EP0000352B1 - 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
EP0000352B1
EP0000352B1 EP78100271A EP78100271A EP0000352B1 EP 0000352 B1 EP0000352 B1 EP 0000352B1 EP 78100271 A EP78100271 A EP 78100271A EP 78100271 A EP78100271 A EP 78100271A EP 0000352 B1 EP0000352 B1 EP 0000352B1
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Prior art keywords
tert
butyl
dibenz
phenoxy
oxaphosphorin
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EP0000352A1 (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 is straight-chain or branched alkyl, e.g. B. methyl, i-propyl or tert-butyl.
  • R 3 and R 5 are especially C 1 -C 8 alkyl, e.g. B. methyl, ethyl, i-propyl, tert-butyl, tert-pentyl or tert-octyl, C 3 -C 4 alkenyl, e.g. B. allyl or methallyl, C 3 -C 4 alkynyl, e.g. B. propargyl, C 5 -C 12 cycloalkyl, e.g. Cyclohexyl, C 7 -C 8 alkyl) -C 5 -C 8 cycloalkyl, e.g. B.
  • R 3 and R 5 can also be substituted alkyl, such as 1,1-dimethyl-4-ethoxycarbonyl-butyl, or di- (C 1 -C 8 alkyl) -phosphonomethyl, e.g. B.
  • R 5 can also be: C 1 -C 18 alkoxycarbonyl-methyl, e.g. B.
  • R 4 has in particular the meaning given for R 3 / R 5 in general and as preferred and is in particular (C 1 -C 18 alkoxy) carbonyl, e.g. B. methoxycarbonyl or n-octadecyloxycarbonyl, phenoxycarbonyl, or (C 1 -C 12 alkyl) phenoxycarbonyl, e.g. B. 2,4-di-tert-butylphenoxycarbonyl, or (C 5 -C 7 cycloalkoxy) carbonyl, e.g. B. Cyclohexyloxycarbonyl.
  • the phosphonites of the formulas I and II can be prepared by methods known per se, in particular by esterification or transesterification reactions, for. B. by making a phosphonite of the formulas wherein R 10 is a reactive group and R, and x have the meaning given above, with a phenol of the formula wherein R 3 , R 4 , and Rg have the meaning given above.
  • a reactive group R 10 is, for example, halogen, especially chlorine; Alkoxy or optionally substituted phenoxy.
  • the implementation can be done in a conventional manner, for. B. by heating, preferably to above about 80 ° C, especially above 150 ° C, such as 150-240 °, z. B. 220 °, wherein HR 10 is split off, wherein R 10 has the meaning given above; or in the presence of bases such as amines, e.g. B. triethylamine, pyridine, N, N-dimethylaniline or sodium carbonate, preferably in an inert solvent such as aprotic solvents, e.g. B.
  • bases such as amines, e.g. B. triethylamine, pyridine, N, N-dimethylaniline or sodium carbonate, preferably in an inert solvent such as aprotic solvents, e.g. B.
  • amine bases can also be used in excess and serve as solvents (see also DT-OS 2.034.887).
  • P-CI phosphonites are e.g. B. 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 process for stabilizing polymers against thermooxidative degradation during manufacture, insulation, processing and use, which is characterized in that at least one compound of the formula 1/11 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 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, if appropriate 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. B. as films, fibers, tapes, profiles or as a binder for paints, adhesives or putties.
  • antioxidants examples include 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 B. 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
  • the mixture obtained is extruded in a laboratory single-screw extruder at a nozzle 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 injection molding plates is assessed by measuring the yellowness index in accordance with 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) from pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 0.07 parts were used.
  • a different polypropylene powder Shell Carlona HY 61/1090/1324 from pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 0.07 parts were used.
  • An oxygen flow of 41 / h is passed through 25 g of oil at 150 ° C. for 4 hours.
  • the oil contains 20 mg Fe (III) / kg oil and 20 mg Cu (II) / kg oil as a catalyst. After completion of the test, the amount of the acid formed in the oil is determined.
  • 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 registration device. After the pressure vessel has been rinsed with acid and set to 6.25 bar (90 psi), it is rotated axially in a bath at a constant temperature (150 ° C). The time to loss of pressure of 1.7 bar (25 psi) is determined.

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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 C1-C8 Alkyl ist,
  • x 0,1 oder 2 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, oder C7-C14 Alkaryl sind,
  • R4 eine der für R3/R5 gegebenen Bedeutungen hat oder (C1-C8 Alkoxy)-carbonyl, (C5-C7 Cycloalkoxy)-carbonyl, Phenoxycarbonyl, (C1-C12 Alkyl)-phenoxycarbonyl, C1-C18 AIkoxy oder 2-(C1-C8 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, und
  • Rg Wasserstoff, und falls R3 Wasserstoff ist, auch Methyl bedeutet.
Accordingly, the invention relates to phosphonites of the formulas I and II
Figure imgb0001
 wherein
  • R 1 is C 1 -C 8 alkyl,
  • x is 0.1 or 2,
  • R 3 and R 5 independently of one another hydrogen, optionally substituted C 1 -C 25 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C 5 -C 12 cycloalkyl, - C 6 -C 13 a-methylcycloalkyl, C 7 -C 14 aralkyl, or C 7 -C 14 alkaryl,
  • R 4 has one of the meanings given for R 3 / R 5 or (C 1 -C 8 alkoxy) carbonyl, (C 5 -C 7 cycloalkoxy) carbonyl, phenoxycarbonyl, (C 1 -C 12 alkyl) phenoxycarbonyl, C 1 -C 18 alkoxy or 2- (C 1 -C 8 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, and
  • Rg is hydrogen, and if R 3 is hydrogen, also means methyl.

R1 ist geradkettiges oder verzweigtes Alkyl, z. B. Methyl, i-Propyl oder tert.-Butyl.R 1 is straight-chain or branched alkyl, e.g. B. methyl, i-propyl or tert-butyl.

R3 und R5 sind 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, C7-C8 Alkyl)-C5-C8 Cycloalkyl, z. B. a-Methylcyclohexyl, C7-C14 Aralkyl, z. B. Benzyl, a-Methylbenzyl oder a,a-Dimethylbenzyl, C7-C14 Alkaryl, wie (C1-C8 Alkyl)-phenyl, z. B. Tolyl. R3 und R5 kann auch substituiertes Alkyl sein, wie 1,1-Dimethyl-4-äthoxycarbonyl-butyl, oder Di-(C1-C8 Alkyl)-phosphonomethyl, z. B. Diäthylphosphonomethyl, oder Aminoalkyl, insbesondere Aminomethyl, wie (C1-C18 Alkyl)-aminomethyl oder Di-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 Al- kanoylthio)-methyl, N-alkyliertes (C1-C18 Carba- moyloxy)-methyl, n-alkyliertes (C1-C18 Carba- moylthio)-methyl oder N-alkyliertes (C1-C18 Thio- carbamoylthio)-methyl, z. B. Acetoxymethyl, Propionylthiomethyl, N,N-Di-n-butyl-carbamoyloxy- methyl, N,N-Di-n-butyl-carbamoylthio-methyl, N,N-Di-n-butyl-thiocarbamoylthio-methyl oder N,N-Di-n-octyl-thiocarbamoylthio-methyl. R5 kann zudem auch sein: C1-C18 Alkoxycarbonyl-methyl, z. B. Methoxycarbonylmethyl oder n-Octadecyloxycarbonylmethyl, oder 2-(C1-C18 Alkoxycarbonyl)-äthyl, wie 2-(Methoxycarbonyl)-äthyl, oder Cyanomethyl.R 3 and R 5 are especially C 1 -C 8 alkyl, e.g. B. methyl, ethyl, i-propyl, tert-butyl, tert-pentyl or tert-octyl, C 3 -C 4 alkenyl, e.g. B. allyl or methallyl, C 3 -C 4 alkynyl, e.g. B. propargyl, C 5 -C 12 cycloalkyl, e.g. Cyclohexyl, C 7 -C 8 alkyl) -C 5 -C 8 cycloalkyl, e.g. B. a-methylcyclohexyl, C 7 -C 14 aralkyl, e.g. B. benzyl, a-methylbenzyl or a, a-dimethylbenzyl, C 7 -C 14 alkaryl, such as (C 1 -C 8 alkyl) phenyl, e.g. B. Tolyl. R 3 and R 5 can also be substituted alkyl, such as 1,1-dimethyl-4-ethoxycarbonyl-butyl, or di- (C 1 -C 8 alkyl) -phosphonomethyl, e.g. B. diethylphosphonomethyl, or aminoalkyl, especially aminomethyl, such as (C 1 -C 18 alkyl) aminomethyl or di-alkyl) aminomethyl, e.g. B. 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 thio - carbamoylthio) methyl, e.g. B. acetoxymethyl, propionylthiomethyl, N, N-di-n-butyl-carbamoyloxy-methyl, N, N-di-n-butyl-carbamoylthio-methyl, N, N-di-n-butyl-thiocarbamoylthio-methyl or N, N-di-n-octyl-thiocarbamoylthio-methyl. R 5 can also be: C 1 -C 18 alkoxycarbonyl-methyl, e.g. B. methoxycarbonylmethyl or n-octadecyloxycarbonylmethyl, or 2- (C 1 -C 18 alkoxycarbonyl) ethyl, such as 2- (methoxycarbonyl) ethyl, or cyanomethyl.

R4 hat insbesondere die für R3/R5 allgemein und als bevorzugt angegebene Bedeutung und ist insbesondere (C1-C18 Alkoxy)-carbonyl, z. B. Methoxycarbonyl oder n-Octadecyloxycarbonyl, Phenoxycarbonyl, oder (C1-C12 Alkyl)-phenoxycarbonyl, z. B. 2,4-Di-tert.-butyl-phenoxycarbonyl, oder (C5-C7 Cycloalkoxy)-carbonyl, z. B. Cyclohexyloxycarbonyl.R 4 has in particular the meaning given for R 3 / R 5 in general and as preferred and is in particular (C 1 -C 18 alkoxy) carbonyl, e.g. B. methoxycarbonyl or n-octadecyloxycarbonyl, phenoxycarbonyl, or (C 1 -C 12 alkyl) phenoxycarbonyl, e.g. B. 2,4-di-tert-butylphenoxycarbonyl, or (C 5 -C 7 cycloalkoxy) carbonyl, e.g. B. Cyclohexyloxycarbonyl.

Besonders bevorzugt sind Phosphonite der Formel I, worin

  • x 0 ist,
  • R3 und R5 unabhängig voneinander Wasserstoff, C1-C12 Alkyl, Cyclohexyl, α-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.
Particularly preferred are phosphonites of formula I, wherein
  • x is 0,
  • R 3 and R 5 are independently hydrogen, C 1 -C 12 alkyl, cyclohexyl, α-methylcyclohexyl, benzyl, a, a-dimethylbenzyl, phenyl or (C 1 -C 18 alkoxy) carbonyl-C 1 -C 8 alkyl are and
  • 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.

Vor allem betrifft die Erfindung Phosphonite der Formel I, worin

  • x 0 ist,
  • R3 und R5 unabhängig voneinander C1-C12 Alkyl,Cyclohexyl, α-Methylcyclohexyl, Benzyl oder a,a-Dimethylbenzyl sind, oder eines von R3 und R4 Wasserstoff ist und das andere obige Bedeutung hat, und
  • R4 Wasserstoff, C1-C12 Alkyl, (C1-C18 Alkoxy)-carbonyl oder 2-(C1-C18 Alkoxycarbonyl)-äthyl ist.
In particular, the invention relates to phosphonites of the formula I in which
  • x is 0,
  • R 3 and R 5 are independently C 1 -C 12 alkyl, cyclohexyl, α-methylcyclohexyl, benzyl or a, a-dimethylbenzyl, 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.

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-(2,6-Di-isopropyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 4. 6-(2,6-Di-tert.-butyl-4-n-octadecyloxycarbonyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 5. 6-[2,6-Di-tert.-butyl-4-diäthylphosphono- phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 6. 6-(2-Methyl-4-di-n-butylaminomethyl-6-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 7. 6-[2,6-(Di-1,1-dimethyl-4-äthoxycarbonyl- butyl)-4-methyl-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 8. 6-(2-Methyl-4-n-octadecyloxycarbonylme- thyl-6-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 9. 6-(2,6-Di-i-propyl-4-(2-methoxycarbonyl- äthyl)-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 10. 6-[2-Methyl-4-(2,4-di-tert.-butyl-phenoxycarbonyl)-6-tert.-butyl-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 11. 6-(2-Cyclohexyl-4-tert.-octyl-phenoxy)-di- benz[c,e]-[1,2]oxaphosphorin,
  • 12. 6-(2-Methyl-4-diäthylphosphonomethyl-6-α,α-dimethyl-benzyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 13. 2-tert.-Butyl-6-(2,4-di-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 14. 2,4-Di-tert.-butyl-6-(2,4-di-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 15. 2,4-Di-tert.-butyl-6-(2,6-di-i-propyl-4-tert.-octyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 16. 2,4-Di-tert.-butyl-6-[2-methyl-4-(2-n-octade- cyloxycarbonyläthyl)-6-tert.-butylphenoxy]-di- benz[c,e]-[1,2]oxaphosphorin,
  • 17. 2,4-Di-tert.-butyl-6-(2,6-di-tert.-butyl-4-me- thylphenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 18. 2,4-Di-tert.-butyl-6-(2,6-di-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 19. 6-(2,6-Di-tert.-butyl-4-diäthylphosphonomethyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 20. 6-(2,6-Di-tert.-butyl-4-tert.-octyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 21. 6-(2-tert.-Butyl-4-methyl-6-α-methylcyclohexyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 22. 6-[2,6-Di-(α,α-dimethylbenzyl)-4-n-octadecyl- oxycarbonylmethyl-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 23. 6-(2-tert.-Butyl-4-methyl-6-tert.-pentyl- phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 24. 6-(2-tert.-Butyl-4,6-di-tert.-octyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 25. 6-[2,6-Di-tert.-butyl-4-(2,4-di-tert.-butyl- phenoxy-carbonyl)-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 26. 6-[2,6-Di-tert.-pentyl-4-(2-äthoxycarbonyl- äthyl)-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin,
  • 27. 6-[2-tert.-Butyl-4-methyl-6-(1,1-dimethyl-4- äthoxycarbonyl-butyl)-phenoxy]-dibenz(c,e]-[1,2]oxaphosphorin,
  • 28: 6-(2,6-Di-tert.-butyl-4-cyanomethyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin,
  • 29. 6-(2-tert.-Butyl-5-methyl-phenoxy)-di- benz[c,e]-[1,2]oxaphosphorin,
  • 30. 6-(2,4-Di-tert.-butyl-5-methyl-phenoxy)-di- benz[c,e]-[1,2]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- (2,6-di-isopropylphenoxy) dibenz [c, e] - [1,2] oxaphosphorin,
  • 4. 6- (2,6-di-tert-butyl-4-n-octadecyloxycarbonyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin,
  • 5. 6- [2,6-di-tert-butyl-4-diethylphosphonophenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 6. 6- (2-methyl-4-di-n-butylaminomethyl-6-tert-butylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 7. 6- [2,6- (di-1,1-dimethyl-4-ethoxycarbonylbutyl) -4-methylphenoxy] dibenz [c, e] - [1,2] oxaphosphorine,
  • 8. 6- (2-methyl-4-n-octadecyloxycarbonylmethyl-6-tert-butylphenoxy) dibenz [c, e] - [1,2] oxaphosphorin,
  • 9. 6- (2,6-di-i-propyl-4- (2-methoxycarbonylethyl) phenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 10. 6- [2-methyl-4- (2,4-di-tert-butyl-phenoxycarbonyl) -6-tert-butyl-phenoxy] -dibenz [c, e] - [1,2] oxaphosphorin,
  • 11. 6- (2-cyclohexyl-4-tert-octyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin,
  • 12. 6- (2-methyl-4-diethylphosphonomethyl-6-α, α-dimethyl-benzyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin,
  • 13. 2-tert-butyl-6- (2,4-di-tert-butyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin,
  • 14. 2,4-di-tert-butyl-6- (2,4-di-tert-butyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin,
  • 15. 2,4-di-tert-butyl-6- (2,6-di-i-propyl-4-tert-octyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin,
  • 16. 2,4-Di-tert-butyl-6- [2-methyl-4- (2-n-octadecyloxycarbonylethyl) -6-tert-butylphenoxy] di-benz [c, e] - [ 1,2] oxaphosphorin,
  • 17. 2,4-di-tert-butyl-6- (2,6-di-tert-butyl-4-methylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 18. 2,4-di-tert-butyl-6- (2,6-di-tert-butyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorine,
  • 19. 6- (2,6-di-tert-butyl-4-diethylphosphonomethylphenoxy) dibenz [c, e] - [1,2] oxaphosphorin,
  • 20. 6- (2,6-di-tert-butyl-4-tert-octyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin,
  • 21. 6- (2-tert-butyl-4-methyl-6-α-methylcyclohexylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 22. 6- [2,6-di- (α, α-dimethylbenzyl) -4-n-octadecyloxycarbonylmethylphenoxy] dibenz [c, e] - [1,2] oxaphosphorine,
  • 23. 6- (2-tert-butyl-4-methyl-6-tert-pentylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 24. 6- (2-tert-butyl-4,6-di-tert-octylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 25. 6- [2,6-di-tert-butyl-4- (2,4-di-tert-butylphenoxycarbonyl) phenoxy] dibenz [c, e] - [1,2] oxaphosphorin,
  • 26. 6- [2,6-di-tert-pentyl-4- (2-ethoxycarbonylethyl) phenoxy] dibenz [c, e] - [1,2] oxaphosphorin,
  • 27. 6- [2-tert-butyl-4-methyl-6- (1,1-dimethyl-4-ethoxycarbonyl-butyl) phenoxy] dibenz (c, e] - [1,2] oxaphosphorine,
  • 28: 6- (2,6-di-tert-butyl-4-cyanomethylphenoxy) dibenz [c, e] - [1,2] oxaphosphorine,
  • 29. 6- (2-tert-butyl-5-methylphenoxy) di benz [c, e] - [1,2] oxaphosphorine,
  • 30. 6- (2,4-di-tert-butyl-5-methylphenoxy) di-benz [c, e] - [1,2] oxaphosphorine.

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

Figure imgb0002
worin R10 eine reaktionsfähige Gruppe ist und R, und x die oben angegebene Bedeutung haben, mit einem Phenol der Formel
Figure imgb0003
worin R3, R4, und Rg 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. B. by making a phosphonite of the formulas
Figure imgb0002
 wherein R 10 is a reactive group and R, and x have the meaning given above, with a phenol of the formula
Figure imgb0003
 wherein R 3 , R 4 , and Rg 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 über etwa 80° C, insbesondere über 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 Überschuss verwendet werden können und dabei als Lösungsmittel dienen (vgl. auch DT-OS 2.034.887).The implementation can be done in a conventional manner, for. B. by heating, preferably to above about 80 ° C, especially above 150 ° C, such as 150-240 °, z. B. 220 °, wherein HR 10 is split off, wherein R 10 has the meaning given above; or in the presence of bases such as amines, e.g. B. triethylamine, pyridine, N, N-dimethylaniline or sodium carbonate, preferably in an inert solvent such as aprotic solvents, e.g. B. ligroin, toluene, dimethylformamide, dimethylacetamide, sulfolane, methyl ethyl ketone, acetonitrile or ethyl acetate, but amine bases can also be used in excess and serve as solvents (see also DT-OS 2.034.887).

Die Ausgangsstoffe sind bekannt oder können, sofern sie neu sind, in Analogie zu bekannten hergestellt werden. P-CI 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-CI phosphonites are e.g. B. 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 Wärme 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-I, Polymethylpenten-1.
  • 2. Mischungen der unter 1 genannten Homopolymeren, wie z. B. Gemische von Polypropylen und Polyäthylen und Polyisobutylen.
  • 3. Copolymere der dem unter 1 genannten Homopolymeren zugrundeliegenden Monomeren, wie Äthylen-Propylen-Copolymere, Propylen-Buten-I-Copolymere, Propylen-Isobutylen-Copolymere, Äthylen-Buten-I-Copolymere, sowie Terpolymere von Äthylen und Propylen mit einem Dien, wie z. B. Hexadien, Di-cyclopentadien oder Äthylidennorbornen.
  • 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.
  • 12. Schmieröle auf synthetischer oder mineralischer Basis.
Suitable substrates are e.g. B .:
  • 1. Polymers derived from monounsaturated hydrocarbons, such as polyolefins, such as. As polyethylene, low and high density, which can optionally be crosslinked, polypropylene, polyisobutylene, polymethylbutene-I, polymethylpentene-1.
  • 2. Mixtures of the homopolymers mentioned under 1, such as. B. Mixtures of polypropylene and polyethylene and polyisobutylene.
  • 3. Copolymers of the monomers on which the homopolymer mentioned under 1 is based, such as ethylene-propylene copolymers, propylene-butene-I copolymers, propylene-isobutylene copolymers, ethylene-butene-I copolymers, and also terpolymers of ethylene and propylene with a diene , such as B. hexadiene, di-cyclopentadiene 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.
  • 12. Lubricating oils on a synthetic or mineral basis.

Ein weiterer Gegenstand vorliegender Erfin- , dung 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 1/11 zusetzt.Another object of the present invention is a process for stabilizing polymers against thermooxidative degradation during manufacture, insulation, processing and use, which is characterized in that at least one compound of the formula 1/11 is added to the polymer.

Die Verbindungen der Formel I/II werden den Substraten in einer Konzentratioh 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.Preferably 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 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, if appropriate 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. B. as films, fibers, tapes, profiles or as a binder 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 subsituierten 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 B. 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.-butylphenol 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-butylphenol and 30 ml of triethylamine are used for 15 hours reacted 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)-di- benz[c,e]-[1,2]oxaphosphorin schmilzt bei 128 bis 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 to 130 ° C (compound 1).

In analoger Weise erhält man folgende Verbindungen:

  • 2. 6-(2,6-Di-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. 152° C,
  • 3. 6-(2,6-Di-tert.-butyl-4-isopropyl-phenoxy)-di- benz[c,e]-[1,2]oxaphosphorin, F. 95-96° C,
  • 4. 6-[2,6-Di-tert.-butyl-4-(2-methoxycarbonyl- äthyl)-phenoxyl]-dibenz[c,e]-[1,2]oxaphosphorin, F. 100° C,
  • 5. 6-[2,6-Di-tert.-butyl-4-(2-n-octadecyloxycarbonyl-äthyl)-phenoxy]-dibenz[c,e]-[1,2]oxaphosphorin, F. 75° C,
  • 6. 6-(2,4,6-Tri-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. 149° C,
  • 7. 6-(2,4,6-Tri-isopropyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. 112° C,
  • 8. 6-(2,4-Di-tert.-butyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. < 50° C,
  • 9. 6-(2,4-Di-tert.-butyl-6-methyl-phenoxy)-di- benz[c,e]-[1,2]oxaphosphorin, F. 110°C,
  • 10. 6-(2-tert.-Butyl-6-methyl-phenoxy)-dibenz-[c,e]-[1,2]oxaphosphorin, F. 98-100° C,
  • 11. 6-(2,4-Di-tert.-octyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. 109° C,
  • 12. 6-{2,4-Di-(α,α-dimethylbenzyl)phenoxy-di- benz[c,e]-[1,2]oxaphosphorin, F. 1300 C,
  • 13. 6-(2,4-Di-tert.-amyl-phenoxy)-dibenz[c,e]-[1,2]oxaphosphorin, Kp. 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,
  • 15. 6-(2,6-Di-tert.-butyl-4-methoxy-phenoxy)-dibenz[c,e]-E1,2]oxaphosphorin, F. 104-105° C,
  • 16. 6-(1,1,3,3-Tetramethyl-6-tert.butyl-5-indan- oxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. 140° C,
  • 17. 6-(1,1,3,3-Tetramethyl-6-tert.octyl-5-indan- oxy)-dibenz[c,e]-[1,2]oxaphosphorin, F. 126° C,
  • 18. 6-(2,4-Dimethyl-6-t.butylphenoxy)-dibenz-[c,e]-[1,2]oxaphosphorin, F. 126°C.
The following connections are obtained in an analogous manner:
  • 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, mp 95-96 ° C,
  • 4. 6- [2,6-di-tert-butyl-4- (2-methoxycarbonyl-ethyl) -phenoxyl] -dibenz [c, e] - [1,2] oxaphosphorin, mp 100 ° C,
  • 5. 6- [2,6-Di-tert-butyl-4- (2-n-octadecyloxycarbonyl-ethyl) -phenoxy] -dibenz [c, e] - [1,2] oxaphosphorin, mp 75 ° 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-isopropylphenoxy) dibenz [c, e] - [1,2] oxaphosphorin, mp 112 ° 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-methylphenoxy) di-benz [c, e] - [1,2] oxaphosphorine, mp 110 ° 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] oxaphosphorin, mp 109 ° C,
  • 12. 6- {2,4-di- (α, α-dimethylbenzyl) phenoxy-di- benz [c, e] - [1,2] oxaphosphorin, F. 130 0 C,
  • 13. 6- (2,4-di-tert.-amyl-phenoxy) -dibenz [c, e] - [1,2] oxaphosphorin, bp 180 ° C / 0.05 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] -E1,2] oxaphosphorin, mp 104-105 ° C,
  • 16. 6- (1,1,3,3-tetramethyl-6-tert-butyl-5-indane-oxy) -dibenz [c, e] - [1,2] oxaphosphorin, mp 140 ° C,
  • 17. 6- (1,1,3,3-tetramethyl-6-tert.octyl-5-indane-oxy) -dibenz [c, e] - [1,2] oxaphosphorin, mp 126 ° C,
  • 18. 6- (2,4-Dimethyl-6-t.butylphenoxy) dibenz- [c, e] - [1,2] oxaphosphorine, mp 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 Schüttelapparat 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 Düsentemperatur extrudiert und anschliessend granuliert. Das zu Vergleichszwecken benötigte Granulat ohne Zusatz wird auf analoge Weise hergestellt. Vor der Weiterverarbeitung werden die Granulate in einem Vakuum-Ofen während 12 Stunden bei 120° C getrocknet.The mixture obtained is extruded in a laboratory single-screw extruder at a nozzle 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).

Figure imgb0004
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 injection molding plates is assessed by measuring the yellowness index in accordance with 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 oven aging at 140 ° C. (Higher yellowness index = greater yellowing).
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 Pentaerythrit-tetrakis-[3-(3,5-ditertiärbutyl-4-hy- droxy-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 andererseits 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-hydroxyphenyl)-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) from pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 0.07 parts were used.
Figure imgb0007

Beispiel 22 PolyäthylenExample 22 Polyethylene

100 Teile hochmolekulares Polyäthylen-Pulver, (Lupolen 52 602 der Firma BASF) wurden mit 0,05 Teilen Pentaerythrit-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
Figure imgb0009
 100 parts of high molecular weight polyethylene powder (Lupolen 52 602 from BASF) were mixed with 0.05 part of pentaerythritol tetrakis [3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] and those according to the invention given in the table below Compounds mixed and kneaded in the 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
Figure imgb0009

Beispiel 23Example 23

Prüfung des Oxidationsverhaltens von Turbinen- und HydraulikölenTesting the oxidation behavior of turbine and hydraulic oils

a) Beschleunigte «Circle»-Methodea) Accelerated "Circle" method

(Modifizierte Methode IP 280)(Modified method IP 280)

Durch 25 g Öl wird bei 150° C während 4 Stunden ein Sauerstoffstrom von 41/h durchgeleitet. Das Öl enthält als Katalysator 20 mg Fe (III)/kg Öl und 20 mg Cu (II)/kg ÖI. Nach Abschluss der Prüfung bestimmt man Menge der gebildeten, im Öl gelösten Menge Säure.An oxygen flow of 41 / h is passed through 25 g of oil at 150 ° C. for 4 hours. The oil contains 20 mg Fe (III) / kg oil and 20 mg Cu (II) / kg oil as a catalyst. After completion of the test, the amount of the acid formed in the oil is determined.

b) Oxidation in der rotierenden Bombe:b) Oxidation in the rotating bomb:

«ROBOT» gemäss ASTM D 2272/IP 229"ROBOT" according to ASTM D 2272 / IP 229

Das zu prüfende Öl wird zusammen mit Wasser und einer Kupferspirale als Katalysator in ein Glasgefäss gebracht und das Glasgefäss in ein mit Druckregistriervorrichtung versehenes Druckgefäss gestellt. Nachdem das Druckgefäss mit Sauersoff 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.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 registration device. After the pressure vessel has been rinsed with acid and set to 6.25 bar (90 psi), it is rotated axially in a bath at a constant temperature (150 ° C). The time to loss of pressure of 1.7 bar (25 psi) is determined.

Claims (11)

1. A phosphonite of the formulae I and II
Figure imgb0011
wherein
R1 is C1-C8-alkyl,
x is 0, 1 or 2,
R3 and R5 independently of one another are each hydrogen, unsubstituted or substituted C1-C25-alkyl, C3-C4-alkenyl, C3-C4-alkynyl, C5-C12-cycloalkyl, C6-C13-α-methylcycloalkyl, C7-C14-aralkyl or C7-C14-alkaryl,
R4 has one of the meanings given for R3/R5, or is (C1-C18-alkoxy)-carbonyl, (C5-C7-cycloal- koxy)-carbonyl, phenoxycarbonyl, (C1-C12- alkyl)-phenoxy-carbonyl, C1-C18-alkoxy or 2-(C1-C18-alkoxy-carbonyl)-ethyl, the condition being that not all three radicals R3, R4 and R5 are simultaneously hydrogen, and that, if R3 and R5 are tert-butyl, R4 is not methyl, and
Rg is hydrogen and, if R5 is hydrogen, also methyl.
2. A phosphonite according to Claim 1 of the formula I, wherein
x is nought,
R3 and R5 independently of one another are each hydrogen, C1-C12-alkyl, cyclohexyl, a-methylcyclohexyl, benzyl, a,a-dimethylbenzyl or (C1-C18-alkoxy)-carbonyl-C1-C8-alkyl, and
R4 has one of the meanings given for R3/Rs, or is (C1-C18-alkoxy)-carbonyl or 2-(C1-C18-alkoxy-carbonyl)-ethyl.
3. A phosphonite according to Claim 1 of the formula I, wherein
x is nought,
R3 and R5 independently of one another are C1-C12-alkyl, cyclohexyl, a-methylcyclohexyl, benzyl or a,a-dimethylbenzyl, or one of R3 and R4 is hydrogen, and the other has the above meaning, and
R4 is hydrogen, C1-C12-alkyl, (C1-C18-alkoxy)-carbonyl or 2-(C1-C18-alkoxycarbonyl)-ethyl.
4. A phosphonite according to Claim 1 of the formula I wherein Rg is hydrogen.
5. A phosphonite according to Claim 1, namely: 6-(2,6-di-isopropyl-4-tert-butyl-phenoxy)-di- benz[c,e]-[1,2]oxaphosphorine.
6. A stabilised organic material containing a phosphonite of the formula I according to Claim 1.
7. A stabilised organic material according to Claim 7, which material is a polyolefin.
8. A stabilised organic material according to Claim 7, which material is a lubricating oil.
9. A phosphonite according to Claim 1, namely: 6-(2,4-di-tert-octyl-phenoxy)-dibenz[c,e]-[1,2]-oxaphosphorine.
10. A phosphonite according to Claim 1, namely: 6-(2,6-di-tert-butyl-phenoxy)-dibenz[c,e]-[1,2]-oxaphosphorine.
11. A phosphonite according to Claim 1, namely: 6-(2,6-di-tert-butyl-4-isopropyl-phenoxy)-di- benz[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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US4351759A (en) * 1978-01-03 1982-09-28 Ciba-Geigy Corporation Alkylated 2,2'-biphenylene phosphites and stabilized compositions
EP0005441B1 (en) * 1978-04-14 1982-05-19 Ciba-Geigy Ag Aminodibenzoxaphosphorines, process for their preparation and their use as stabilisators
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
EP0181289B1 (en) * 1984-11-07 1988-09-07 Ciba-Geigy Ag Process for stabilizing a photographic material containing a magenta coupler
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
EP0223739A1 (en) * 1985-11-06 1987-05-27 Ciba-Geigy Ag Dibenzoxaphosphorine
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
EP0850946A1 (en) * 1996-12-24 1998-07-01 Ciba SC Holding AG Cyclic phosphinic acid derivatives as stabilizers
KR20170125374A (en) 2015-02-27 2017-11-14 사빅 글로벌 테크놀러지스 비.브이. Polyetherimides with improved color and their preparation
CN107278213B (en) 2015-02-27 2020-10-23 沙特基础工业全球技术有限公司 Method for preparing low color polyetherimides by halogen displacement and low color polyetherimides
US10435511B2 (en) 2015-05-29 2019-10-08 Sabic Global Technologies B.V. Polyetherimide of improved color and process of preparing
DE102018201295A1 (en) * 2018-01-29 2019-08-01 MTU Aero Engines AG MODULE FOR A FLOW MACHINE

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