WO1991002738A1 - Halogenures d'aryl ester amide d'acide phosphonique, aryl ester amides d'acide phosphonique, procede de preparation et leur utilisation pour stabiliser les matieres plastiques - Google Patents

Halogenures d'aryl ester amide d'acide phosphonique, aryl ester amides d'acide phosphonique, procede de preparation et leur utilisation pour stabiliser les matieres plastiques Download PDF

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Publication number
WO1991002738A1
WO1991002738A1 PCT/EP1990/001361 EP9001361W WO9102738A1 WO 1991002738 A1 WO1991002738 A1 WO 1991002738A1 EP 9001361 W EP9001361 W EP 9001361W WO 9102738 A1 WO9102738 A1 WO 9102738A1
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Prior art keywords
radical
butyl
ester
aryl
acid
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PCT/EP1990/001361
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German (de)
English (en)
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Manfred BÖHSHAR
Hans-Jerg Kleiner
Gerhard Pfahler
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Hoechst Aktiengesellschaft
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Priority claimed from DE3928291A external-priority patent/DE3928291A1/de
Priority claimed from DE4022501A external-priority patent/DE4022501A1/de
Application filed by Hoechst Aktiengesellschaft filed Critical Hoechst Aktiengesellschaft
Priority to KR1019920700432A priority Critical patent/KR920702366A/ko
Publication of WO1991002738A1 publication Critical patent/WO1991002738A1/fr

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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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/26—Amides of acids of phosphorus containing P-halide groups
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/146—Esters of phosphorous acids containing P-halide groups
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4883—Amides or esteramides thereof, e.g. RP(NR'2)2 or RP(XR')(NR''2) (X = O, S)
    • 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
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings
    • 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
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/6533—Six-membered rings
    • 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
    • C08K5/5399—Phosphorus bound to nitrogen

Definitions

  • Phosphoric acid aryl ester amide halides Phosphoric acid aryl ester amide halides, phosphonous acid aryl ester amides, process for their preparation and their use for stabilizing plastics
  • the present invention relates to new phosphorous acid aryl ester amide halides, monophosphonous acid aryl ester amides and diphosphonic acid bis [aryl ester amides],
  • Such stabilizers consist, for example, of a phenolic antioxidant and one or more
  • the most common stabilizers include e.g.
  • Phosphonous ester amides have been described by stepwise reaction of phosphonous dihalides with alcohols or phenols and amines in the presence of acid acceptors [Houben-Weyl, Methods of Organic Chemistry,
  • phosphonous acid monoester monoamides which are suitable for use as stabilizers for polymers are converted by reaction of alkyl or arylphosphonous acid dihalides, for example
  • EP laid-open specification 42 359 can only be carried out to a limited extent, which is of course disadvantageous if industrial production is considered.
  • the aromatic derivatives only phenyl-dichlorophosphane is a technically available product, through which only derivatives of benzene-phosphonic acid are accessible. This is confirmed by the fact that, apart from all (no less than 17) examples, EP-EP 42 359 contains the unsubstituted phenyl radical.
  • the present invention now relates to
  • R 1 as a monovalent radical is a phenyl radical which is 1 to 3
  • substituents or a naphthyl radical which can carry 1 to 5 substituents, at least one of the substituents being an alkoxy radical or alkylthio radical each having 1 to 8, preferably 1 to 6 carbon atoms, or an aryl or aryloxy radical each having 6 to 10 , preferably 6 to 8 carbon atoms or halogen with an atomic number of 9 to 35 and the other substituents - at
  • Naphthylrest also exclusively - represent a non-aromatic hydrocarbon radical with 1 to 8 carbon atoms, and R 1 as a divalent radical is a phenylene radical, the
  • R * - a non-aromatic hydrocarbon radical with 1 to 18 carbon atoms, an aryl or an optionally
  • R 3 is hydrogen, an alkoxy or alkylthio radical with each
  • R 4 and R 5 are each, independently of one another, C 1 -C 22 alkyl,
  • Ring system with 5 to 7 ring atoms which can additionally contain a hetero atom (O, N, S) bonded via at least one C atom and
  • n 1 or 2.
  • R 11 as a divalent radical form a biphenylene radical
  • R 2 and R 3 each form a branched butyl radical
  • R 4 and R 5 each form a butyl radical or together with the N atom form the morpholide radical.
  • R 1 is the trimethylphenyl radical
  • R 2 and R 3 is the methyl or a branched butyl radical
  • R 4 and R 5 together with the
  • R represent or in which R the tert. -Butyl-1-phenyl radical, R 2 the tert-butyl radical, R 3 the methoxy or tert. Butyl radical and R 4 and R 5 together.
  • v.en represent the morpholide residue with the N atom.
  • R 1 is unsubstituted or substituted naphthyl
  • the substituents can each be the same or different.
  • the alkyl in the substituents of the aromatic radicals R 1 is, for example, one of the various hexyl or octyl radicals, but preferably has 1 to 4 carbon atoms and is, for example, methyl,
  • C 5 -C 8 cycloalkyl may be mentioned as a non-aromatic hydrocarbon radical, such as that below under R 2 listed residues.
  • R 1 as a divalent radical, for example, the
  • R 1 contains 3 substituents, the two o-positions should not contain more than 5 carbon atoms. In substituted naphthyl radicals which contain more than two substituents, these are expediently distributed over both rings.
  • Suitable radicals R 2 and R 3 are, for example, non-aromatic
  • Hydrocarbon radicals with 1 to 18 carbon atoms such as alkyl or cycloalkyl, furthermore aromatic radicals which
  • R 2 or R 3 are 4 to 12 and in particular 6 to 10
  • Called hydrocarbon radicals alkyl, such as methyl, ethyl, the various propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl and octadecyl radicals, and
  • Cycloalkyl with 5 to 10 carbon atoms such as cyclopentyl
  • Cyclohexyl, cycloheptyl and cyclohexylmethyl (ie both the hydrogenated benzyl radical and the methylcyclohexyl radical); C 6 -C 10 aryl and arylmethyl may also be mentioned, the term aryl in each case including alkylaryl, carrying a maximum of three of the substituents mentioned under R 2 and, including these, having a maximum of 14 carbon atoms. If one of the radicals R 2 or R 3 is an alkyl radical, tertiary alkyl groups with 4-10 C atoms, such as
  • R 2 or R 3 are phenyl, benzyl, ⁇ -methylbenzyl and ⁇ , ⁇ -dimethylbenzyl.
  • R 4 and R 5 are, for example, the radicals indicated for R. If they are alkyl, C 1 -C 12 -alkyl groups are preferred.
  • R 4 and R 5 are as C 2 -C 21 oxa or thiaalkyl, for example methoxymethyl, methylthiamethyl, ethoxymethyl,
  • Alkoxypropyl and alkylthiapropyl groups such as methoxypropyl, ethylthiapropyl, butoxypropyl, octylthiapropyl,
  • R 4 and R 5 are as C 3 -C 18 alkenyl, for example allyl, Mtthallyl, n-hexen-3-yl, n-octen-4-yl, n-undecen-10-yl or n-octadecen-17-yl . Allyl and methallyl are preferred.
  • R 4 and R 5 are as C 3 -C 18 alkynyl, for example propargyl, n-butyn-1-yl, n-butyn-2-yl or n-hexyn-1-yl. Are preferred
  • R 4 and R 5 form a pyrrolidine, oxazolidine, piperidine, morpholine, hexamethyleneimine or piperazine ring with the N atom to which they are attached, these can
  • Such ring systems are preferably unsubstituted.
  • R 4 or R 5 are piperidin-4-yl groups, it can be the unsubstituted piperidin-4-yl or that
  • Piperidine can be substituted with up to 5 alkyl groups.
  • the 2,2,6,6-tetramethylpiperidin-4-yl radical is particularly preferred.
  • the invention also relates to a method for
  • R 2 , R 3 , R 4 and R 5 have the meaning given above and X is chlorine or bromine, to the phosphonous ester amides (I).
  • the process according to the invention is therefore also applicable to the reaction of those compounds of the formula R 1 (MgX) n in which R 1 represents, for example, the tolyl, dimethylphenyl, trimethylphenyl or tert-butylphenyl radical.
  • an aprotic, organic solvent such as an ether, e.g. diethyl, dipropyl or
  • Protective gas is particularly suitable for nitrogen and argon.
  • the reaction temperature for Grignarding is generally between 20 and 125 ° C, preferably between 30 and 70 ° C.
  • Phosphorous acid ester amide halide (II) which advantageously with an inert, aprotic solvent, e.g. an aliphatic hydrocarbon fraction, hexane, cyclohexane, toluene, xylene or one of the abovementioned ethers, is metered in, advantageously at a temperature below 0 ° C.
  • aprotic solvent e.g. an aliphatic hydrocarbon fraction, hexane, cyclohexane, toluene, xylene or one of the abovementioned ethers
  • the products (I) can be obtained from the crude products by any process, but preferably by crystallization
  • R 4 and R 5 are each ethyl [Izv. Akad.
  • Nauk. SSSR, Ser. Khim., (9), 2131-2133 (1968)] can be carried out in a simple manner by a method which also
  • the object of the invention is to be produced.
  • this known connection has no technical significance. It is particularly suitable as a starting material for
  • the invention thus also relates to a process for the preparation of these compounds (II), which thereby
  • R 2 , R 3 , R 4 and R 5 have the meanings that for
  • This process can be carried out in any conventional manner. It is preferred to work in an inert
  • Hydrocarbons such as pentane, hexane, heptane, benzene, toluene, xylene, chlorobenzene and ethers such as diethyl, dipropyl,
  • the compounds of the formula (II) are expediently prepared by adding to the solution of
  • the mixing is carried out, for example, by stirring and expediently until the reaction is complete. Then from precipitated ammonium salt separated.
  • the solvents can be removed from the filtrate in a customary manner, advantageously by distillation, expediently distilling under reduced pressure.
  • Bases which are advantageously diluted with one of the abovementioned solvents are, in particular, tertiary amines, such as triathylamine and pyridine. An excess of amine
  • HNR 4 R 5 can also act as an acid-binding agent.
  • the products (II) obtained in this procedure are usually obtained in a purity which is readily sufficient for the reaction with the Grignard compounds. Another cleaning, e.g. vacuum or thin-film distillation is therefore generally not necessary.
  • the invention relates to the use of the compounds of the formula (I) by themselves or in combination with a phenolic antioxidant for stabilizing plastics, such as polycarbonates, preferably
  • Polymerization plastics such as polyolefins, especially polypropylene.
  • the compounds of the formula (I) give the plastics in the molding compositions improved stability against degradation by light, oxygen and heat. For this application, however, the purity of the crude reaction product obtained (85-93% according to 31 P-NMR) is often sufficient. Isolation in pure form is then not necessary.
  • the present invention thus also relates to a
  • Plastic molding material containing a thermoplastic or thermosetting plastic and a phosphonous acid aryl ester amide of the formula (I) in the ratio of (90 to 99.99): (0.01 to 10).
  • the plastic molding composition according to the invention contains a thermoplastic or thermosetting organic polymer, for example one of the following: 1. Polymers of mono- and diolefins, for example
  • High, medium or low density polyethylene (which may or may not be crosslinked), polypropylene,
  • Cycloolefins such as cyclopentene or norbornene.
  • Copolymers of mono- and diolefins with one another or with other vinyl monomers such as e.g. Ethylene-propylene copolymers, propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate- Copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene with propylene and a diene, such as hexadiene,
  • Polystyrene 5. Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives, e.g. Styrene-butadiene, styrene-maleic anhydride, styrene-acrylonitrile,
  • styrene copolymers Mixtures of high impact strength from styrene copolymers and another polymer, such as a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; as well as block copolymers of styrene, e.g. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene /
  • Butylene styrene or styrene ethylene / propylene styrene butylene styrene or styrene ethylene / propylene styrene.
  • ABS polybutadiene, styrene and acrylonitrile on polybutadiene (ABS), Styrene and maleic anhydride on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene,
  • Vinyl compounds such as Polyvinyl chloride (PVC),
  • PVDC Polyvinylidene chloride
  • PVF polyvinyl fluoride
  • PVDF Polyvinylidene fluoride
  • Vinyl chloride-vinylidene chloride vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate. 8. Polymers derived from ⁇ , ⁇ -unsaturated carboxylic acids and their derivatives, such as polyacrylates and
  • Polymethacrylates polyacrylamides and polyacrylonitriles.
  • Derive amines or their acyl derivatives or acetals such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate,
  • Polyethylene glycols polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene (POM), as well as such
  • PUR Polyurethanes
  • lactams such as polyamide-4, polyamide-6, polyamide-6/6, polyamide-6/10, polyamide-11, polyamide-12,
  • Polyethers such as with polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
  • Polyester which is derived from dicarboxylic acids and diols
  • Derive lactones such as polyethylene terephthalate
  • PBTP Polybutylene terephthalate
  • poly-1,4-dimethylolcyclohexane terephthalate poly-1,4-dimethylolcyclohexane terephthalate
  • poly- (2,2-bis (4-hydroxyphenyl) propane polybutylene terephthalate
  • PC Polycarbonates
  • Crosslinking agents as well as their halogen-containing, flame-retardant modifications.
  • Crosslinkable acrylic resins which are derived from substituted acrylic acid esters, such as from epoxy acrylates,
  • Urethane acrylates or polyester acrylates 24. Alkyd resins, polyester resins and acrylate resins mixed with melamine resins, urea resins, polyisocyanates or
  • Epoxy resins are cross-linked.
  • crosslinked epoxy resins derived from polyepoxides, e.g. of bis-glycidyl ethers or of
  • Natural polymers such as cellulose, natural rubber, gelatin and their polymer-homologously chemically modified derivatives, such as cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methyl cellulose.
  • Aqueous dispersions of natural or synthetic rubber is preferably a polyolefin, especially polypropylene.
  • molding compound according to the invention is 90 to 99.99,
  • the molding compound contains a stabilizer
  • phenolic antioxidant optionally a phenolic antioxidant.
  • the phenolic antioxidant is e.g. an ester of 3,3-bis (3'-t-butyl-4'-hydroxyphenyl) butanoic acid of the formula (V)
  • R ° is preferably a C 2 -C 4 alkylene radical, in particular a C 2 alkylene radical.
  • the phenolic antioxidant can also be an ester of ⁇ - (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid of the formula (VI)
  • the alcohol component being a / polyvalent
  • preferably monohydric to tetravalent alcohol having 1 to 30, preferably 1 to 20, carbon atoms, such as
  • the new stabilizers are incorporated into the organic polymers using generally customary methods.
  • the incorporation can, for example, by adding the
  • Compounds can be incorporated directly into the polymer or mixed into a solution, suspension or emulsion of the polymer, optionally with the solvent subsequently evaporated.
  • Amount to be added to polymers is 0.01 to 10
  • the new compounds can also take the form of a
  • Masterbatches containing these compounds for example in a concentration of 1 to 50, preferably 2.5 to 20% by weight, are added to the polymers to be stabilized.
  • the molding composition according to the invention can also contain other antioxidants, such as: 1. Alkylated monophenols, for example
  • N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamic acid octyl ester N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamic acid octyl ester.
  • esters of ß- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols such as with
  • the molding composition according to the invention can still have
  • UV absorber and light stabilizer contain other additives such as: 1. UV absorber and light stabilizer
  • Octylphenyl salicylate dibenzoylresorcinol, bis- (4-t-butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-t-butyl-4-hydroxy-benzoic acid-2,4,4-di-t-butylphenyl ester, 3,5-di- t-butyl-4-hydroxybenzoic acid hexadecyl ester.
  • ⁇ -cyano-ß ß-diphenylacrylic acid ethyl ester or iso-octyl ester
  • ⁇ -carbomethoxy-cinnamic acid methyl ester ⁇ -cyano-ß-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester
  • ⁇ -carbomethoxy-p-methoxy- cinnamic acid methyl ester N- (ß-carbomethoxy-ß-cyano-vinyl) -2-methyl-indoline.
  • Triphenyl phosphite diphenylalkyl phosphite, phenyl dialkyl phosphite, trisnonylphenyl phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythrityl diphosphite, tris (2, 4-di-1-butylphenyl) phosphite,
  • esters of ⁇ -thio-dipropionic acid for example the
  • 2-mercaptobenzimidazole zinc alkyl dithiocarbamate, dioctadecyl disulfide, dioctadecyl monosulfide, pentaerythritol tetrakis ( ⁇ -dodecyl mercapto) propionate; 5.
  • Basic co-stabilizers for example
  • Melamine polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamines, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids or phenolates, for example CaStearate, Zn stearate, Mg stearate, Na ricinoleate,
  • Tin catechinate hydroxides and oxides of
  • Alkaline earth metals or aluminum for example CaO, MgO, ZnO;
  • Calcium carbonate silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and
  • Plasticizers plasticizers, lubricants, emuigators, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.
  • the various additional additives of the aforementioned groups 1 to 6 are added to the polymers to be stabilized in an amount of 0.01 to 10, preferably 0.01 to 5
  • the proportion of additives in groups 7 and 8 is generally 1 to 80, preferably 10 to 50,% by weight, based on the total molding composition.
  • organic polymers stabilized according to the invention can be used in various forms, e.g. as
  • Phenols and amines used as starting materials HNR 4 R 5 (IV) are mostly known compounds; otherwise they can be produced using analog processes.
  • aryl phosphorous dichloride was determined by means of 31 P-NMR spectroscopy and was generally between 70 and 92%.
  • Phosphoric acid (2,4-di-tert-butyl-phenyl) ester-morpholide chloride Starting from 153.6 g of phosphoric acid-2,4-di-tert-butyl-phenyl-ester dichloride and 43.6 g
  • Morpholine 165 g of a colorless solid with a melting point of approximately 70 ° C. and a content of 94% [ 31 P-NMR: ⁇ CDCl 3 156.9 ppm] of the above compound were obtained.
  • Phosphoric acid (2,4-dimethylphenyl) ester morpholide chloride Starting from 111.52 g of phosphoric acid 2,4-dimethylphenyl dichloride and 43.6 g of morpholine, about 120 g of a yellow Oil containing 90%
  • the resulting solution or suspension of the organometallic compound was
  • Magnesium salt the solvent was distilled off first in a vacuum of the water jet pump and then in a high vacuum, and the colorless or light beige residue was pulverized and dried in a high vacuum.
  • the content of the desired product in the raw materials was determined by 31 P-NMR spectroscopy. He was lying in the
  • Bromomityitylene and 68.43 g of phosphoric acid (2,4-dimethylphenyl) ester morpholide chloride became approx. 90 g of yellowish material with a softening point of 90-95 ° C and a content of
  • Tetrahydrofuran is dissolved, implemented.
  • aryl ester amides (I) according to the invention listed below were used for the experiments: a) (2,4,6-trimethyl-1-phenyl) -phosphonous acid- (2 ', 4'-di-tert-butyl- phenyl) -ester-morpholide b) (2,4,5-trimethyl-1-phenyl) -phosphonous acid- (2 ', 4'-di-tert-butyl-phenyl) -ester-morpholide c) 4-biphenyl- phosphonous acid (2 ', 4'-di-tert-butylphenyl) ester morpholide d) 1-naphthyl-phosphonous acid (2', 4'-di-tert-butylphenyl) ester morpholide e) 1- Naphthyl-phosphonous acid- (2 ', 4'-di-tert-butylphenyl) -ester-homo-piperidide f)
  • Example 34 Comparative Examples A to C 100.0 parts by weight of unstabilized polypropylene powder
  • spray plates with the dimensions 60 ⁇ 60 ⁇ 1 mm were produced from the granules of the first pass and the yellowing was measured immediately and after warm storage (7 days at 100 ° C.).
  • Screw diameter 20 mm; Length 20 D, nozzle 30 mm long 2 mm diameter; Speed: 125 rpm; Temperature program:
  • Table 2a Color gradient (Yellowness Index YI according to ASTM D 1925-70)
  • Table 2b Color gradient on 1 mm spray plates immediately after
  • Table 4a Color gradient (Yellowness Index according to ASTM D 1925-70)
  • Table 4b Color gradient on 1 mm spray plates immediately after

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Abstract

Procédé de préparation d'aryl ester amides d'acide phosphonique de la formule (I), où R1 est soit un résidu univalent représentant certains résidus d'hydrocarbures aromatiques pouvant comporter des substituants, soit un résidu divalent représentant un résidu de phénylène, naphtylène biphényle pouvant comporter à titre de substituants des résidus d'hydrocarbures aromatiques; R2 est un résidu d'hydrocarbures non aromatiques, aryl ou un résidu d'aryl méthyle éventuellement substitué; R3 est l'hydrogène, alkoxy ou alkylthio ou un groupe mentionné sous R2, et n = 1 ou 2. Un halogénure R1(-X)n, où R1 et n ont la signification ci-dessus et X est un halogène ayant un poids atomique d'au moins 35, est mis en réaction avec du magnésium pour obtenir les composés Grignard correspondants R1(MgX)n, qui sont ensuite mis en réaction avec des halogénures d'aryl ester amide d'acide phosphonique de la formule (II), où R2 à R5 ont la signification ci-dessus et X est le chlore ou le brome, afin d'obtenir les ester amides d'acide phosphonique (I). L'invention concerne également certains composés des formules (I) et (II), un procédé de préparation de composés de la formule (II), l'utilisation des composés de la formule (I), en tant que tels ou en association avec un antioxidant phénolique afin de stabiliser les matières plastiques, ainsi que les matières plastiques moulées ainsi stabilisées.
PCT/EP1990/001361 1989-08-26 1990-08-18 Halogenures d'aryl ester amide d'acide phosphonique, aryl ester amides d'acide phosphonique, procede de preparation et leur utilisation pour stabiliser les matieres plastiques WO1991002738A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019920700432A KR920702366A (ko) 1989-08-26 1990-08-18 아릴 할로포스포르아미다이트, 아릴 포스폰아미다이트, 그의 제조방법 및 플라스틱을 안정화시키기 위한 그의 용도

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEP3928291.0 1989-08-26
DE3928291A DE3928291A1 (de) 1989-08-26 1989-08-26 Phosphorigsaeure-arylester-amid-halogenide, phosphonigsaeurearylester-amide, verfahren zu ihrer herstellung und deren verwendung zur stabilisierung von kunststoffen
DEP4022501.1 1990-07-14
DE4022501A DE4022501A1 (de) 1990-07-14 1990-07-14 Kunststoff-formmasse

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WO1991002738A1 true WO1991002738A1 (fr) 1991-03-07

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PCT/EP1990/001361 WO1991002738A1 (fr) 1989-08-26 1990-08-18 Halogenures d'aryl ester amide d'acide phosphonique, aryl ester amides d'acide phosphonique, procede de preparation et leur utilisation pour stabiliser les matieres plastiques

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EP (1) EP0489050A1 (fr)
JP (1) JPH05500044A (fr)
KR (1) KR920702366A (fr)
CA (1) CA2065406A1 (fr)
WO (1) WO1991002738A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1207182A1 (fr) * 2000-11-02 2002-05-22 Cheil Industries Inc. Composition ignifuge de résine thermoplastique
EP1425347A1 (fr) * 2001-09-13 2004-06-09 Cheil Industries Inc. Composition de resine thermoplastique ignifuge

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0042359A1 (fr) * 1980-06-16 1981-12-23 Ciba-Geigy Ag Monoester monoamide d'acide phosphoneux et des polymers organiques stabilisés les contenant

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0042359A1 (fr) * 1980-06-16 1981-12-23 Ciba-Geigy Ag Monoester monoamide d'acide phosphoneux et des polymers organiques stabilisés les contenant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BULLETIN OF THE ACADEMY OF SCIENCES OF THE USSR, DIVISION OF CHEMICAL SCIENCE, Vol. 31, 1983, O.L. BUTKOVA et al., "Synthesis of Bonding Bidentate Organosilicon Phosphorus Ligands", pages 2106-2108. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1207182A1 (fr) * 2000-11-02 2002-05-22 Cheil Industries Inc. Composition ignifuge de résine thermoplastique
EP1425347A1 (fr) * 2001-09-13 2004-06-09 Cheil Industries Inc. Composition de resine thermoplastique ignifuge
EP1425347A4 (fr) * 2001-09-13 2005-01-26 Cheil Ind Inc Composition de resine thermoplastique ignifuge

Also Published As

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EP0489050A1 (fr) 1992-06-10
CA2065406A1 (fr) 1991-02-27
JPH05500044A (ja) 1993-01-14
KR920702366A (ko) 1992-09-03

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