EP0000352A1 - 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
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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EP
European Patent Office
Prior art keywords
tert
butyl
dibenz
methyl
phenoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP78100271A
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German (de)
English (en)
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EP0000352B1 (fr
Inventor
Michael Dr. Rasberger
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Novartis AG
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Ciba Geigy AG
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Publication of EP0000352A1 publication Critical patent/EP0000352A1/fr
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Classifications

    • 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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  • 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)
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)

Application Number Priority Date Filing Date Title
CH843177 1977-07-07
CH8431/77 1977-07-07

Publications (2)

Publication Number Publication Date
EP0000352A1 true EP0000352A1 (fr) 1979-01-24
EP0000352B1 EP0000352B1 (fr) 1982-05-05

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ID=4340240

Family Applications (1)

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EP78100271A Expired EP0000352B1 (fr) 1977-07-07 1978-06-29 Diesters cycliques aromatiques d'acide phosphoneux et les produits organiques stabilisés par eux

Country Status (7)

Country Link
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)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005441A1 (fr) * 1978-04-14 1979-11-28 Ciba-Geigy Ag Aminodibenzoxaphosphorines, procédé pour leur préparation et leur utilisation comme stabilisateurs
EP0181289A3 (en) * 1984-11-07 1986-08-20 Ciba-Geigy Ag Process for stabilizing a photographic material containing a magenta coupler
EP0223739A1 (fr) * 1985-11-06 1987-05-27 Ciba-Geigy Ag Dibenzoxaphosphorine
EP0850946A1 (fr) * 1996-12-24 1998-07-01 Ciba SC Holding AG Dérivés cycliques d'acides phosphiniques comme stabilisants
US20190234225A1 (en) * 2018-01-29 2019-08-01 MTU Aero Engines AG Module for a turbomachine

Families Citing this family (11)

* 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
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
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
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
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

Citations (1)

* 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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5652937B2 (fr) * 1973-02-09 1981-12-15

Patent Citations (1)

* 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

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005441A1 (fr) * 1978-04-14 1979-11-28 Ciba-Geigy Ag Aminodibenzoxaphosphorines, procédé pour leur préparation et leur utilisation comme stabilisateurs
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 (fr) * 1985-11-06 1987-05-27 Ciba-Geigy Ag Dibenzoxaphosphorine
EP0850946A1 (fr) * 1996-12-24 1998-07-01 Ciba SC Holding AG Dérivés cycliques d'acides phosphiniques comme stabilisants
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

Also Published As

Publication number Publication date
US4276232A (en) 1981-06-30
DE2861779D1 (en) 1982-06-24
BR7804372A (pt) 1979-03-13
EP0000352B1 (fr) 1982-05-05
JPS5416480A (en) 1979-02-07
ES471530A1 (es) 1979-09-01
CA1117963A (fr) 1982-02-09

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