C S -C 7 cycloalkoxy) - carbonyl, e.g. cyclohexyloxycarbonyl. R 4 as -PO- (OR 8 ) 2 is especially one in which R 8 is C 1 -C 18 alkyl, such as diethylphosphono, di-n-butylphosphono or di-n-octylphosphono.

  • R4 ist als -OR8 insbesondere C1-C18 Alkoxy, z.B. Methoxy.R 4 is -OR 8, in particular C 1 -C 18 alkoxy, for example methoxy.
  • R7 ist insbesondere Wasserstoff oder C1-C18 Alkyl, z.B. Methyl. R7 is in particular hydrogen or C 1 -C 18 alkyl, for example methyl.
  • R9 ist insbesondere Wasserstoff.R 9 is especially hydrogen.
  • Bevorzugt sind Phosphonite der Formel I, worinPhosphonites of the formula I are preferred in which
  • R 1 C1-C8 Alkyl ist, R 1 is C 1 -C 8 alkyl,
  • x 0,1 oder 2 ist, y 0 ist,x is 0.1 or 2, y is 0,
  • R3 und R5 unabhängig voneinander Wasserstoff, gegebenenfalls substituiertes C1-C25 Alkyl, C3-C4 Alkenyl, C3-C4 Alkinyl, C5-C12 C cloalkyl, C6-C13 a- Methylcycloalkyl, C7-C14 Aralkyl, C7-C14 Alkaryl oder C6-C14 Aryl sind,R 3 and R 5 are independently hydrogen, optionally substituted C 1 -C 25 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 Al k y l, C 5 -C 12 C clo a lk yl, C 6 - C 13 a- M ethylcycloalkyl, C7 -C14 aralkyl, C 7 -C 14 alkaryl or C 6 -C 14 aryl,
  • R4 eine der für R3/R5 gegebenen Bedeutungen hat oder (C1-C18 Alkoxy)-carbonyl, (C5-C7 Cycloalk- oxy)-carbonyl, Phenoxycarbonyl, (C1-C12 Alkyl)-phenoxycarbonyl, C1-C18 Alkoxy oder 2-(C1-C18 Alkoxycarbonyl)-äthyl ist,R 4 is a 3 / R 5 has the meanings given for R, or (C 1 -C 18 Alkox y) carbonyl, (C 5 -C 7 Cycloalk- oxy) -carbonyl, phenoxycarbonyl, (C 1 -C 12 alkyl) - phenoxycarbonyl, C 1 -C 18 alkoxy or 2- (C 1 -C 18 alkoxycarbonyl) ethyl,
  • wobei nicht alle drei Reste R3, R4 und R5 zugleich Wasserstoff sind, undwhere not all three radicals R 3 , R 4 and R 5 are simultaneously hydrogen, and
  • wobei im Fall von R3 und R5 gleich tert.-Butyl R4 nicht Methyl ist.where in the case of R 3 and R 5 is tert-butyl R 4 is not methyl.
  • Besonders bevorzugt sind Phosphonite der Formel I, worinParticularly preferred are phosphonites of formula I, wherein
  • x und y 0 sind,x and y are 0,
  • R3 und R5 unabhängig voneinander Wasserstoff, C1-C12 Alkyl, Cyclohexyl, a-Methylcyclohexyl, Benzyl, a,a-Dimethylbenzyl, Phenyl oder (C1-C18 Alkoxy)-carbonyl-C1-C8-alkyl sind, undR 3 and R 5 are independently hydrogen, C 1 -C 12 alkyl, cyclohexyl, a-methylcyclohexyl, benzyl, a, a-dimethylbenzyl, phenyl or (C 1 -C 18 alkoxy) carbonyl-C 1 -C 8 alkyl are and
  • R4 eine der für R3/R5 gegebenen Bedeutungen hat oder (C1-C18 Alkoxy)-carbonyl, oder 2-(C1-C18 Alkoxycarbonyl)-äthyl ist;R 4 has one of the meanings given for R 3 / R 5 or is (C 1 -C 18 alkoxy) carbonyl, or 2- (C 1 -C 18 alkoxycarbonyl) ethyl;
  • wobei nicht alle drei Reste R3, R4 und R5 zugleich Wasserstoff sind, undwhere not all three radicals R3 , R 4 and R 5 are simultaneously hydrogen, and
  • wobei im Fall von R3 und R5 gleich tert.-Butyl R4 nicht Methyl ist.where in the case of R 3 and R 5 is tert-butyl R 4 is not methyl.

Vor allem betrifft die Erfindung Phosphonite der Formel I, worin

  • x und y 0 sind,
  • R3 und R5 unabhängig voneinander C1-C12 Alkyl, Cyclohexyl, a-Methylcyclohexyl, Benzyl, a,a-Dimethylbenzyl oder Phenyl sind, oder eines von R3 und R4 Wasserstoff ist und das andere obige Bebeutung hat, und
  • R4 Wasserstoff, C1-C12 Alkyl, (C1-C18 Alkoxy)-carbonyl oder 2-(C1-C18 Alkoxycarbonyl)-äthyl ist,
  • wobei im Fall von R3 und R5 gleich tert.-Butyl R4 nicht Methyl ist.
In particular, the invention relates to phosphonites of the formula I in which
  • x and y are 0,
  • R 3 and R 5 are independently C 1 -C 12 alkyl, cyclohexyl, a-methylcyclohexyl, benzyl, a, a-dimethylbenzyl or phenyl, or one of R 3 and R 4 is hydrogen and the other has the above meaning, and
  • R 4 is hydrogen, C 1 -C 12 alkyl, (C 1 -C 18 alkoxy) carbonyl or 2- (C 1 -C 18 alkoxycarbonyl) ethyl,
  • where in the case of R 3 and R 5 is tert-butyl R 4 is not methyl.

Bevorzugt sind insbesondere die folgenden Verbindungen, neben den in den Beispielen genannten Verbindungen:

  • 1. 6-(2,6-Di-äthyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 2. 6-(2,4,6-Tri-methyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 3. 6-(2-Phenyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 4. 6-(2,6-Di-isopropyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 5. 6-(2,6-Di-phenyl-4-methoxy-phenoxy)-dibenz[c,e]-[l,2]-oxaphosphorin,
  • 6. 6-(2,6-Di-tert.-butyl-4-n-octadecyloxycarbonyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 7. 6-[2,6-Di-tert.-butyl-4-diäthylphosphono-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 8. 6-(2-Methyl-4-di-n-butylaminomethyl-6-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 9. 6-[2,6-Di-tert.-butyl-4-(N,N-di-n-octylthiocarbamoyl- thiomethyl)-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 10. 6-[2,6-(Di-1,1-dimethyl-4-äthoxycarbonyl-butyl)-4-methyl-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 11. 6-(2-Methyl-4-n-octadecyloxycarbonylmethyl-6-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 12. 6-(2,6-Di-i-propyl-4-(2-methoxycarbonyl-äthyl)-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 13. 6-[2-Methyl-4-(2,4-di-tert.-butyl-phenoxycarbonyl)-6-tert.-butyl-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 14. 6-(2-Cyclohexyl-4-tert.-octyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 15. 6-(2-Methyl-4-diäthylphosphonomethyl-6-a,a-dimethylbenzyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 16. 6-(2,4-Di-i-propyl-6-phenyl-phenoxy)-dibenz[c,e]-[1,2]-oxaphosphorin,
  • 17. 2-tert.-Butyl-6-(2,4-di-tert.-butyl-phenoxy)-dibenz-[c,e]-[1,2]oxaphosphorin,
  • 18. 2,4-Di-tert.-butyl-6-(2,4-di-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 19. 2,4-Di-tert.-butyl-6-(2,6-di-i-propyl-4-tert.-octyl- phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 20. 4-tert.-Butyl-6-(2,4-di-tert.-butyl-6-phenyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 21. 2,4-Di-tert.-butyl-6-[2-methyl-4-(2-n-octadecyloxy- carbonyläthyl)-6-tert.-butylphenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 22. 2,4-Di-tert.-butyl-6-(2,6-di-tert.-butyl-4-methyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 23. 2,4-Di-tert.-butyl-6-(2,6-di-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 24. 6-(2,6-Di-tert.-butyl-4-diäthylphosphonomethyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 25. 6-(2,6-Di-tert.-butyl-4-tert.-octyl-phenoxy)-dibenz-[c,e,]-[1,2]oxaphosphorin,
  • 26. 6-(2-tert.-Butyl-4-methyl-6-a-methylcyclohexyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 27. 6-[2,6-Di-(a,a-dimethylbenzyl)-4-n-octadecyloxycarbonyl- methyl-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 28. 6-(2-tert.-Butyl-4-methyl-6-tert.-pentyl-phenoxy)-dibenz[c,e]-[l,2]oxaphosphorin,
  • 29. 6-(2-tert.-Butyl-4,6-di-tert.-octyl-phenoxy)-dibenz-[c,e]-[1,2]oxaphosphorin,
  • 30. 6-[2,6-Di-tert.-butyl-4-(2,4-di-tert.-butyl-phenoxycarbonyl)-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 31. 6-[2,6-Di-tert.-pentyl-4-(2-äthoxycarbonyl-äthyl)-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 32. 6-[2-tert.-Butyl-4-methyl-6-(1,1-dimethyl-4-äthoxy- carbonyl-butyl)-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 33 6-(2,6-Di-tert.-butyl-4-cyanomethyl-phenoxy)-dibenz-[c,e]-[1,2]oxaphosphorin.
  • 34. 6-(2-tert.-Butyl-5-methyl-phenoxy)-dibenz [c,e]-[1,2]oxaphosphorin.
  • 35. 6-(2,4-Di-tert.butyl-5-methyl-phenoxy)-dibenz [c,e]-[l,2]oxaphosphorin.
In particular, the following compounds are preferred, in addition to the compounds mentioned in the examples:
  • 1. 6- (2,6-di-ethylphenoxy) dibenz [c, e] - [1,2] oxaphosphorin,
  • 2. 6- (2,4,6-tri-methylphenoxy) dibenz [c, e] - [1,2] oxaphosphorin,
  • 3. 6- (2-phenylphenoxy) dibenz [c, e] - [1,2] oxaphosphorin,
  • 4. 6- (2,6-di-isopropylphenoxy) dibenz [c, e] - [1,2] oxaphosphorin,
  • 5. 6- (2,6-diphenyl-4-methoxyphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 6. 6- (2,6-di-tert-butyl-4-n-octadecyloxycarbonyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin,
  • 7. 6- [2,6-di-tert-butyl-4-diethylphosphonophenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 8. 6- (2-methyl-4-di-n-butylaminomethyl-6-tert-butylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 9. 6- [2,6-di-tert-butyl-4- (N, N-di-n-octylthiocarbamoyl-thiomethyl) phenoxy] dibenz [c, e] - [1,2] oxaphosphorine,
  • 10. 6- [2,6- (di-1,1-dimethyl-4-ethoxycarbonyl-butyl) -4-methylphenoxy] dibenz [c, e] - [1,2] oxaphosphorin,
  • 11. 6- (2-methyl-4-n-octadecyloxycarbonylmethyl-6-tert-butylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 12. 6- (2,6-di-i-propyl-4- (2-methoxycarbonyl-ethyl) -phenoxy] -dibenz [c, e] - [1,2] oxaphosphorin,
  • 13. 6- [2-methyl-4- (2,4-di-tert-butyl-phenoxycarbonyl) -6-tert-butyl-phenoxy] -dibenz [c, e] - [1,2] oxaphosphorine,
  • 14. 6- (2-cyclohexyl-4-tert-octylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 15. 6- (2-methyl-4-diethylphosphonomethyl-6-a, a-dimethylbenzylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 16. 6- (2,4-di-i-propyl-6-phenylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 17. 2-tert-butyl-6- (2,4-di-tert-butyl-phenoxy) -dibenz- [c, e] - [1,2] oxaphosphorine,
  • 18. 2,4-di-tert-butyl-6- (2,4-di-tert-butyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin,
  • 19. 2,4-di-tert-butyl-6- (2,6-di-i-propyl-4-tert-octylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 20. 4-tert-butyl-6- (2,4-di-tert-butyl-6-phenylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 21. 2,4-Di-tert-butyl-6- [2-methyl-4- (2-n-octadecyloxycarbonylethyl) -6-tert-butylphenoxy] -dibenz [c, e] - [1, 2] oxaphosphorin,
  • 22. 2,4-di-tert-butyl-6- (2,6-di-tert-butyl-4-methylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 23. 2,4-di-tert-butyl-6- (2,6-di-tert-butyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin,
  • 24. 6- (2,6-di-tert-butyl-4-diethylphosphonomethylphenoxy) dibenz [c, e] - [1,2] oxaphosphorin,
  • 25. 6- (2,6-di-tert-butyl-4-tert-octyl-phenoxy) -dibenz- [c, e,] - [1,2] oxaphosphorin,
  • 26. 6- (2-tert-butyl-4-methyl-6-a-methylcyclohexylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 27. 6- [2,6-di- (a, a-dimethylbenzyl) -4-n-octadecyloxycarbonylmethylphenoxy] dibenz [c, e] - [1,2] oxaphosphorine,
  • 28. 6- (2-tert-butyl-4-methyl-6-tert-pentylphenoxy) dibenz [c, e] - [1,2] oxaphosphorin,
  • 29. 6- (2-tert-butyl-4,6-di-tert-octyl-phenoxy) -dibenz- [c, e] - [1,2] oxaphosphorine,
  • 30. 6- [2,6-di-tert-butyl-4- (2,4-di-tert-butyl-phenoxycarbonyl) -phenoxy] -dibenz [c, e] - [1,2] oxaphosphorin,
  • 31. 6- [2,6-di-tert-pentyl-4- (2-ethoxycarbonylethyl) phenoxy] dibenz [c, e] - [1,2] oxaphosphorin,
  • 32. 6- [2-tert-Butyl-4-methyl-6- (1,1-dimethyl-4-ethoxycarbonylbutyl) phenoxy] dibenz [c, e] - [1,2] oxaphosphorine ,
  • 33 6- (2,6-Di-tert-butyl-4-cyanomethylphenoxy) dibenz- [c, e] - [1,2] oxaphosphorine.
  • 34. 6- (2-tert-Butyl-5-methylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine.
  • 35. 6- (2,4-Di-tert-butyl-5-methylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine.

Die Phosphonite der Formeln I und II können nach an sich bekannten Methoden hergestellt werden, insbesondere durch Veresterungs- bzw. Umesterungsrekationen, z.B. dadurch, dass man ein Phosphonit der Formeln

Figure imgb0002
worin R10 eine reaktionsfähige Gruppe ist und R1, R2, x und y die oben angegebene Bedeutung haben, mit einem Phenol der Formel
Figure imgb0003
worin R3, R4,R5 und R9 die oben angegebene Bedeutung haben umsetzt.The phosphonites of the formulas I and II can be prepared by methods known per se, in particular by esterification or transesterification reactions, for example by using a phosphonite of the formulas
Figure imgb0002
 wherein R 10 is a reactive group and R 1 , R 2 , x and y have the meaning given above, with a phenol of the formula
Figure imgb0003
 where R 3 , R 4 , R 5 and R 9 have the meaning given above.

Eine reaktionsfähige Gruppe R10 ist beispielsweise Halogen, insbesondere Chlor; Alkoxy oder gegebenenfalls substituiertes Phenoxy.A reactive group R 10 is, for example, halogen, especially chlorine; Alkoxy or optionally substituted phenoxy.

Die Umsetzung kann in an sich bekannter Weise geschehen, z.B. durch Erhitzen, bevorzugt auf Uber etwa 80°C, insbesondere Uber 150°C, wie 150-240°, z.B. 220°, wobei H R10 abgespalten wird, wobei R10 die oben angegebene Bedeutung hat; oder aber in Gegenwart von Basen, wie Aminen, z.B. Triäthylamin, Pyridin, N,N-Dimethylanilin oder Natriumcarbonat, bevorzugt in einem inerten Lösungsmittel, wie aprotische Lösungsmittel, z.B. Ligroin, Toluol, Dimethylformamid, Dimethylacetamid, Sulfolan, Methyläthylketon, Acetonitril oder Essigester, wobei aber auch Aminbasen im Ueberschuss verwendet werden können und dabei als Lösungsmittel dienen (vgl. auch DT-OS 2.034.887).The reaction can be carried out in a manner known per se, for example by heating, preferably to above about 80 ° C., in particular above 150 ° C., such as 150-240 °, for example 220 °, HR 10 being split off, R 10 being the above Has meaning; or in the presence of bases, such as amines, for example triethylamine, pyridine, N, N-dimethylaniline or sodium carbonate, preferably in an inert solvent, such as aprotic solvents, for example ligroin, toluene, dimethylformamide, dimethylacetamide, sulfolane, methyl ethyl ketone, acetonitrile or ethyl acetate, but it is also possible to use excess amine bases and serve as solvents (cf. also DT-OS 2,034,887).

Die Ausgangsstoffe sind bekannt oder können, sofern sie neu sind, in Analogie zu bekannten hergestellt werden. P-Cl Phosphonite sind z.B. aus der DT-OS 2.034.887 bekannt, während die Ausgangsphenole seit langem bekannte Verbindungen und vielfach handelsüblich sind.The starting materials are known or, if they are new, can be prepared analogously to known ones. P-Cl phosphonites are e.g. known from DT-OS 2.034.887, while the starting phenols are long-known compounds and are often commercially available.

Die Verbindungen der Formel I/II können gemäss der vorliegenden Erfindung als Stabilisatoren für Kunststoffe und Elastomere gegen deren Schädigung durch Einwirkung von Sauerstoff, Licht und Wäreme verwendet werden. Beispiele für solche Kunststoffe sind die in der DT-OS 2.456.864 auf den Seiten 12-14 aufgeführten Polymeren.According to the present invention, the compounds of the formula I / II can be used as stabilizers for plastics and elastomers against their damage by the action of oxygen, light and heat. Examples of such plastics are the polymers listed in DT-OS 2,456,864 on pages 12-14.

Geeignete Substrate sind z.B.:

  • 1. Polymere, die sich von einfach ungesättigten Kohlenwasserstoffen ableiten, wie Polyolefine, wie z.B. Polyäthylen, niederer und hoher Dichte, das gegebenenfalls vernetzt sein kann, Polypropylen, Polyisobutylen, Polymethylbuten-1, Polymethylpenten-1.
  • 2. Mischungen der unter 1 genannten Homopolymeren, wie z.B. Gemische von Polypropylen und Polyäthylen, Polypropylen und Polybuten-1, Polypropylen und Polyisobutylen.
  • 3. Copolymere der dem unter 1 genannten Homopolymeren zugrundeliegenden Monomeren, wie Aethylen-Propylen-Copolymere, Propylen-Buten-1-Copolymere, Propylen-Isobutylen-Copolymere, Aethylen-Buten-1-Copolymere, sowie Terpolymere von Aethylen und Propylen mit einem Dien, wie z.B. Hexadien, Di-cyclopentadien oder Aethylidennorbornen.
  • 4. Polystyrol und seine Copolymeren, wie SAN, ABS, IPS, ASA und EP modifizierte Styrolcopolymerisate.
  • 5. Polyamide.
  • 6..Lineare Polyester.
  • 7. Polyurethane.
  • 8. Polycarbonate.
  • 9. Elastomere, wie Polybutadien, SBR, Polyisopren, Polychloropren und Nitrilkautschuk.
  • 10.Thermoplastische Elastomere, wie SBS, SIS und S-EP-S.
  • 11. Polyvinylchlorid etc..
  • 12. Schmieröle auf synthetischer oder mineralischer Basis.
Suitable substrates include:
  • 1. Polymers which are derived from monounsaturated hydrocarbons, such as polyolefins, such as, for example, low and high density polyethylene, which can optionally be crosslinked, polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1.
  • 2. Mixtures of the homopolymers mentioned under 1, such as, for example, mixtures of polypropylene and polyethylene, polypropylene and polybutene-1, polypropylene and polyisobutylene.
  • 3. Copolymers of the monomers on which the homopolymer mentioned under 1 is based, such as ethylene-propylene copolymers, propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, and terpolymers of ethylene and propylene with a diene , such as hexadiene, dicyclopentadiene or ethylidene norbornene.
  • 4. Polystyrene and its copolymers, such as SAN, ABS, IPS, ASA and EP modified styrene copolymers.
  • 5. Polyamides.
  • 6..Linear polyester.
  • 7. Polyurethanes.
  • 8. Polycarbonates.
  • 9. Elastomers such as polybutadiene, SBR, polyisoprene, polychloroprene and nitrile rubber.
  • 10.Thermoplastic elastomers such as SBS, SIS and S-EP-S.
  • 11. Polyvinyl chloride etc.
  • 12. Lubricating oils on a synthetic or mineral basis.

Ein weiterer Gegenstand vorliegender Erfindung ist ein Verfahren zum Stabilisieren von Polymeren gegen den thermooxidativen Abbau während Herstellung, Isolierung, Verarbeitung und Gebrauch, das dadurch gekennzeichnet ist, dass man dem Polymeren mindestens eine Verbindung der Formel I/II zusetzt.Another object of the present invention is a method for stabilizing polymers against thermo-oxidative degradation during manufacture, insulation, processing and use, which is characterized in that that at least one compound of the formula I / II is added to the polymer.

Die Verbindungen der Formel I/II werden den Substraten in einer Konzentration von 0,005 bis 5 Gew.-%, berechnet auf das zu stabilisierende Material, einverleibt.The compounds of the formula I / II are incorporated into the substrates in a concentration of 0.005 to 5% by weight, calculated on the material to be stabilized.

Vorzugsweise werden 0,01 bis 1,0, besonders bevorzugt 0,02 bis 0,5 Gew.-% der Verbindungen, berechnet auf das zu stabilisierende Material, in dieses eingearbeitet. Die Einarbeitung kann beispielsweise durch Einmischen mindestens einer der Verbindungen der Formel I/II und gegebenenfalls weiterer Additive nach den in der Technik üblichen Methoden, vor oder während der Formgebung, oder auch durch Aufbringen der gelösten oder dispergierten Verbindungen auf das Polymere, gegebenenfalls unter nachträglichem Verdunsten des Lösungsmittels,erfolgen.0.01 to 1.0, particularly preferably 0.02 to 0.5% by weight of the compounds, calculated on the material to be stabilized, are preferably incorporated into the latter. The incorporation can be carried out, for example, by mixing in at least one of the compounds of the formula I / II and, if appropriate, further additives by the methods customary in industry, before or during shaping, or by applying the dissolved or dispersed compounds to the polymer, optionally with subsequent evaporation of the solvent.

Die neuen Verbindungen können auch in Form eines Masterbatches, der diese Verbindungen beispielsweise in einer Konzentration von 2,5 bis 25 Gew.-% enthält, den zu stabilisierenden Kunststoffen zugesetzt werden.The new compounds can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example in a concentration of 2.5 to 25% by weight.

Im Falle von vernetztem Polyäthylen werden die Verbindungen vor der Vernetzung beigefügt.In the case of cross-linked polyethylene, the compounds are added before cross-linking.

Die Erfindung betrifft daher auch die durch Zusatz von 0,01 bis 5 Gew.-% einer Verbindung der Formel I/II stabilisierten Kunststoffe, die gegebenenfalls noch andere Zusätze enthalten können. Die so stabilisierten Kunststoffe können in verschiedenster Form angewendet werden z.B. als Folien, Fasern, Bändchen, Profile oder als Bindemittel für Lacke, Klebemittel oder Kitte.The invention therefore also relates to the plastics stabilized by the addition of 0.01 to 5% by weight of a compound of the formula I / II, which may also contain other additives. The plastics stabilized in this way can be used in various forms, e.g. as foils, fibers, tapes, profiles or as binders for paints, adhesives or putties.

Als Beispiele weiterer Additive, mit denen zusammen die Stabilisatoren eingesetzt werden können, sind zu nennen: Antioxydantien, UV-Absorber und Lichtschutzmittel, wie 2-(2'-Hydroxyphenyl)-benztriazole, 2,4-Bis-(2'-hydroxyphenyl)-6-alkyl-s-triazine, 2-Hydroxybenzophenone, 1,3-Bis-(2'-hydroxybenzoyl)-benzole, Ester von gegebenenfalls substituierten Benzoesäuren, Acrylate, des weiteren Nickelverbindungen, sterisch gehinderte Amine, Oxalsäurediamide, Metalldesaktivatoren, Phosphite, peroxidzerstörende Verbindungen, Polyamidstabilisatoren, basische Co-Stabilisatoren, Nukleierungsmittel oder sonstige Zusätze wie z.B. Weichmacher, Gleitmittel, Emulgatoren, Füllstoffe, Russ, Asbest, Kaolin, Talk, Glasfasern, Pigmente, optische Aufheller, Flammschutzmittel, Antistatica.Examples of other additives with which the stabilizers can be used are: antioxidants, UV absorbers and light stabilizers, such as 2- (2'-hydroxyphenyl) benzotriazoles, 2,4-bis (2'-hydroxyphenyl) -6-alkyl-s-triazines, 2-hydroxybenzophenones, 1,3-bis (2'-hydroxybenzoyl) benzenes, esters of optionally substituted benzoic acids, acrylates, further nickel compounds, sterically hindered amines, oxalic acid diamides, metal deactivators, phosphites, peroxide-destroying compounds, polyamide stabilizers, basic co-stabilizers, nucleating agents or other additives such as Plasticizers, lubricants, emulsifiers, fillers, carbon black, asbestos, kaolin, talc, glass fibers, pigments, optical brighteners, flame retardants, antistatic agents.

Die Erfindung wird mit dem nachfolgenden Beispiel näher erläutert.The invention is explained in more detail with the following example.

Beispiele 1-18Examples 1-18

10 g 6-Chlor-dibenz[c,e]-[1,2]oxaphosphorin (0,0426 Mol), 10 g 2,6-Di-isopropyl-4-tert.-butyl-phenol und 30 ml Triäthylamin werden für 15 Stunden bei einer Innentemperatur von 110°C zur Reaktion gebracht.10 g of 6-chloro-dibenz [c, e] - [1,2] oxaphosphorine (0.0426 mol), 10 g of 2,6-di-isopropyl-4-tert-butyl-phenol and 30 ml of triethylamine are used for Reacted for 15 hours at an internal temperature of 110 ° C.

Nach beendeter Reaktion nimmt man das Reaktionsgut in 100 ml Toluol auf, filtriert die Lösung, engt das Filtrat unter vermindertem Druck ein und kristallisiert den Rückstand aus Acetonitril um. Das 6-(2,6-Di-isopropyl-4-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin schmilzt bei 128-130°C (Verbindung 1).When the reaction is complete, the reaction mixture is taken up in 100 ml of toluene, the solution is filtered, the filtrate is concentrated under reduced pressure and the residue is recrystallized from acetonitrile. The 6- (2,6-di-isopropyl-4-tert-butyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorine melts at 128-130 ° C (compound 1).

In analoger Weise erhält man folgende Verbindungen:The following connections are obtained in an analogous manner:

  • 2. 6-(2,6-Di-tert.-butyl-phenoxy)-dibenz[-c,e]-[1,2]oxaphosphorin, F. 152°C,2. 6- (2,6-di-tert-butyl-phenoxy) -dibenz [-c, e] - [1,2] oxaphosphorin, mp 152 ° C,
  • 3. 6-(2,6-Di-tert.-butyl-4-isopropyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. 95-96°C,3. 6- (2,6-di-tert-butyl-4-isopropyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin, mp 95-96 ° C,
  • 4. 6-[2,6-Di-tert.-butyl-4-(2-methoxycarbonyl-äthyl)-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin, F. 100°C,4. 6- [2,6-di-tert-butyl-4- (2-methoxycarbonyl-ethyl) -phenoxy] -dibenz [c, e] - [1,2] oxaphosphorin, mp 100 ° C,
  • 5. 6-[2,6-Di-tert.-butyl-4-(2-n-octadecyloxycarbonyl- äthyl)-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin, F. 75°C,5. 6- [2,6-di-tert-butyl-4- (2-n-octadecyloxycarbonyl-ethyl) -phenoxy] -dibenz [c, e] - [1,2] oxaphosphorine, mp 75 ° C ,
  • 6. 6-(2,4,6-Tri-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. 149°C,6. 6- (2,4,6-tri-tert-butyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin, mp 149 ° C,
  • 7. 6-(2,4,6-Tri-isopropyl-phenoxy)-dibenz[c,e]-[l,2]oxaphosphorin, F. 112°C,7. 6- (2,4,6-tri-isopropylphenoxy) -dibenz [c, e] - [l, 2] oxaphosphorin, mp 112 ° C,
  • 8. 6-(2,4-Di-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. <50°C,8. 6- (2,4-di-tert-butyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin, mp <50 ° C,
  • 9. 6-(2,4-Di-tert.-butyl-6-methyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. 110°C,9. 6- (2,4-di-tert-butyl-6-methylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine, mp 110 ° C,
  • 10. 6-(2-tert.-Butyl-6-methyl-phenoxy)-dibenz[c,e]-[1,2]-oxaphosphorin, F. 98-100°C,10. 6- (2-tert-butyl-6-methylphenoxy) dibenz [c, e] - [1,2] -oxaphosphorin, mp 98-100 ° C,
  • 11. 6-(2,4-Di-tert.-octyl-phenoxy)-dibenz[c,e]-[1,2]oxa- phorphorin, F. 109°C.11. 6- (2,4-Di-tert-octyl-phenoxy) -dibenz [c, e] - [1,2] oxa-phorphorin, mp 109 ° C.
  • 12. 6- {2,4-Di-(a,a-dimethylbenzyl)phenoxy} -dibenz [c,e]-[1,2]oxaphosphorin, F. 130°C,12. 6- {2,4-di- (a, a-dimethylbenzyl) phenoxy} -dibenz [c, e] - [1,2] oxaphosphorin, mp 130 ° C,
  • 13. 6-(2,4-Di-tert.amyl-phenoxy)-dibenz[c,e]-[1,2] oxaphosphorin, Kp. 180°C/0,05 mm Hg,13. 6- (2,4-di-tert.amylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine, bp 180 ° C / 0.05 mm Hg,
  • 14. 6-(2-tert.Butyl-phenoxy)-dibenz[c,e]-[1,2] oxaphosphorin, Kp. 163°C/0,04 mm Hg,14. 6- (2-tert-butyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin, bp 163 ° C / 0.04 mm Hg,
  • 15. 6-(2,6-Di-tert.butyl-4-methoxy-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. 104-105°C15. 6- (2,6-di-tert-butyl-4-methoxy-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin, mp 104-105 ° C
  • 16. 6-(1,1,3,3-Tetramethyl-6-tert.butyl-5- indanoxy)-dibenz[c,e]-[1,2]oxaphosphorin F. 140°C16. 6- (1,1,3,3-Tetramethyl-6-tert-butyl-5-indanoxy) -dibenz [c, e] - [1,2] oxaphosphorine F. 140 ° C
  • 17. 6-(1,1,3,3-Tetramethyl-6-tert.octyl-5-indanoxy)-dibenz[c,e]-[1,2]oxaphosphorin F. 126°C17. 6- (1,1,3,3-tetramethyl-6-tert.octyl-5-indanoxy) dibenz [c, e] - [1,2] oxaphosphorine m.p. 126 ° C
  • 18. 6-(2,4-Dimethyl-6-t.butylphenoxy)-dibenz [c,e]-[1,2]oxaphosphorin F. 126°C.18. 6- (2,4-Dimethyl-6-t.butylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine F. 126 ° C.
Beispiel 19Example 19

100 Teile Polycarbonat-Granulat (welches zuvor in einem Vacuum-Ofen während 12 Stunden bei 120°C getrocknet worden war) werden in einem SchUttelapparat mit 0,1 Teile der Verbindung 11 gemischt.100 parts of polycarbonate granules (which had previously been dried in a vacuum oven at 120 ° C. for 12 hours) are mixed with 0.1 part of compound 11 in a shaker.

Das erhaltene Gemisch wird in einem Labor-Einschneckenextruder bei 280°C DUsentemperatur extrudiert und anschliessend granuliert. Das zu Vergleichszwecken benötigte Granulat ohne Zusatz wird auf analoge Weise hergestellt. Vor der Weiterverarbeitung werden die Granulate in einem VakuumOfen während 12 Stunden bei 120°C getrocknet.The mixture obtained is extruded in a laboratory single-screw extruder at a die temperature of 280 ° C. and then granulated. The granules without additives required for comparison purposes are produced in an analogous manner. Before further processing, the granules are dried in a vacuum oven at 120 ° C for 12 hours.

Die Prüfung auf Wirksamkeit des Stabilisators gegen das Vergilben des Materials erfolgt in einer Labor-Spitzgussmaschine bei maximal 310°C. Die Vergilbung der 2 mm dicken Spitzgussplatten wird durch Messung des Yellowness Index nach ASTM 1925-63 beurteilt. Die Werte in der Tabelle zeigen, dass die stabilisatorhaltigen Platten sowohl direkt nach deren Herstellung, als auch nach Ofenalterung bei 140°C eine geringere Vergilbung aufweisen. (Höheren Yellowness Index = stärkere Vergilbung).The effectiveness of the stabilizer against yellowing of the material is tested in a laboratory injection molding machine at a maximum of 310 ° C. The yellowing of the 2 mm thick die cast plates is assessed by measuring the Yellowness Index according to ASTM 1925-63. The values in the table show that the plates containing the stabilizer show less yellowing both immediately after their manufacture and after aging in the oven at 140 ° C. (Higher yellowness index = greater yellowing).

Figure imgb0004
Figure imgb0004

Beispiel 20Example 20

100 Teile Polypropylen Pulver (Propathene HF 20 der Firma ICI) werden mit 0,1 Teil Calciumstearat, mit der Verbindung 11 in den in den untenstehenden Tabellen angegebenen Mengen und mit Pentaerythrit­tetrakis-[3-(3,5-ditertiärbutyl-4-hydroxy-phenyl)-propionat) (0,1 Teil in Tabelle A und 0,05 Teilen in Tabelle B) vermischt.100 parts of polypropylene powder (Propathene HF 20 from ICI) are mixed with 0.1 part of calcium stearate, with compound 11 in the amounts given in the tables below and with pentaerythritol tetrakis [3- (3,5-ditertiary butyl-4-hydroxy- phenyl) propionate) (0.1 part in Table A and 0.05 part in Table B).

Diese Gemische werden einerseits 5x hintereinander in einem Einschneckenextruder bei maximal 260°C anderseits 3x hintereinander im gleichen Extruder bei 280°C extrudiert, in jedem Fall mit 100 Umdrehungen pro Minute. Jeweils nach der 1. 3. und 5., beziehungsweise nach der 1. und 3. Extrusion wird der Schmelzindex des Polymeren, gemessen, wobei die Belastung 2160 g, die Temperatur 230°C und die Messgrösse g/10 Min. ist. Der Abbau des Polymeren äussert sich in einem Ansteigen des Schmelzindex.

Figure imgb0005
Figure imgb0006
 These mixtures are extruded 5 times in a row in a single-screw extruder at a maximum of 260 ° C and 3 times in a row in the same extruder at 280 ° C, in any case at 100 revolutions per minute. The melt index of the polymer is measured in each case after the 1st, 3rd and 5th, or after the 1st and 3rd extrusion, the load being 2160 g, the temperature 230 ° C. and the measurement variable g / 10 min. The degradation of the polymer manifests itself in an increase in the melt index.
Figure imgb0005
Figure imgb0006

Beispiel 21Example 21

Es wurde wie in Beispiel 20 verfahren, wobei ein anderes Polypropylen Pulver verwendet wurde (Shell Carlona HY 61/ 1090/1324) von Pentaerythrit-tetrakis-[3-(3,5-ditertiär- butyl-4-hydroxy-phenyl)-propionat] wurden 0,07 Teile eingesetzt.

Figure imgb0007
The procedure was as in Example 20, but using a different polypropylene powder (Shell Carlona HY 61 / 1090/1324) of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate ] 0.07 parts were used.
Figure imgb0007

Beispiel 22 PolyäthylenExample 22 Polyethylene

100 Teile hochmolekulares Polyäthylen-Pulver, (Lupolen 52602 der Firma BASF) wurden mit 0,05 Teilen Pentaery - thrit-tetrakis-[3-(3,5-ditertiärbutyl-4-hydroxyphenyl)-propionat] und den in der untenstehenden Tabelle angegebenen erfindungsgemässen Verbindungen gemischt und im Brabender Plastographen der Firma bei 220°C bei 50 Umdrehungen pro Minute geknetet. Während dieser Zeit wird der Knetwiderstand als Drehmoment kontinuierlich registriert. Im Verlauf der Knetzeit beginnt das Polymere nach längerer Konstanz zu vernetzen, was anhand der raschen Zunahme des Drehmoments festgestellt werden kann. Die Wirksamkeit der Stabilisatoren äussert sich in einer Verlängerung der Konstantzeit.

Figure imgb0008
100 parts of high molecular weight polyethylene powder (Lupolen 52602 from BASF) were mixed with 0.05 part of pentaerythritol-tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionate] and those given in the table below Compounds according to the invention mixed and kneaded in a Brabender plastograph from the company at 220 ° C. at 50 revolutions per minute. During this time, the kneading resistance is continuously recorded as torque. In the course of the kneading time, the polymer begins to crosslink after a long period of constancy, which can be determined from the rapid increase in the torque. The effectiveness of the stabilizers manifests itself in an extension of the constant time.
Figure imgb0008

Beispiel 23Example 23

PrUfung des Oxidationsverhaltens von Turbinen- und Hydraulikölen

  • a) Beschleunigte "CIGRE"-Methode
    (Modifizierte Methode IP 280)
    Durch 25 g Oe1 wird bei 150°C während 4 Stunden ein Sauerstoffstrom von 4 1/h durchgeleitet. Das Oel enthält als Katalysator 20 mg Fe (III)/kg Oel und 20 mg Cu (II)/kg Oel. Nach Abschluss der Prüfung bestimmt man Menge der gebildeten, im Oel gelösten Menge Säure.
  • b) Oxidation in der rotierenden Bombe: "ROBOT" gemäss ASTM D 2272/IP 229
Testing the oxidation behavior of turbine and hydraulic oils
  • a) Accelerated "CIGRE" method
    (Modified method IP 280)
    An oxygen flow of 4 l / h is passed through 25 g of Oe1 at 150 ° C. for 4 hours. The oil contains 20 mg Fe (III) / kg oil and 20 mg Cu (II) / kg oil as catalyst. After completion of the test, the amount of acid formed in the oil is determined.
  • b) Oxidation in the rotating bomb: "ROBOT" according to ASTM D 2272 / IP 229

Das zu prüfende Oel wird zusammen mit Wasser und einer Kupferspirale als Katalysator in ein Glasgefäss gebracht und das Glasgefäss in ein mit Druckregistiervorrichtung versehenes Druckgefäss gestellt. Nachdem das Durckgefäss mit Sauerstoff gespült und auf 6.25 bar (90 psi) eingestellt wurde, wird es in einem Bad bei konstanter Temperatur (150°C) axial rotiert. Die Zeit bis zum Eintreten eines Druckverlustes von 1.7 bar (25 psi) wird bestimmt.

Figure imgb0009
The oil to be tested is placed in a glass vessel together with water and a copper spiral as a catalyst and the glass vessel is placed in a pressure vessel provided with a pressure registering device. After the pressure vessel has been flushed with oxygen and set to 6.25 bar (90 psi), it is rotated axially in a bath at a constant temperature (150 ° C). The time until a pressure drop of 1.7 bar (25 psi) occurs is determined.
Figure imgb0009

Claims (10)

1. Phosphonit der Formeln I und II
Figure imgb0010
worin R1 und R2 unabhängig voneinander ein gegebenenfalls substituierter Kohlenwasserstoffrest oder Halogen sind, x und y unabhängig voneinander 0, 1, 2 oder 3 sind, R3 und R5 unabhängig voneinander Wasserstoff oder ein gegebenenfalls substituierter Kohlenwasserstoffrest sind, und R4 Wasserstoff, ein gegebenenfalls substituierter Kohlenwasserstoffrest, -CO-X-R6, -PO-(OR8)2 oder -OR8 ist, worin X -0- oder -NR7- ist, R6 und R7 unabhängig voneinander Wasserstoff oder ein gegebenenfalls substituierter Kohlenwasserstoffrest sind, und R8 ein gegebenenfalls substituierter Kohlenwasserstoffrest ist, wobei nicht alle drei Reste R3,R4 und R5 zugleich Wasserstoff sind, und wobei im Fall von R3 und R5 gleich tert.-Butyl R4 nicht Methyl ist, und R9 Wasserstoff, und falls R3 Wasserstoff ist, auch Methyl bedeutet. 1. Phosphonite of the formulas I and II
Figure imgb0010
 wherein R 1 and R 2 are, independently of one another, an optionally substituted hydrocarbon radical or halogen, x and y are independently 0, 1, 2 or 3, R 3 and R 5 are independently hydrogen or an optionally substituted hydrocarbon radical, and R 4 is hydrogen, an optionally substituted hydrocarbon radical, -CO-XR 6 , -PO- (OR 8 ) 2 or -OR 8 , wherein X is -0- or -NR 7 -, R 6 and R 7 are independently hydrogen or an optionally substituted hydrocarbon radical, and R 8 is an optionally substituted hydrocarbon radical, where not all three radicals R 3 , R 4 and R 5 are simultaneously hydrogen, and where in the case of R 3 and R 5 is tert-butyl R 4 is not methyl, and R 9 is hydrogen, and if R 3 is hydrogen, also means methyl. 2. Phosphonit nach Anspruch 1 der Formel I, worin R 1 C1-C8 Alkyl ist, x 0,1 oder 2 ist, y 0 ist, R3 und R5 unabhängig voneinander Wasserstoff, gegebenenfalls substituiertes C1-C25 Alkyl, C3-C4 Alkenyl, C3-C4 Alkinyl, C5-C12 Cycloalkyl, C6-C13 a-Methylcycloalkyl, C7-C14 Aralkyl, C7-C14 Alkaryl oder C6-C14 Aryl sind, R4 eine der für R3/RS gegebenenen Bedeutungen hat oder (C1-C18 Alkoxy)-carbonyl, (C5-C7 Cycloalk- oxy)-carbonyl, Phenoxycarbonyl, (C1-C12 Alkyl)-phenoxycarbonyl, C1-C18 Alkoxy oder 2-(C1-C18 Alkoxycarbonyl)-äthyl ist, wobei nicht alle drei Reste R3, R4 und R5 zugleich Wasserstoff sind, und wobei im Fall von R3 und R5 gleich tert.-Butyl R4 nicht Methyl ist. 2. Phosphonite according to claim 1 of formula I, wherein R 1 is C 1 -C 8 alkyl, x is 0.1 or 2, y is 0, R 3 and R 5 are independently hydrogen, optionally substituted C 1 -C 25 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 A lki n y l, C 5 -C 12 cycloalkyl, C 6 -C 13 a- Are methylcycloalkyl, C 7 -C 14 aralkyl, C 7 -C 14 alkaryl or C 6 -C 14 aryl, R 4 is a R 3 / R S gege benenen meanings, or (C 1 -C 18 alkoxy) carbonyl, (C 5 -C 7 Cycloalk- ox y) carbonyl, y Phenox carboxylic yl, (C 1 -C 12 Is alkyl) phenoxycarbonyl, C 1- C 18 alkoxy or 2- (C 1- C 18 alkoxycarbonyl) ethyl, where not all three radicals R 3 , R 4 and R 5 are simultaneously hydrogen, and where in the case of R 3 and R 5 is tert-butyl R 4 is not methyl. 3. Phosphonit nach Anspruch 1 der Formel I, worin x und y 0 sind, R3 und R5 unabhängig voneinander Wasserstoff, C1-C12 Alkyl, Cyclohexyl, a-Methylcyclohexyl, Benzyl, a,a-Dimethylbenzyl, Phenyl oder (C1-C18 Alkoxy)-carbonyl-C1-C8-alkyl sind, und R4 eine der für R3/R5 gegebenen Bedeutungen hat oder (C1-C18 Alkoxy)-carbonyl, oder 2-(C1-C18 Alkoxycarbonyl)-äthyl ist, wobei nicht alle drei Reste R3, R4 und R5 zugleich Wasserstoff sind, und wobei im Fall von R3 und R5 gleich tert.-Butyl R4 nicht Methyl ist. 3. phosphonite according to claim 1 of formula I, wherein x and y are 0, R 3 and R 5 are independently hydrogen, C1-C12 alkyl, cyclohexyl, a-methylcyclohexyl, benzyl, a, a-dimethylbenzyl, phenyl or (C 1 -C 18 alkoxy) carbonyl-C 1 -C 8 alkyl, and R 4 has one of the meanings given for R 5 3 / R or (C 1 -C 18 alk o x y) carbonyl, or 2- (C 1 -C 18 alkoxycarbonyl) ethyl is where not all three radicals R 3 , R 4 and R 5 are simultaneously hydrogen, and where in the case of R 3 and R 5 is tert-butyl R 4 is not methyl. 4. Phosphonit nach Anspruch 1 der Formel I, worin x und y 0 sind, R3 und R5 unabhängig voneinander Cl-C12 Alkyl, Cyclohexyl, a-Methylcyclohexyl, Benzyl, a,a-Dimethylbenzyl oder Phenyl sind, oder eines von R3 und R4 Wasserstoff ist und das andere obige Bebeutung hat, und R4 Wasserstoff, C1-C12 Alkyl, (C1-C18 Alkoxy)-carbonyl oder 2-(C1-C18 Alkoxycarbonyl)-äthyl ist, wobei im Fall von R3 und R5 gleich tert.-Butyl R4 nicht Methyl ist. 4. phosphonite according to claim 1 of formula I, wherein x and y are 0, R 3 and R 5 are independently C 1 -C 12 alkyl, cyclohexyl, a-methylcyclohexyl, benzyl, a, a-dimethylbenzyl or phenyl, or one of R 3 and R 4 is hydrogen and the other has the above meaning, and R 4 is hydrogen, C 1 -C 12 alkyl, (C 1 -C 18 alkox y ) carbonyl or 2- (C1-C18 alkoxycarbonyl) ethyl, in the case of R 3 and R 5 being tert-butyl R 4 is not methyl. 5. Phosphonit nach Anspruch 1 der Formel I, worin R9 Wasserstoff ist.5. Phosphonite according to claim 1 of formula I, wherein R 9 is hydrogen. 6. Phosphonit nach Anspruch 1, nämlich das 6-(2,6-Di-isopropyl-4-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]-oxaphosphorin.6. Phosphonite according to claim 1, namely the 6- (2,6-di-isopropyl-4-tert-butyl-phenoxy) -dibenz [c, e] - [1,2] -oxaphosphorin. 7. Stabilisiertes organisches Material enthaltend ein Phosphonit der Formel I nach Anspruch 1.7. Stabilized organic material containing a phosphonite of the formula I according to claim 1. 8. Stabilisiertes organisches Material nach Anspruch 7, dadurch gekennzeichnet, dass das Material ein Polyolefin ist.8. Stabilized organic material according to claim 7, characterized in that the material is a polyolefin. 9. Stabilisiertes organisches Material nach Anspruch 7, dadurch gekennzeichnet, dass das Material ein Schmieröl ist.9. Stabilized organic material according to claim 7, characterized in that the material is a lubricating oil. 10. Phosphonit nach Anspruch 1, nämlich das 6-(2,4-Di-tert.octyl-phenoxy-dibenz[c,e]-[1,2]oxaphosphorin.10. Phosphonite according to claim 1, namely the 6- (2,4-di-tert.octyl-phenoxy-dibenz [c, e] - [1,2] oxaphosphorine.
EP78100271A 1977-07-07 1978-06-29 Cyclic aromatic diesters of phosphonous acid and the organic materials stabilized by them Expired EP0000352B1 (en)

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EP0005441A1 (en) * 1978-04-14 1979-11-28 Ciba-Geigy Ag Aminodibenzoxaphosphorines, process for their preparation and their use as stabilisators
EP0181289A2 (en) * 1984-11-07 1986-05-14 Ciba-Geigy Ag Process for stabilizing a photographic material containing a magenta coupler
EP0223739A1 (en) * 1985-11-06 1987-05-27 Ciba-Geigy Ag Dibenzoxaphosphorine
EP0850946A1 (en) * 1996-12-24 1998-07-01 Ciba SC Holding AG Cyclic phosphinic acid derivatives as stabilizers
US20190234225A1 (en) * 2018-01-29 2019-08-01 MTU Aero Engines AG Module for a turbomachine

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US4423303A (en) * 1980-05-06 1983-12-27 Tokyo Shibaura Denki Kabushiki Kaisha Apparatus for treating powdery materials utilizing microwave plasma
JPS5957904A (en) * 1982-09-25 1984-04-03 Natl Res Inst For Metals Production of ultrafine particle of metallic nitride
US4439564A (en) * 1982-09-29 1984-03-27 The B. F. Goodrich Co. 5-Membered cyclic phosphonates and compositions thereof
JPS61242902A (en) * 1985-04-19 1986-10-29 Natl Res Inst For Metals Production of ultrafine particle of high-melting metallic oxide
JPS61291406A (en) * 1985-06-07 1986-12-22 Res Dev Corp Of Japan Method for producing ultra-fine particle of oxide and apparatus therefor
ES2051794T3 (en) * 1987-05-23 1994-07-01 Bayer Ag STABILIZED ALIPHATIC POLYCARBONATES.
US5914361A (en) * 1996-08-26 1999-06-22 Sumitomo Chemical Company, Limited Cyclic phosphonites and their use as stabilizers for organic materials
KR20170125374A (en) 2015-02-27 2017-11-14 사빅 글로벌 테크놀러지스 비.브이. Polyetherimides with improved color and their preparation
WO2016138388A1 (en) 2015-02-27 2016-09-01 Sabic Global Technologies B.V. Process to make low color polyetherimide by halo-displacement and low color polyetherimide
CN107849245B (en) 2015-05-29 2020-10-23 沙特基础工业全球技术有限公司 Color improved polyetherimides and methods of manufacture

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
EP0005441A1 (en) * 1978-04-14 1979-11-28 Ciba-Geigy Ag Aminodibenzoxaphosphorines, process for their preparation and their use as stabilisators
EP0181289A2 (en) * 1984-11-07 1986-05-14 Ciba-Geigy Ag Process for stabilizing a photographic material containing a magenta coupler
EP0181289A3 (en) * 1984-11-07 1986-08-20 Ciba-Geigy Ag Process for stabilizing a photographic material containing a magenta coupler
US4732997A (en) * 1984-11-07 1988-03-22 Ciba-Geigy Ag Dibenzoxaphosphorin compounds
EP0223739A1 (en) * 1985-11-06 1987-05-27 Ciba-Geigy Ag Dibenzoxaphosphorine
EP0850946A1 (en) * 1996-12-24 1998-07-01 Ciba SC Holding AG Cyclic phosphinic acid derivatives as stabilizers
US5932642A (en) * 1996-12-24 1999-08-03 Ciba Specialty Chemicals Corporation Cyclic phosphinic acid derivatives as stabilizers
US20190234225A1 (en) * 2018-01-29 2019-08-01 MTU Aero Engines AG Module for a turbomachine

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