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WO1992016537A1 - Diphosphites alkyle-aromatiques - Google Patents

Diphosphites alkyle-aromatiques Download PDF

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Publication number
WO1992016537A1
WO1992016537A1 PCT/US1992/001587 US9201587W WO9216537A1 WO 1992016537 A1 WO1992016537 A1 WO 1992016537A1 US 9201587 W US9201587 W US 9201587W WO 9216537 A1 WO9216537 A1 WO 9216537A1
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Prior art keywords
diphosphite
alkyl
aromatic
pentaerythritol
weight
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PCT/US1992/001587
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English (en)
Inventor
Hassan Y. Elnagar
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Ethyl Corp
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Ethyl Corp
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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
    • C07F9/6578—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 sulfur atoms with or without oxygen atoms, as ring hetero atoms
    • 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
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
    • 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
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters

Definitions

  • This invention relates to alkyl-aromatic diphosphites which have a cyclic caged structure and which have utility as antioxidants, stabilizers, and flame retardants for organic materials.
  • Kirpichnikov et al. Russian Chemical Reviews, Vol. 52 (11), 1983, pp. 1051-1063, teach that effective stabilization of polymers can be achieved by the use of synergistic mixtures of phosphites having different types of activity, i.e., inhibition of radical processes (a sterically-hindered aromatic phosphite) and serving as an acceptor of molecular polymer reaction products (aliphatic and mixed alkyl aryl phosphites).
  • phosphorus compounds are of interest as potential replacements for halogen compounds as flame retardants for normally flammable organic materials because of the hazards involved in the use of the halogen compounds.
  • Known phosphorus compounds have been found to be generally inferior to the halogen compounds, especially the bromine compounds, which have been the flame retardants of choice for many organic polymers; and it would therefore be advantageous to discover new phosphorus compounds which might be superior to the known phosphorus compounds in this regard.
  • R and R' in the formulas representing hydrocarbyl groups, R" being a divalent linki group, and n being 0 or 1.
  • novel diphosphites have different degrees of hydrolytic stability b consistently have better resistance to hydrolysis than commercial diphosphites, a they can be provided with even greater hydrolytic stability by combining them wi acid scavengers before or after they are recovered from their synthesis reaction mixtures.
  • the 2,2'-bridged bisphenols which can be used to prepare the novel diphosphites are compounds in which (1) the bridge at the 2,2'-position is provided by a direct bond between the benzene rings or by a divalent bridge, e.g., a sulfur, sulfoxide, sulfone, or alkylidene bridge, generally an alkylidene group containing 1-18 carbons, such as a methylene, ethylidene, propylidene, butylidene, isobutylidene, pentylidene, hexylidene, octylidene, or decylidene bridge, and (2) the hydrocarbyl groups which are ortho and para to the hydroxy groups may be the same or different and may be, e.g., alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, or hexyl;
  • the bisphenols having an ethylidene bridge are sometimes preferred because of the particularly good degree of hydrolytic stability exhibited by the diphosphites prepared from them, and it is also apt to be preferred for the hydrocarbyl substituents on the rings to be alkyl groups containing 1-6 carbons. However, satisfactory diphosphites are also obtained from the other bisphenols.
  • the bisphenols may be reacted with pentaerythritol dichlorophosphite that is formed in situ; but it is preferred to react the bisphenols with preformed pentaerythritol dichlorophosphite, since the latter reaction is both faster and cleaner.
  • a preformed pentaerythritol dichlorophosphite When a preformed pentaerythritol dichlorophosphite is to be used, it may be a compound that has been recovered from its synthesis reaction mixture, i.e., the reaction mixture in which it was prepared. However, it is preferably an unisolated compound; and the synthesis of the alkyl-aromatic diphosphite is effected by (1) adding the appropriate bisphenol to the pentaerythritol dichlorophosphite-containing reaction mixture resulting from the reaction of pentaerythritol with phosphorus trichloride at 20-150 °C in the presence of a basic catalyst and (2) maintaining contact between the bisphenol and pentaerythritol dichlorophosphite at 20-150 ° C until the alkyl-aromatic diphosphite is formed.
  • Pentaerythritol dichlorophosphite is conveniently prepared by adding phosphorus trichloride to pentaerythritol in a suitable organic solvent and allowing reaction to occur at 20-150 ' C, preferably 35-45 ° C, and most preferably at the reflux temperature of the reaction mixture, in an inert atmosphere, such as nitrogen, in the presence of a basic catalyst. Either reactant may be used in excess without preventing the formation of the desired product, but it is preferred to employ the reactants in substantially stoichiometric amounts, i.e., in a phosphorus trichloride/pentaerythritol mol ratio of about 2/1.
  • a common organic solvent e.g., an aliphatic or aromatic hydrocarbon, such as hexanes, benzene, toluene, or xylene, or a halogenated hydrocarbon, such as chlorobenzene, methylene chloride, or chloroform. Methylene chloride is especially preferred.
  • Utilizable basic catalysts include, e.g., alkali metal amides, such as sodium or lithium amide. However, the preferred basic catalysts are tert-amines.
  • tert-amines conventionally employed as basic catalysts may be used, including, e.g., Iriethylamine, tributylamine, triphenylamine, and phenyldimethylamine.
  • the preferred tert-amines are quinoline, pyridine, and alkylpyridines, especially pyridine.
  • the alkyl-aromatic diphosphite synthesis is conducted by combining the appropriate bisphenol with pentaerythritol dichlorophosphite or with pentaerythritol and phosphorus trichloride in a suitable organic solvent, such as those mentioned above, and allowing reaction to occur at 20-150 " C, preferably 40-50 ° C, and most preferably at the reflux temperature of the reaction mixture, in the presence of a basic catalyst, such as those mentioned above.
  • the preferred solvent for use in the alkyl-aromatic diphosphite synthesis is methylene chloride
  • the preferred catalyst is pyridine
  • the reactants are preferably employed in substantially stoichiometric amounts, i.e., in a bisphenol/pentaerythritol dichlorophosphite mol ratio of about 1/1.
  • the desired alkyl-aromatic diphosphite can also be prepared when either reactant is employed in excess of the stoichiometric amount, even w the bisphenol and pentaerythritol dichlorophosphite are utilized in the 2/1 mol r that would be expected to lead to the formation of a compound corresponding to formula:
  • the alkyl-aromatic diphosphite product may be recovered by conventional means; it is preferably crystallized one or more times from a suitable solvent, such isopropanol, to provide a purer product.
  • diphosphites of the invention are diphosphites which have a cyclic ca structure and contain both an aliphatic phosphite structure and a mixed alkyl- phosphite structure in a single molecule. They have good thermal and hydrol stability and can be effectively used as antioxidants or stabilizers tor organic materi which are normally susceptible to oxidative deterioration (including, e.g., discolorati
  • Organic materials which may benefit from the incorporation of the novel diphosphites as antioxidants and/or flame retardants include natural polymers, such as cellulose, rubber, and their derivatives, e.g., cellulose acetate, propionate, or butyrate or methyl cellulose, as well as the many synthetic polymers which are known to be normally susceptible to oxidative deterioration and/or to be normally flammable.
  • natural polymers such as cellulose, rubber, and their derivatives, e.g., cellulose acetate, propionate, or butyrate or methyl cellulose
  • synthetic polymers which are known to be normally susceptible to oxidative deterioration and/or to be normally flammable.
  • synthetic polymers are:
  • polymers and interpolymers of ethylenically-unsaturated hydrocarbons such as ethylene, propylene, butylene, isobutylene, 4-methyl-l-pentene, styrene, butadiene, and piperylene, including the homopolymers, the copolymers, and other interpolymers thereof with one another, and the copolymers and interpolymers of at least one of them with one or more copolymerizable non-hydrocarbons, such as vinyl acetate, acrylonitrile, methacrylonitrile, methyl acrylate, and methyl methacrylate, (2) halogen-containing polymers, such as polyvinyl chloride and fluoride, r>oryvinylidene chloride, vinyl chloride-vinylidene chloride copolymers, polychloroprene, and chlorinated rubbers,
  • halogen-containing polymers such as polyvinyl chloride and fluoride, r>oryvin
  • various other polymers such as epoxy polymers, polycarbonates, polyurethanes, polyureas, polyamides, polyesters, polyethers, polysulfones, phenol- formaldehyde resins, urea-formaldehyde resins, and melamine-formaldehyde resins.
  • the organic material is a polyethylene, polypropylene, polystyrene, ABS (acrylonitrile-butadiene-styrene terpolymer), polyalkylene terephthalate, or polycarbonate composition which, like the other polymeric compositions that may be modified in accordance with the invention, may contain one or more of the ingredients conventionally employed in such compositions, such as light stabilizers (e.g., hindered amine light stabilizers), ultraviolet light absorbers, metal deactivators, pigments, dyes, lubricants, nucleation agents, and fillers.
  • light stabilizers e.g., hindered amine light stabilizers
  • the alkyl-aromatic diphosphites are combined with the organic materials by any suitable technique known for the inco oration of phosphites into organic materials.
  • the amount incorporated may be a flame -retardant amount, generally 0.05-15%, preferably 0.1-1.5%, based on the weight of the normally flammable organic material; or an antioxidant amount, generally 0.005-5%, preferably 0.01-2%, based on the weight of the organic material which is normally susceptible to oxidative deterioration.
  • the alkyl-aromatic diphosphite When used as an antioxidant, the alkyl-aromatic diphosphite may be used alone or in combination with a phenolic antioxidant, which, when employed, is used in an antioxidant amount, such as the antioxidant amounts mentioned above, and which may be any of the sterically-hindered phenols known to be effective as antioxidants, such as 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2 '-ethylidene- bis(4,6-di-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), and the many other known phenolic antioxidants.
  • a particularly preferred phenolic antioxidant for use with the novel diphosphites is l,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybe__-yl)- benzene.
  • thioester synergists such as dilauryl thiodipropionate and distearyl thiodipropionate.
  • the diphosphites of the invention have good hydrolytic stability per se, it has been found that they can be made even more resistant to hydrolysis by stabilizing them with at least 0.5% by weight of an acid scavenger, based on the weight of the diphosphite.
  • the acid scavengers may be blended with the diphosphites after they have been recovered from their synthesis mixtures, just as the stabilizers of U.S. Patent 4,402,858 (Capolupe et al.) and European Patent Application 0 400 454 (Enlow et al.) are blended with the different phosphites of those publications to stabilize them against hydrolysis during storage and later use.
  • U.S. Patent 4,402,858 Cosmeticupe et al.
  • European Patent Application 0 400 454 Enlow et al.
  • crystallization solvents which might be preferred for those properties, e.g., acetonitrile, and alcohols, such as methanol, ethanol, 1-propanol, 2- propanol, 2-butanol, and t-butanol, can lead to decomposition of organophosphorus compounds via hydrolysis and/or transesterification during recovery processes utilizing them.
  • Incorporation of an acid scavenger into the synthesis reaction mixture before the diphosphite is allowed to crystallize minimizes such decomposition and thus can increase the yield and purity of the product as well as stabilizing the diphosphite against hydrolysis during storage and later use.
  • the acid scavenger used to stabilize the diphosphite may be any compound capable of scavenging the acidic residues present in the diphosphite as prepared. However, it is preferably a metal carboxylate, oxide, or carbonate, such as a lithium, sodium, potassium, copper, zinc, cadmium, magnesium, calcium, barium, aluminum, or other metal carbonate, oxide, or salt of a carboxylic acid, e.g., a carboxylic acid containing 6-20 carbons, such as hexanoic, heptanoic, octanoic, decanoic, dodecanoic, tetradecanoic, hexadecanoic, stearic, or eicosanic acid; or an alkanolamine, such as ethanolamine or triisopropanolamine.
  • the particularly preferred stabilizers are calcium stearate, triisopropanolamine, zinc oxide, sodium carbonate, magnesium aluminum hydroxy carbonates,
  • the amount used is at least 0.5%, preferably at least 1%, based on the weight of the diphosphite. Even greater stabilization can sometimes be achieved with larger amounts of the acid scavenger, but it is seldom necessary to utilize more than 5% of the acid scavenger to achieve essentially complete prevention of acidic decomposition.
  • the amount of acid scavenger used is most commonly in the range of 0.5-10%, preferably 1-5%, based on the weight of the diphosphite.
  • EXAMPLE 1 Preparation of AN- 1169 Charge a suitable reaction vessel with 99.8 mmols of pentaerythritol, 100 mL of methylene chloride, and 12.3 mmols of pyridine. Add 200 mmols of PC1 3 quickly, and maintain the mixture under a nitrogen atmosphere. Heat the mixture to about 40 ° C. As the reaction proceeds, neutralize the generated HC1 with a caustic scrubber. After one hour, when the reaction mixture becomes completely clear, add 105 mmols of 2,2'-ethylidenebis(4,6-di-t-butylphenol) in one portion, and continue heating at about 44 ° C overnight.
  • EXAMPLE 2 Preparation of AN-1170 Repeat the reaction of Example 1 except for substituting 119.8 mmols of 2,2'- methylenebis(6-t-butyl-4-methylphenol) for the bisphenol charge of that example and then continuing the heating for 5.7 hours. At the end of the reaction, dilute the slurry with 150 mL of methylene chloride, purge the reaction mixture with ammonia to precipitate ammonium chloride, remove the ammonium chloride by filtration, add the filtrate to 120 mL of isopropanol, and distill off the methylene chloride under reduced pressure.
  • EXAMPLE 3 Preparation of AN-1171 Repeat the reaction of Example 1 except for substituting 110 mmols of 2,2'- methylenebis(4,6-di-t-butylphenol) for the bisphenol charge of that example and then continuing the heating for two hours, after which most of the solvent has evaporated and a white slurry is obtained. Discontinue heating, and recover and purify the product as in Example 2 to provide 41g (67%) of a white solid which is identified by spectral analyses as 2,2'-methylenebis(4,6-di-t-butylphenyl)-methylene-(2",6",7"-trioxa- 1-phos- phabicyclo-[2.2.2]-octanyl)phosphite. When this example is essentially repeated except for doubling the amount of bisphenol so as to use two molar equivalents instead of one, only one of the molar equivalents enters into the reaction, and the same product is formed.
  • EXAMPLE 4 Preparation of AN-1172 Repeat the reaction of Example 1 except for substituting 117 mmols of 2,2'- isobutylidenebis(4,6-dimethylphenol) for the bisphenol charge of that example and then heating at about 62 " C for 45 minutes, after which most of the methylene chloride has evaporated and the mixture has become a thick slurry. Add 100 mL of methylene chloride to redissolve the solidfying mixture, bubble ammonia gas through the solution to form ammonium chloride, and separate the ammonium chloride by filtration.
  • EXAMPLE 6 Preparation of AN-1182 Charge a suitable reaction vessel with a slurry of 99.8 mmols of pentaerythritol and 199.6 mmols of PC1 3 in 100 mL of methylene chloride, add 1.0 mL of pyridine, and heat the mixture so that a gentle reflux is maintained. Apply a slightly positive pressure of nitrogen atmosphere, and neutralize the generated HC1 with a caustic scrubber as the reaction proceeds. After 30 minutes, when the reaction mixture becomes completely clear, quickly add 119 mmols of 2,2'-methylidenebis(6-t-butyl-4- ethylphenol) and continue heating for four hours.
  • Example 6 except for adding 0.5% of calcium stearate, based on the weight of diphosphite, prior to crystallization.
  • EXAMPLE 8 Preparation of AN-1185 Repeat the reaction of Example 6 except for substituting 111.6 mmols of 2,2'- thiobis(6-t-butyl-4-methylphenol) for the bisphenol charge of that example and then continuing heating for 3.5 hours. Add an additional 10 mL of pyridine to complete the reaction, also add 100 mL of methylene chloride, and continue heating for another two hours.
  • Example 6 Repeat the reaction of Example 6 except for substituting 109.8 mmols of 2,2'- decylidenebis(2,4-dimethylphenol) for the bisphenol charge of that example and then continuing the heating for 1.5 hours. After an ammonia work-up, followed by filtration to remove ammonium chloride, crystallize the product twice from 100 mL of isopropanol to provide 22.9g (40%) of a white solid having a melting point of 145.1-
  • EXAMPLE 11 Preparation of AN- 1199 Repeat the reaction of Example 10 except for heating the reaction mixture for 70 minutes before adding a bisphenol, substituting 55 mmols of 2,2'-methylenebis(4,6- dimethylphenol) for the bisphenol of that example, and then continuing the heating for 1.5 hours. After diluting the reaction mixture with 100 mL of methylene chloride, purging with ammonia, filtering, and adding 100 mL of isopropanol, add 0.5g of DHT- 4C (an anhydrous talcite sold by Kyowa Chemical Industry) to neutralize any acid trace.
  • DHT- 4C an anhydrous talcite sold by Kyowa Chemical Industry
  • Part B Repeat Part A except for replacing the AN-1182 of Example 6 with the calcium stearate-stabilized AN-1182 of Example 7 (AN-1182/CaSt). The test results are shown in Table I.
  • EXAMPLE 13 Hydrolytic Stability Testing Dissolve five 560 mg samples of the AN-1182 of Example 6 in 5.0 mL of a 95/5 mixture of tetrahydrofuran and water, and add 5.5 mg of a stabilizer to each of the solutions — the stabilizers being, respectively, zinc oxide, calcium stearate, triisopropan ⁇ olamine ( ⁇ PA), sodium carbonate, and DHT-4C. Maintain the solutions at room temperature under nitrogen and monitor them periodically by gas chromatography (GC) to determine the extent of hydrolysis of the AN-1182. The test results are shown in Table II.
  • Part A Prepare four blends of polypropylene powder and 0.01% of calcium stearate as an acid neutralizer and lubricant. Retain one of the blends (Blend A) as a control, and modify the others by blending therewith 0.1% of the following diphosphites:
  • Part B Test the compositions of Part A for melt flow index and yellowness index by extruding them in a Brabender twin screw extruder at 150-245-245 ° C and 30 rpm under nitrogen and then making five passes through a Brabender single screw extruder at 260-260-260-260 ° C and 30 rpm with ambient air. The test results are shown in Table III. TABLE III
  • Part A Prepare six blends of polypropylene powder containing 0.05% of 2,4,6-tris(3,5-di-t-butyl-4-hydro_yber_zyl)benzene and 0.01% of calcium stearate. Retain one of the blends (Blend E) as a control, and modify the others by blending therewith 0.05% of the following diphosphites:

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Abstract

On peut préparer de nouvelles diphosphites alkyle-aromatiques possédant des pouvoirs anti-oxydants et ignifuges et correspondant à la formule (I), en faisant réagir un bisphénol à liaison en pont en position 2,2' correspondant à la formule (II) avec de la dichlorophosphite de pentaérythritol à des températures comprises entre 20 et 150 °C en présence d'un catalyseur basique. Dans les formules (I) et (II), R et R' représentent des groupes hydrocarbyles, R'' représente un groupe de liaison en pont divalente et n est égal à 0 ou à 1. Ces diphosphites se caractérisent par une bonne stabilité hydrolytique en soi et on peut les rendre encore plus résistantes à l'hydrolyse en les stabilisant avec au moins 0,5 % en poids d'un piègeur d'acide, de préférence avant qu'elles soient récupérées de leurs mélanges de réaction de synthèse.
PCT/US1992/001587 1991-03-25 1992-02-26 Diphosphites alkyle-aromatiques Ceased WO1992016537A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0558040A3 (en) * 1992-02-27 1995-02-15 Ethyl Corp Process for stabilizing organophosphorus compounds
US5565600A (en) * 1991-03-25 1996-10-15 Albemarle Corporation Alkyl-aromatic diphosphites
WO1996035694A1 (fr) * 1995-05-09 1996-11-14 Akzo Nobel N.V. Phosphite et phosphonate de (pentaerythritol phosphate alcool) (neopentylene glycol cyclique)
WO1996035695A1 (fr) * 1995-05-09 1996-11-14 Akzo Nobel N.V. Composes phosphonate et phosphite contenant du phosphate-alcool de pentaerythritol

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3192243A (en) * 1962-04-10 1965-06-29 Delaware Chemicals Inc Phosphorous derivatives of pentaerythritol
US4305866A (en) * 1976-03-04 1981-12-15 Borg-Warner Chemicals, Inc. Polyolefins stabilized with cyclic diphosphites

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3192243A (en) * 1962-04-10 1965-06-29 Delaware Chemicals Inc Phosphorous derivatives of pentaerythritol
US4305866A (en) * 1976-03-04 1981-12-15 Borg-Warner Chemicals, Inc. Polyolefins stabilized with cyclic diphosphites

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Journal of General Chemistry of the USSR, vol. 57, no. 12, part 2, December 1987, N.A. MUKMENEVA et al.: "Synthesis of pentaerythritol diphosphites with enhanced stability to hydrolysis", pages 2796-2797, see the whole article *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5565600A (en) * 1991-03-25 1996-10-15 Albemarle Corporation Alkyl-aromatic diphosphites
EP0558040A3 (en) * 1992-02-27 1995-02-15 Ethyl Corp Process for stabilizing organophosphorus compounds
WO1996035694A1 (fr) * 1995-05-09 1996-11-14 Akzo Nobel N.V. Phosphite et phosphonate de (pentaerythritol phosphate alcool) (neopentylene glycol cyclique)
WO1996035695A1 (fr) * 1995-05-09 1996-11-14 Akzo Nobel N.V. Composes phosphonate et phosphite contenant du phosphate-alcool de pentaerythritol

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