EP0000757B1 - Procédé pour la préparation de phosphites de triaryle - Google Patents

Procédé pour la préparation de phosphites de triaryle Download PDF

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Publication number
EP0000757B1
EP0000757B1 EP78100550A EP78100550A EP0000757B1 EP 0000757 B1 EP0000757 B1 EP 0000757B1 EP 78100550 A EP78100550 A EP 78100550A EP 78100550 A EP78100550 A EP 78100550A EP 0000757 B1 EP0000757 B1 EP 0000757B1
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EP
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Prior art keywords
salts
process according
atoms
aryl
acids
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Expired
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EP78100550A
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German (de)
English (en)
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EP0000757A1 (fr
Inventor
Rudolf Dr. Maul
Otto Dr. Eberhard
Horst Dr. Zinke
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BASF Schweiz 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds

Definitions

  • the present invention relates to a process for the preparation of triaryl phosphites from phosphorus trihalides and hydroxyaromatics using certain compounds containing phosphorus, nitrogen and / or sulfur as catalysts.
  • triaryl phosphites have been widely used as stabilizers or costabilizers in the processing of, in particular, thermoplastics.
  • the aryl groups can be substituted or unsubstituted. They are generally prepared by reacting phosphorus trihalides with hydroxyaromatics. In this reaction, high temperatures have to be used in order to achieve the most complete conversion possible, in particular when the aryl groups are substituted and the reactivity of the hydroxyl groups is hindered. However, the high temperatures and relatively long reaction times are often not sufficient to achieve complete conversion, but rather a mixture is obtained which essentially consists of mono- and diaryloxyphosphorus halides and triarylphosphites.
  • catalysts include alkali and alkaline earth metal halides such as LiCl, MgCl 2 or CaCl 2 , metals such as Mg or Zn, Lewis acids such as ZnCl 2 or AICI 3 and aromatic heterocycles containing nitrogen as organic compounds such as pyridine, cf. Russian Patent No. 488 821. These solutions are not yet satisfactory and still require heating times that are too long at too high temperatures.
  • the quaternary phosphonium bases proposed as suitable catalysts in Russian Patent No. 488 821 are distinguished by an increased reactivity, but are not sufficiently specific. Especially when using substituted hydroxylaryls, only mixtures of predominantly diarylchlorophosphites and triarylphosphites are obtained.
  • the object of the present invention is to provide a process for the preparation of triaryl phosphites from phosphorus trihalides and hydroxyaromatics which, by using reactive and selective catalysts, enables high yields at lower temperatures and shorter reaction times, especially when using substituted hydroxyaromatics.
  • the present invention relates to a process for the preparation of triaryl phosphites according to claim 1.
  • R in the formula (RO) 3 P in its meaning as aryl is, for example, naphthyl and in particular phenyl, which can be substituted as indicated.
  • the substituents can be in any position on the aryl. Preferably there are no more than three substituents.
  • the substituents are preferably in the 2-, 4- and / or 6-positions.
  • the 2,4-position is particularly preferred. If there are substituents in the 2,6 positions, they should not be those with strong space filling, e.g. tertiary alkyl groups. According to the process according to the invention, reaction mixtures are also obtained in which predominantly undesired chlorophosphites are found.
  • the aryl can be substituted with linear or branched alkyl. This preferably contains 1 to 18, in particular 1 to 12, carbon atoms. Examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, t-octyl, n-nonyl, i-nonyl, decyl , called n-dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl.
  • the alkyl can also be substituted or interrupted by cycloalkyl, e.g. Cyclohexylmethyl or methylcyclohexylethyl.
  • the aryl can also be substituted by cycloalkyl, preferably having 5 or 6 ring carbon atoms, which can also be substituted by alkyl. Examples are: cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, octylcyclohexyl, cyclooctyl.
  • the aryl can also be substituted by aryl, preferably phenyl and aralkyl, preferably benzyl, ⁇ - or ⁇ -phenylethyl.
  • the aryl group can be substituted by alkyl groups with preferably 1 to 8 carbon atoms. Examples are methylphenyl, ethylphenyl, methylbenzyl.
  • hydroxyaromatic compounds of the formula ROH are phenol, Y t - or ⁇ -naphthol, methylnaphthol, 2- or 4-methylphenol, 2-or 4-ethylphenol, 2- or 4-propyl- and isopropylphenol, 2-or 4-n Butyl, i-butyl and t-butylphenol, pentyl, hexyl, heptyl, n-octyl, tert-octyl, nonyl, decyl, dodecyl, octadecylphenol, cyclohexyl, phenyl or benzylphenol, 2,4- or 2,6-dimethyl, diethyl, dipropyl, diisopropyl, di-n-butyl, di-i-butylphenol, 2,4-di-tert-butylphenol, 2-methyl 4-ethylbenzene, 2-methyl-4-tert-
  • phosphorus halides used as starting compounds in the implementation of the phosphor trichloride is particularly preferred. Stoichiometric amounts of the reactants are preferably used in order to avoid additional cleaning operations. Sometimes, however, it can be advantageous if a slight excess, for example up to 10%, of the hydroxyaryles is used.
  • the catalyst is preferably used in amounts of 0.05 to 5 mol%, in particular 0.1 to 2 mol%.
  • the inventive method can be at temperatures from 10 ° C to preferably 150 ° C. be carried out in particular 20 to 130 ° C. Higher temperatures are generally not required, which is particularly advantageous.
  • Suitable solvents are e.g. Ethers such as diethyl ether, tetrahydrofuran and dioxane, aliphatic and aromatic hydrocarbons such as hexane, heptane, petroleum ether, cyclohexane, methylcyclohexane, benzene, toluene and xylene, chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane and carbon tetrachloride.
  • Ethers such as diethyl ether, tetrahydrofuran and dioxane
  • aliphatic and aromatic hydrocarbons such as hexane, heptane, petroleum ether, cyclohexane, methylcyclohexane, benzene, toluene and xylene
  • chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane and carbon tetrachlor
  • the process is carried out in the presence of selected catalysts.
  • the N atoms of the amines and ammonium salts, the amides and the nitrogen-containing heterocycles, the guanidines, amidines and azomethines and their salts, the sulfones, sulfoxides, sulfonium compounds, phosphines, phosphine oxides and phosphine sulfides can optionally alkyl, cycloalkyl interrupted by oxygen or sulfur atoms, Aryl, here especially phenyl, alkaryl, here especially alkylated phenyl, aralkyl, here especially benzyl or alkaralkyl, here especially alkylated benzyl, which preferably have 1 to 18, in particular 1 to 12, carbon atoms.
  • the alkyl contains especially 1 to 6 carbon atoms and cycloalkyl is especially cyclopentyl and cyclohexyl.
  • the catalysts to be used according to the invention as salts are preferably the halides and especially the chlorides.
  • the salts can also be formed in situ by the hydrogen halide formed in the process. Nevertheless, in some cases it is advantageous to use the salts themselves as catalysts.
  • the amines and ammonium salts are a catalyst group. These can be primary, secondary and tertiary amines and their salts.
  • the salts also include the quaternary ammonium salts.
  • the secondary amines, their salts and the quaternary ammonium salts are preferred.
  • the alkyl and cycloalkyl substituted amines such as the cyclic amines, which are assigned to the non-aromatic heterocycles.
  • Examples are: methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, octyl, dodecyl, phenyl, benzyl, dimethyl, diethyl, methylethyl, methylbutyl, methyloctyl, methylphenyl -, ethylbenzyl, trimethyl, triethyl, tributyl, octyldimethyl, dimethylphenylamine and tetramethyl, trimethylethyl, triethylmethyl, tributylmethyl, tetrabutyl, trimethyloctyl, triphenylmethyl and tribenzylmethylammonium chloride or bromide or bromide.
  • ammonium salts examples include methyl, octyl, dimethyl, methylcyclohexyl, dibenzyl, diphenyl, trimethyl, tributyl, tribenzyl and triphenylammonium chloride, bromide and iodide.
  • the amines and ammonium salts can also contain aromatic N-heterocyclic radicals, e.g. Pyridyl. These amines are more effective than the pure aromatic N-heterocycles.
  • Another group of catalysts are the amides of carboxylic and thiocarboxylic acids and the oxygen acids of phosphorus.
  • This group also includes ureas, thioureas and their bis-urea derivatives.
  • the amides can be derived from polyfunctional, preferably monofunctional, carboxylic acids or thiocarboxylic acids, which in particular contain 1 to 14 carbon atoms.
  • the acids can also be derived from aromatic N-heterocycles. It has been found that these amides are significantly more effective than the underlying aromatic N-heterocycles. Cyclic amides such as, for example, s-caprolacetam are also suitable.
  • Examples are formamide, oxalic acid diamide, dimethylformamide, acetamide, thioacet amide, N, N-dimethylacetamide or thioacetamide, picoanilide, thiopicoanilide, benzoic acid amide, terephthalic acid diamide, trimellitic acid triamide.
  • the phosphoric oxygen acids from which the amides can be derived are e.g. phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid or phosphinic acid.
  • Phosphoric acid and phosphonic acids are preferred.
  • Examples of such amides are phosphoric acid triamide, hexamethylphosphoric acid triamide, methylphosphonic acid diamide, phenylphosphonic acid N, N-tetramethyldiamide, N, N '- (dimethyl) phenylphosphonic acid diamide.
  • Examples of the amides of carbonic acid and thionocarbonic acid include urea and thiourea: tetramethylurea or thiourea, diphenyl or dibenzylurea or thiourea, diethylurea, di-n-octylurea or thiourea and bis-urea derivatives such as e.g. Ethylene bisurea, N, N-tetramethylphenylene thiourea.
  • Examples of cyclic ureas are hydantoin and benzimidazolone.
  • Non-aromatic N-heterocycles These can contain more than one N atom as well as 0 and S atoms. They can also be unsaturated. They can be in the form of salts, also in the form of quaternary ammonium bases, and the N atoms can be substituted, preferably with alkyl groups of 1 to 12 carbon atoms. Examples are:
  • the guanides themselves include N-alkylated, benzylated and phenylated derivatives, e.g. Tetramethyl or tetrabutylguanidine, N, N'-bisphenylguanidine.
  • the halides are mainly considered as salts.
  • catalysts are the azomethines and amidines and their salts, preferably the halides. They can be represented by the following formulas: wherein R 4 is phenyl, benzyl, cyclohexyl, a hydrogen atom or alkyl having 1 to 8, preferably 1 to 4 C atoms and R 5 is a hydrogen atom or phenyl, benzyl, cyclohexyl or alkyl having 1 to 18, preferably 1 to 8 C atoms are. Examples include:
  • Acetamidine hydrochloride N-methylacetamidine, benzylidene anilide, N-butylpropionamidine.
  • the sulfones and sulfoxides used as catalysts can be linear or cyclic and they can contain further functional groups, e.g. Ester groups. Examples are: dimethyl sulfone, dimethyl sulfoxide, tetra- or pentamethylene sulfone, tetramethylene xulfoxide, bis-carboisooctyloxidi-. methyl sulfoxide.
  • the sulfonium iodides are preferred, e.g. Trimethylsulfonium iodide, dimethylethylsulfonium iodide, triethylsulfonium iodide.
  • the salts, especially the iodides of the sulfoxides, are also suitable, e.g. Trimethylsulfoxonium iodide.
  • catalysts to be used according to the invention are the primary, secondary and tertiary phosphines, their salts, oxides and sulfides.
  • the tertiary phosphines, their salts, oxides and sulfides are preferred and among the salts the hydrohalides, especially the chlorides, bromides and iodides.
  • the phosphorus atom can contain phenyl, benzyl, cyclohexyl and alkyl having 1 to 12, preferably 1 to 6, carbon atoms.
  • Examples are: methylphosphine, ethylphosphine, hexylphosphine, dodecylphosphine, dimethyl-, ethylmethyl-, diphenyl-, dicyclohexyl-, dibenzyl-, phenylmethylphosphine, triphenyl-, tribenzyl-, tricyclohexyl-, trimethyl-, triethyl-, tripropyl-, tri-pyl-, tri- -, Tripentyl, trihexyl, dimethylphenylphosphine, their hydrochlorides, bromides and iodides as well as oxides and sulfides.
  • the alcohol residues of the esters of phosphonic acids and phosphoric acid are preferably derived from phenols and especially C 1 -C 1s- alkanols and cycloalkanols, for example phenol, 2-methylphenol, cyclohexanol, methanol, ethanol, propanol, butanol, hexanol, octanol, i-octanol , Dodecanol, octadecanol.
  • Examples of phosphonic acids are: phenyl, benzyl, cyclohexyl, methyl, ethyl, propyl, butyl, pentyl and hexylphosphonic acid.
  • the method according to the invention is carried out in devices known for this.
  • the hydroxyaryl, optionally together with a solvent, the phosphorus trihalide is added and, after the catalyst has been added, the reaction mixture is stirred until the reaction is complete. Stirring is preferably carried out with heating to accelerate the reaction.
  • the hydrogen halide formed is advantageously removed continuously during the reaction, vacuum being able to be used for complete separation.
  • the desired triaryl phosphite is isolated by known methods by distillation or crystallization, if appropriate after removing the solvent.
  • triaryl phosphites are surprisingly obtained under mild conditions in relatively short reaction times in high purity and excellent yields. It is particularly advantageous in this process that this also applies to the production of substituted hydroxyaromatics as reactants, particularly those in which the reactivity of the hydroxyl group is impaired by steric hindrance.
  • the triaryl phosphites produced according to the invention are suitable as stabilizers or costabilizers together with e.g. phenolic antioxidants for processing thermoplastic polymers, e.g. Polyolefins.
  • the acidity of the initial charge is then determined by titration with 0.1 N sodium hydroxide solution.
  • reaction mixture is diluted with isopropanol.
  • the crystallized tris (2,4-di-tert-butylphenyl) phosphite is filtered off, washed with isopropanol and dried. 221 g of product (85.4% yield) with a melting point of 186-187 ° C. are obtained.
  • the phosphite is very pure and only contains traces of 2,4-di-tert-butylphenol.

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Claims (8)

1. Procédé de préparation de phosphites de triaryles répondant à la formule (RO)3P dans laquelle R désigne un radical aryle ou un radical aryle porteur d'un ou plusieurs substituants pris dans l'ensemble constitué par les alkyles linéaires ou ramifiés, les cycloalkyles, les aryles et les aralkyles, avec la condition qu'il ne doit pas y avoir deux substituants à atome de carbone tertiaire en α aux deux positions voisines de la liaison éther, par réaction de trihalogénures de phosphore avec des composés aromatiques hydroxyliques de formule ROH, en présence de 0,005 à 10% en moles, par rapport au composé hydroxy-arylique, d'un catalyseur, éventuellement en présence d'un solvant, procédé caractérisé en ce qu'on utilise, comme catalyseur, un composé pris dans les groupes suivants:
- les amines et les sels d'ammoniums,
- les amides des acides carboxyliques et thiocarboxyliques ainsi que de acides oxygénés du phosphore,
- les hétérocycles azotés non aromatiques et leurs sels,
- les guanidines, amidines et azométhines ainsi que leurs sels,
- les sulfones, les sulfoxydes et les sels de sulfoniums,
- les phosphines primaires, secondaires et tertiaires ainsi que leurs sels, leurs oxydes et leurs sulfures, et
- les esters de l'acide phosphorique et des acides phosphoniques.
2. Procédé selon la revendication 1, caractérisé en ce que les sels des hétérocycles azotés, des amines, des guanidines, des amidines, des azométhines ou des phosphines ainsi que les sels d'ammoniums ou de sulfoniums sont des halogénures, plus particulièrement des chlorures.
3. Procédé selon la revendication 1, caractérisé en ce que les amines et les sels d'ammoniums, les atomes d'azote des amides et des hétérocycles azotés, des guanidines, des amidines et des azométhines, les sulfones, les sulfoxydes, les composés de sulfoniums, les phosphines; les oxydes de phosphines et les sulfures de phosphines portent comme substituant des radicaux alkyles, cyclo-alkyles, aryles, alkylaryles, aralkyles ou alkyl-aralkyles, éventuellement interrompus par des atomes d'oxygène ou de soufre, radicaux qui ont de préférence de 1 à 18 atomes de carbone, en particulier de 1 à 12, comme dans le cas, très apprécié du diméthylsulfoxyde ou de la triphénylphosphine.
4. Procédé selon la revendication 1, caractérisé en ce que le catalyseur est une amine secondaire, de préférence la di-isopropylamine, ou un sel d'ammonium, de préférence un sel d'une amine secondaire ou un sel d'ammonium quaternaire, surtout le chlorure de tétraméthylammonium.
5. Procédé selon la revendication 1, caractérisé en ce que les amides dérivent d'acides carboxyliques ou thiocarboxyliques monofonctionnels qui contiennent de 1 à 14 atomes de carbone, et sont de préférence le diméthylformamide, le thio-acétamide, l'anilide de l'acide a-thiopicolique, le chlorhydrate d'acétamidine, la tétraméthyl-thio-urée ou la tétraméthyl-guanidine.
6. Procédé selon la revendication 1, caractérisé en ce que les esters de l'acide phosphorique ou des acides phosphoniques contiennent des radicaux de phénols, d'alcanols ou de cyclo-alcanols, comme c'est le cas pour le méthane-phosphonate de diméthyle, corps très apprécié.
7. Procédé selon la revendication 1, caractérisé en ce que les hétérocycles azotés non aromatiques contiennent en outre, dans le noyau, un atome d'oxygène ou de soufre et ont des cycles comportant de 5 à 7 maillons, comme c'est le cas pour la morpholine ou pour la méthyl-2 A 2-oxazoline, corps très apprécié.
8. Procédé selon la revendication 1, caractérisé en ce qu'on utilise, comme sels de sulfoniums, les iodures, de préférence l'iodure de triméthylsulfonium.
EP78100550A 1977-08-08 1978-07-31 Procédé pour la préparation de phosphites de triaryle Expired EP0000757B1 (fr)

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CH969177 1977-08-08
CH9691/77 1977-08-08

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EP0000757B1 true EP0000757B1 (fr) 1981-08-05

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EP (1) EP0000757B1 (fr)
JP (1) JPS5430140A (fr)
DE (1) DE2860898D1 (fr)

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US4312818A (en) 1982-01-26
JPS5430140A (en) 1979-03-06
DE2860898D1 (en) 1981-11-05
EP0000757A1 (fr) 1979-02-21
JPS6317080B2 (fr) 1988-04-12

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