EP0000352B1 - Diesters cycliques aromatiques d'acide phosphoneux et les produits organiques stabilisés par eux - Google Patents

Diesters cycliques aromatiques d'acide phosphoneux et les produits organiques stabilisés par eux 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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EP
European Patent Office
Prior art keywords
tert
butyl
dibenz
phenoxy
oxaphosphorin
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Expired
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EP78100271A
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German (de)
English (en)
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EP0000352A1 (fr
Inventor
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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lubricants (AREA)

Claims (11)

1. Phosphonite ayant les formules I et Il
Figure imgb0012
dans lesquelles
R1 est un groupe C1-C8 alkyle,
x est 0, 1 ou 2,
R3 et R5 indépendamment l'un de l'autre sont de l'hydrogène, des groupes C1-C25 alkyle éventuellement substitués, C3-C4 alcényle, C3-C4 alcinyle, C5-C12 cycloalkyle, C6-C13 a-méthylcycloalkyle, C7-C14 aralkyle ou C7-C14 alkaryle,
R4 a une des significations mentionnées pour R3/R5 ou bien est un groupe (C1-C18 alcoxy)-carbonyle, (C5-C7 cycloalcoxy)-carbonyle, phénoxycarbonyle, (C1-C12 alkyl)-phénoxycarbonyle, C1-C18 alcoxy ou 2-(C1-C18 alcoxycarbonyl)-éthyle,
étant donné que les restes R3, R4 et R5 ne sont pas tous les trois en même temps de l'hydrogène, et
étant donné que dans le cas où R3 et R5 sont identiquement un groupe tertio-bu- tyle, R4 n'est pas un groupe méthyle, et
Rg est de l'hydrogène, et dans le cas où R5 est de l'hydrogène, R9 est également un groupe méthyle.
2. Phosphonite selon la revendication 1, ayant la formule I dans laquelle
x est 0,
R3 et R5 indépendamment l'un de l'autre sont de l'hydrogène, des groupes C1-C12 alkyle, cyclohexyle, a-méthyl-cyclohexyle, benzyle, α,α-diméthylbenzyle ou (C1-C18 alcoxy)-carbonyl-C1-C8 alkyle, et
R4 a une des significations données pour R3/ R5 ou bien est un groupe (C1-C18 alcoxy)-carbonyle, ou 2-(C1-C18 alkcoxycarbonyl)-éthyle.
3. Phosphonite selon la revendication 1, ayant la formule I, dans laquelle:
x est 0,
R3 et R5 indépendamment l'un de l'autre sont des groupes C1-C12 alkyle, cyclohexyle, a-méthylcyclohexyle, benzyle, ou a,a-dimé- thylbenzyle, ou bien un des R3 et R4 est de l'hydrogène et l'autre a la signification ci- dessus, et
R4 est de l'hydrogène, un groupe C1-C12 alkyle, (C1-C18 alcoxy)-carbonyle ou 2-(C1-C18 alcoxycarbonyl)-ethyle.
4. Phosphonite selon la ravendication.1, ayant la formule dans laquelle R9est de l'hydrogène.
5. Phosphonite selon la revendication 1, notamment la 6-(2,6-Di-isopropyl-4-butylphénoxy)-dibenzo[c,e]-[1,2]oxaphosphorine.
6. Matière organique stabilisée contenant une phosphonite de formule I selon la revendication 1.
7. Matière organique stabilisée selon la revendication 7, caractérisée par le fait que la matière est une polyoléfine.
8. Matière organique selon la revendication 7, caractérisée par le fait que la matière est une huile de graissage.
9. Phosphonite selon la revendication 1, notamment la 6-(2,4-Di-tert.-octyl-phénoxy)-diben- zo[c,e]-[1,2]oxaphosphorine.
10. Phosphonite selon la revendication 1, notamment la 6-(2,6-Di-tert.-butyl-4-phénoxy)-diben- zo[c,e]-[1,2]oxaphosphorine.
11. Phosphonite selon la revendication 1, notamment la 6-(2,6-Di-tert.-butyl-4-isopropyl-phé- noxy)-dibenzo[c,e]-[1,2]oxaphosphorine.
EP78100271A 1977-07-07 1978-06-29 Diesters cycliques aromatiques d'acide phosphoneux et les produits organiques stabilisés par eux Expired EP0000352B1 (fr)

Applications Claiming Priority (2)

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CH843177 1977-07-07
CH8431/77 1977-07-07

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EP0000352B1 true EP0000352B1 (fr) 1982-05-05

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US (1) US4276232A (fr)
EP (1) EP0000352B1 (fr)
JP (1) JPS5416480A (fr)
BR (1) BR7804372A (fr)
CA (1) CA1117963A (fr)
DE (1) DE2861779D1 (fr)
ES (1) ES471530A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4351759A (en) * 1978-01-03 1982-09-28 Ciba-Geigy Corporation Alkylated 2,2'-biphenylene phosphites and stabilized compositions
DE2962873D1 (en) * 1978-04-14 1982-07-08 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 (ja) * 1982-09-25 1984-04-03 Natl Res Inst For Metals 金属窒化物超微粒子の製造法
US4439564A (en) * 1982-09-29 1984-03-27 The B. F. Goodrich Co. 5-Membered cyclic phosphonates and compositions thereof
DE3564872D1 (en) * 1984-11-07 1988-10-13 Ciba Geigy Ag Process for stabilizing a photographic material containing a magenta coupler
JPS61242902A (ja) * 1985-04-19 1986-10-29 Natl Res Inst For Metals 高融点金属酸化物の超微粒子の製造法
JPS61291406A (ja) * 1985-06-07 1986-12-22 Res Dev Corp Of Japan 酸化物超微粒子の製造方法及び装置
EP0223739A1 (fr) * 1985-11-06 1987-05-27 Ciba-Geigy Ag Dibenzoxaphosphorine
DE3873986D1 (de) * 1987-05-23 1992-10-01 Bayer Ag Stabilisiertes neopentylglykol-polycarbonat.
US5914361A (en) * 1996-08-26 1999-06-22 Sumitomo Chemical Company, Limited Cyclic phosphonites and their use as stabilizers for organic materials
EP0850946A1 (fr) * 1996-12-24 1998-07-01 Ciba SC Holding AG Dérivés cycliques d'acides phosphiniques comme stabilisants
US10526449B2 (en) 2015-02-27 2020-01-07 Sabic Global Technologies B.V. Process to make low color polyetherimide by halo-displacement and low color polyetherimide
EP3262101A1 (fr) 2015-02-27 2018-01-03 SABIC Global Technologies B.V. Polyétherimide à couleur améliorée, et ses procédés de fabrication
WO2016196268A1 (fr) 2015-05-29 2016-12-08 Sabic Global Technologies B.V. Polyétherimide de couleur améliorée et procédé de préparation
DE102018201295A1 (de) * 2018-01-29 2019-08-01 MTU Aero Engines AG Modul für eine strömungsmaschine

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3702878A (en) * 1969-12-31 1972-11-14 Sanko Chemical Co Ltd Cyclic organophosphorus compounds and process for making same
JPS5652937B2 (fr) * 1973-02-09 1981-12-15

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US4276232A (en) 1981-06-30
DE2861779D1 (en) 1982-06-24
EP0000352A1 (fr) 1979-01-24
BR7804372A (pt) 1979-03-13
JPS5416480A (en) 1979-02-07
ES471530A1 (es) 1979-09-01
CA1117963A (fr) 1982-02-09

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