EP0000240A1 - Phosphate ester compositions and process for preparing them - Google Patents

Phosphate ester compositions and process for preparing them Download PDF

Info

Publication number
EP0000240A1
EP0000240A1 EP78300009A EP78300009A EP0000240A1 EP 0000240 A1 EP0000240 A1 EP 0000240A1 EP 78300009 A EP78300009 A EP 78300009A EP 78300009 A EP78300009 A EP 78300009A EP 0000240 A1 EP0000240 A1 EP 0000240A1
Authority
EP
European Patent Office
Prior art keywords
phosphate
alkali metal
alkyl
composition
phosphate ester
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
EP78300009A
Other languages
German (de)
French (fr)
Other versions
EP0000240B1 (en
Inventor
Luc Edouard Adrien Marcel Feyt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Agriculture BVBA
Original Assignee
Monsanto Europe NV SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Monsanto Europe NV SA filed Critical Monsanto Europe NV SA
Publication of EP0000240A1 publication Critical patent/EP0000240A1/en
Application granted granted Critical
Publication of EP0000240B1 publication Critical patent/EP0000240B1/en
Expired legal-status Critical Current

Links

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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • 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
    • C07F9/09—Esters of phosphoric acids
    • C07F9/14—Esters of phosphoric acids containing P(=O)-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
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/42—Halides thereof
    • 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
    • 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
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds

Definitions

  • This invention relates to phosphate ester compositions that are useful as flame retardant plasticizers for vinyl chloride polymers.
  • Alkyl diaryl phosphates for example 2-ethylhexyl diphenyl phosphate, are used as plasticizers for vinyl chloride polymers which are to be used under conditions where fire resistant properties in the polymer are required.
  • Commercial alkyl diaryl phosphates normally contain small amounts, for example not more than 5% by weight of the total phosphate,of dialkyl aryl phosphates and triaryl phosphates. It has also been proposed to use halogen-containing phosphate esters for this purpose, but the halogen-containing esters are generally more expensive than hydrocarbyl esters, and their use is considered by some to be undesirable because of possible adverse environmental effects.
  • Triaryl phosphates for example triphenyl phosphate, impart improved flame retardant properties to vinyl chloride polymers compared with the alkyl diaryl phosphates but the latter are the more effective plasticizers as judged by the physical properties of the vinyl chloride polymers containing them, especially by flexibility at low temperatures.
  • triphenyl phosphate is a crystalline solid at ordinary temperatures, and its incorporation into vinyl chloride polymers therefore requires a different 'and generally more complicated procedure than that used for the liquid alkyl diaryl phosphates.
  • a simple way of making such blends is to dissolve the triphenyl phosphate in the alkyl diphenyl phosphate at a temperature at which the triphenyl phosphate dissolves readily, but we have found that triphenyl phosphate crystallizes from such blends on storage at temperatures of 0°C. or below. Blends prepared in this way are therefore not suitable as commercial products.
  • the present invention provides blends of alkyl diphenyl phosphates having good low temperature storage stability and a process for the production of such blends.
  • a phosphate ester composition of the invention is a liquid comprising (i) a first phosphate ester component consisting of at least one C 6-12 alkyl diphenyl phosphate or a mixture of at least one C 6-12 alkyl diphenyl phosphate and at least one di(C 6-12 alkyl) phenyl phosphate in which mixture the amount of the di(C 6-12 alkyl) phenyl phosphate or phosphates is not more than 10 molar percent of the mixture, and (ii) triphenyl phosphate, the ratio by weight of the first phosphate ester component to the triphenyl phosphate in the composition being from 1.8:1 to 5.5:1, the phosphate ester composition-having a low temperature storage stability such that no crystallisation of triphenyl phosphate occurs during storage of the composition during 10 days at -5 C.
  • the process of the invention is one for the production of a liquid phosphate ester composition which comprises reacting a phosphorus oxyhalide with a stoichiometric excess of an alkali metal phenate to form a mixture containing triphenyl phosphate and alkali metal phenate, and reacting the alkali metal phenate in that mixture with a dihalidate reactant comprising at least one C 6-12 alkyl phosphorodihalidate, the proportions of the reactants being selected so that the liquid phosphate ester composition contains (i) a first phosphate ester component consisting of at least one C 6-12 alkyl diphenyl phosphate or a mixture of at least one C 6-12 alkyl diphenyl phosphate with at least one di(C 6-12 alkyl) phenyl phosphate in which mixture the amount of the di(C 6-12 alkyl) phenyl phosphate or phosphates is not more than 10 molar percent of the mixture and (ii
  • the ratio by weight of the first phosphate ester component to the triphenyl phosphate is in range 1.85:1 to 5:1.
  • the actual proportion in any particular instance will depend on a balance between increasing the amount of triphenyl phosphate to improve the flame-retardant properties of the compositions and achieving low temperature stability, the latter being improved as the proportion of triphenyl phosphate decreases.
  • Compositions of the invention may, for example, have weight ratios of the first phosphate ester component to triphenyl phosphate within the range 2:1 to 2.5:1, or within the range 3:1 to 5:1.
  • Storage stabilities of the compositions of the invention are usually better than the minimum requirement that no crystallisation of triphenyl phosphate should occur during storage for 10 days at -5°C.
  • storage stabilities such that no crystallisation of triphenyl phosphate occurs during storage for 10 days or longer at temperatures below -5°C., for example 10 days at -10°C. or -13°C, or 20 days at -20°C. are often observed.
  • the dihalidate reactant for use in the process of the invention can be prepared by the reaction of a C 6-12 alkanol or a mixture of C 6-12 alkanols with phosphorus oxyhalide, using 1 mole of alkanol per mole of phosphorus oxyhalide, with removal of the hydrogen halide generated by this reaction.
  • a small amount of di(C 6-12 alkyl)phosphorohalidate usually not exceeding one-tenth on a molar basis of the amount of the dihalidate reactant,is formed, as well as the C 6-12 alkyl phosphorodihalidate which is the major product.
  • the final liquid phosphate ester composition will normally contain an amount of di(C 6-12 alkyl) phenyl phosphate corresponding to the amount of di(C 6-12 alkyl) phosphorohalidate in the dihalidate reactant.
  • the steps of the process as defined above appear to be critical for the production of a product having the required degree of low temperature stability.
  • the concurrent formation of the alkyl diphenyl phosphate and the triphenyl phosphate by the reaction of a mixture of phosphorus oxyhalide and alkyl phosphorodihalidate with an alkali metal phenate in the appropriate proportions gives a product which is significantly less stable.
  • an amount of phosphorus oxyhalide corresponding to the required amount of triphenyl phosphate is added with agitation and cooling to an aqueous solution of alkali metal phenate containing sufficient alkali metal phenate to react with the whole of the phosphorus oxyhalide and with the dihalidate reactant to be added subsequently.
  • the reaction of the phosphorus oxyhalide with the alkali metal phenate is highly exothermic, and the temperature is preferably controlled below 50 C., preferably in the range 15-30°C.
  • alkali metal phenate solution containing free alkali metal hydroxide for example up to 20% on a molar basis of the amount of alkali metal phenate.
  • reaction mixture is then preferably cooled to 5-15 C., preferably after the addition, if necessary, of sufficient water to retain in solution the alkali metal halide formed during the process, and the agitation discontinued.
  • the reaction mixture thereafter separates into an aqueous layer containing alkali metal halide, and an organic layer comprising the phosphate ester composition.
  • the organic layer is separated from the aqueous layer, and can be purified by conventional techniques, including for example washing with water and vacuum treatment.
  • the phosphorus oxyhalide usually employed in practice is phosphorus oxychloride,but phosphorus oxybromide, for example, could be used; and the usual alkali metal phenate is sodium phenate, but potassium phenate could be used.
  • the C 6-12 alkyl group can be a straight or branched-chain group, for example a n-hexyl, n-octyl, 2-ethylhexyl, n-decyl or n-dodecyl group, the corresponding alcohols used to prepare the dihalidate reactant being n-hexanol, n-octanol, 2-ethylhexanol, n-decanol and n-dodecanol.
  • a mixture of alcohols can be used, resulting in the first phosphate ester component containing more than one C 6-12 alkyl diphenyl phosphate.
  • a phosphate ester composition of the invention may contain only the first phosphate ester component and the triphenyl phosphate, but minor amounts of other ingredients? such as diluents, compatible plasticizers or flame retardants may be added if desired.
  • compositions are those that contain no significant amounts of other ingredients, and in such compositions, the weight ratio ranges referred to above include compositions containing from 65% to 75% by weight of the first phosphate ester component, the balance (i.e. from 35% to 25% by weight of the composition) being triphenyl phosphate, and compositions containing from 75 to 85%, for example 80%, by weight of the first phosphate ester component, the balance being triphenyl phosphate.
  • Particularly useful compositions contain 68-72% by weight 2-ethylhexyl diphenyl phosphate, 4-8% by weight di(2-ethylhexyl) phenyl phosphate, the balance being triphenyl phosphate.
  • the phosphate ester compositions of the present invention can be used as flame retardaht plasticizers for vinyl chloride polymers in the same manner and in substantially the same amounts as the klkyl diphenyl phosphates used hitherto.
  • the term "vinyl chloride polymer” includes polyvinyl chloride homopolymer and polymers obtained by the copolymerization of vinyl chloride with a minor amount of one or more monomers copolymerizable with vinyl chloride, for example olefins such as ethylene and propylene, vinyl ethers and alkyl acrylates and methacrylates.
  • a 22% by weight solution of sodium hydroxide was prepared by diluting 368 grams of 46% by weight sodium hydroxide solution with 402 grams of water. To this solution,347 grams of phenol were added gradually, keeping the temperature of the solution at 15-20°C.
  • Phosphorus oxychloride (78.3 grams) was added gradually to the sodium phenate solution in a stirred and cooled reactor, the rate of addition being adjusted to maintain the temperature of the reactants at 20-25°C.
  • the 2-ethylhexyl phosphorodichloridate was then added, again keeping the temperature at 20-25°C., and stirring (without cooling) was continued for 45 minutes after the addition of the phosphorodichloridate was complete.
  • Water 300 grams was then added and stirring was continued for a further 15 minutes and during subsequent cooling to 15 0 C. Stirring was then stopped, and the mixture was allowed to settle for 60 minutes, forming two layers, an upper aqueous layer and a lower organic layer.
  • the two layers were separated, and the organic layer was washed twice at 90°C, with an equal volume of 2% by weight sodium hydroxide solution containing a small amount of a sequestering agent, and a further four times with an equal volume of water at a temperature of 70-80°C. After the final wash the phosphate ester product was steam stripped under vacuum to remove any residual low-boiling material, and then filtered.
  • the phosphate ester composition prepared as described above contained about 66% by weight of 2-ethylhexyl diphenyl phosphate, about 4% by weight of di(2-ethylhexyl) phenyl phosphate and 30% by weight of triphenyl phosphate.
  • the composition showed no signs of crystallization during 6 weeks storage at -13°C. or at -20°C.
  • a composition containing the same proportions of phosphate ester ingredients but prepared by dissolving triphenyl phosphate in the other component showed turbidity after one week and an extensive deposit after two weeks at -13°C.
  • compositions within the scope of the invention were prepared by the same procedure as that described in Example 1, but with different amounts of reactants in stages b) and c).
  • the amounts of reactants, together with the proportions of 2-ethylhexyl diphenyl phosphate (EDP), di(2-ethylhexyl) phenyl phosphate (DPP) and triphenyl phosphate (TPP) in the products, are shown in the table below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Flame retarding and plasticizing compositions for vinyl-chloride polymers comprising (i) a first phosphat ester component containing at least one C6-12 alkyl diphenyl phosphate and (ii) triphenyl phosphate having proportions of (i) to (ii) in the range of 1.8:1 to 5.5:1 are stable homogeneous liquids at low temperatures when prepared by a process in which a phosphorus oxyhalide is reacted with an excess of an alkali metal phenate to form a mixture containing triphenyl phosphate and alkali metal phenate, and the alkali metal phenate in that mixture is reacted with a C6-12 alkyl phosphrordichloridate.

Description

  • This invention relates to phosphate ester compositions that are useful as flame retardant plasticizers for vinyl chloride polymers.
  • Alkyl diaryl phosphates, for example 2-ethylhexyl diphenyl phosphate, are used as plasticizers for vinyl chloride polymers which are to be used under conditions where fire resistant properties in the polymer are required. Commercial alkyl diaryl phosphates normally contain small amounts, for example not more than 5% by weight of the total phosphate,of dialkyl aryl phosphates and triaryl phosphates. It has also been proposed to use halogen-containing phosphate esters for this purpose, but the halogen-containing esters are generally more expensive than hydrocarbyl esters, and their use is considered by some to be undesirable because of possible adverse environmental effects.
  • Triaryl phosphates, for example triphenyl phosphate, impart improved flame retardant properties to vinyl chloride polymers compared with the alkyl diaryl phosphates but the latter are the more effective plasticizers as judged by the physical properties of the vinyl chloride polymers containing them, especially by flexibility at low temperatures. Moreover, triphenyl phosphate is a crystalline solid at ordinary temperatures, and its incorporation into vinyl chloride polymers therefore requires a different 'and generally more complicated procedure than that used for the liquid alkyl diaryl phosphates.
  • We have found that certain blends of alkyl diphenyl phosphates and triphenyl phosphate can be prepared containing sufficient triphenyl phosphate to impart improved flame retardant properties to vinyl chloride polymers plasticized with the blends, while not significantly detracting from the physical and processing properties of the thus- plasticized polymers relative to the same vinyl chloride polymers plasticized with alkyl diaryl phosphates alone.
  • A simple way of making such blends is to dissolve the triphenyl phosphate in the alkyl diphenyl phosphate at a temperature at which the triphenyl phosphate dissolves readily, but we have found that triphenyl phosphate crystallizes from such blends on storage at temperatures of 0°C. or below. Blends prepared in this way are therefore not suitable as commercial products.
  • The present invention provides blends of alkyl diphenyl phosphates having good low temperature storage stability and a process for the production of such blends.
  • A phosphate ester composition of the invention is a liquid comprising (i) a first phosphate ester component consisting of at least one C6-12 alkyl diphenyl phosphate or a mixture of at least one C6-12 alkyl diphenyl phosphate and at least one di(C6-12 alkyl) phenyl phosphate in which mixture the amount of the di(C6-12 alkyl) phenyl phosphate or phosphates is not more than 10 molar percent of the mixture, and (ii) triphenyl phosphate, the ratio by weight of the first phosphate ester component to the triphenyl phosphate in the composition being from 1.8:1 to 5.5:1, the phosphate ester composition-having a low temperature storage stability such that no crystallisation of triphenyl phosphate occurs during storage of the composition during 10 days at -5 C.
  • The process of the invention is one for the production of a liquid phosphate ester composition which comprises reacting a phosphorus oxyhalide with a stoichiometric excess of an alkali metal phenate to form a mixture containing triphenyl phosphate and alkali metal phenate, and reacting the alkali metal phenate in that mixture with a dihalidate reactant comprising at least one C6-12 alkyl phosphorodihalidate, the proportions of the reactants being selected so that the liquid phosphate ester composition contains (i) a first phosphate ester component consisting of at least one C6-12 alkyl diphenyl phosphate or a mixture of at least one C6-12 alkyl diphenyl phosphate with at least one di(C6-12 alkyl) phenyl phosphate in which mixture the amount of the di(C6-12 alkyl) phenyl phosphate or phosphates is not more than 10 molar percent of the mixture and (ii) triphenyl phosphate, the ratio by weight of the first phosphate ester component to the triphenyl phosphate being from 1.8:1 to 5.5:1.
  • In preferred compositions, the ratio by weight of the first phosphate ester component to the triphenyl phosphate is in range 1.85:1 to 5:1. The actual proportion in any particular instance will depend on a balance between increasing the amount of triphenyl phosphate to improve the flame-retardant properties of the compositions and achieving low temperature stability, the latter being improved as the proportion of triphenyl phosphate decreases. Compositions of the invention may, for example, have weight ratios of the first phosphate ester component to triphenyl phosphate within the range 2:1 to 2.5:1, or within the range 3:1 to 5:1.
  • Storage stabilities of the compositions of the invention are usually better than the minimum requirement that no crystallisation of triphenyl phosphate should occur during storage for 10 days at -5°C. For example, storage stabilities such that no crystallisation of triphenyl phosphate occurs during storage for 10 days or longer at temperatures below -5°C., for example 10 days at -10°C. or -13°C, or 20 days at -20°C. are often observed.
  • The dihalidate reactant for use in the process of the invention can be prepared by the reaction of a C6-12 alkanol or a mixture of C6-12 alkanols with phosphorus oxyhalide, using 1 mole of alkanol per mole of phosphorus oxyhalide, with removal of the hydrogen halide generated by this reaction. Under normal process conditions, a small amount of di(C6-12 alkyl)phosphorohalidate, usually not exceeding one-tenth on a molar basis of the amount of the dihalidate reactant,is formed, as well as the C6-12 alkyl phosphorodihalidate which is the major product. In practice it is unnecessary to remove the di(C6-12 alkyl) phosphorohalidate, so that the final liquid phosphate ester composition will normally contain an amount of di(C6-12 alkyl) phenyl phosphate corresponding to the amount of di(C6-12 alkyl) phosphorohalidate in the dihalidate reactant.
  • The steps of the process as defined above appear to be critical for the production of a product having the required degree of low temperature stability. For example, the concurrent formation of the alkyl diphenyl phosphate and the triphenyl phosphate by the reaction of a mixture of phosphorus oxyhalide and alkyl phosphorodihalidate with an alkali metal phenate in the appropriate proportions gives a product which is significantly less stable.
  • In a preferred way of operating the process, an amount of phosphorus oxyhalide corresponding to the required amount of triphenyl phosphate is added with agitation and cooling to an aqueous solution of alkali metal phenate containing sufficient alkali metal phenate to react with the whole of the phosphorus oxyhalide and with the dihalidate reactant to be added subsequently. The reaction of the phosphorus oxyhalide with the alkali metal phenate is highly exothermic, and the temperature is preferably controlled below 50 C., preferably in the range 15-30°C.
  • When the addition of the phosphorus oxyhalide is complete, addition of the dihalidate reactant to the reaction mixture is begun, again with agitation and cooling of the reaction mixture to keep the temperature below a preferred 50 C., for example within the range 15-30°C.
  • It is preferred to employ a small excess, for example from 2 to 10% more than the stoichiometric amount, of the alkali metal phenate overall. It is also preferred to use an alkali metal phenate solution containing free alkali metal hydroxide, for example up to 20% on a molar basis of the amount of alkali metal phenate.
  • When the addition of the dihalidate reactant is complete, stirring may be continued for a further period to ensure completion of the reaction. The reaction mixture is then preferably cooled to 5-15 C., preferably after the addition, if necessary, of sufficient water to retain in solution the alkali metal halide formed during the process, and the agitation discontinued. The reaction mixture thereafter separates into an aqueous layer containing alkali metal halide, and an organic layer comprising the phosphate ester composition. The organic layer is separated from the aqueous layer, and can be purified by conventional techniques, including for example washing with water and vacuum treatment.
  • The phosphorus oxyhalide usually employed in practice is phosphorus oxychloride,but phosphorus oxybromide, for example, could be used; and the usual alkali metal phenate is sodium phenate, but potassium phenate could be used.
  • In the compositions of the invention, the C6-12 alkyl group can be a straight or branched-chain group, for example a n-hexyl, n-octyl, 2-ethylhexyl, n-decyl or n-dodecyl group, the corresponding alcohols used to prepare the dihalidate reactant being n-hexanol, n-octanol, 2-ethylhexanol, n-decanol and n-dodecanol. A mixture of alcohols can be used, resulting in the first phosphate ester component containing more than one C6-12 alkyl diphenyl phosphate.
  • .A phosphate ester composition of the invention may contain only the first phosphate ester component and the triphenyl phosphate, but minor amounts of other ingredients? such as diluents, compatible plasticizers or flame retardants may be added if desired.
  • The preferred compositions are those that contain no significant amounts of other ingredients, and in such compositions, the weight ratio ranges referred to above include compositions containing from 65% to 75% by weight of the first phosphate ester component, the balance (i.e. from 35% to 25% by weight of the composition) being triphenyl phosphate, and compositions containing from 75 to 85%, for example 80%, by weight of the first phosphate ester component, the balance being triphenyl phosphate. Particularly useful compositions contain 68-72% by weight 2-ethylhexyl diphenyl phosphate, 4-8% by weight di(2-ethylhexyl) phenyl phosphate, the balance being triphenyl phosphate.
  • The phosphate ester compositions of the present invention can be used as flame retardaht plasticizers for vinyl chloride polymers in the same manner and in substantially the same amounts as the klkyl diphenyl phosphates used hitherto. The term "vinyl chloride polymer" includes polyvinyl chloride homopolymer and polymers obtained by the copolymerization of vinyl chloride with a minor amount of one or more monomers copolymerizable with vinyl chloride, for example olefins such as ethylene and propylene, vinyl ethers and alkyl acrylates and methacrylates.
  • The invention is illustrated by the following Examples.
    • EXAMPLE I a) Preparation of alkyl phosphorodichloridate.
  • 2-Ethylhexanol (137 grams) was added gradually to a stirred and cooled reactor containing 162 grams of phosphorus oxychloride while keeping the temperature of the reaction mixture at 13-17°C. To remove hydrogen chloride formed during the reaction, the pressure in the reactor was reduced to 70 mbar and the temperature was raised to 250C. These conditions were maintained for 60 minutes and the 2-ethylhexyl phosphorodichloridate was then cooled to 15°C. and the vacuum released.
    • b) Preparation of sodium phenate solution.
  • A 22% by weight solution of sodium hydroxide was prepared by diluting 368 grams of 46% by weight sodium hydroxide solution with 402 grams of water. To this solution,347 grams of phenol were added gradually, keeping the temperature of the solution at 15-20°C.
    • c) Preparation of phosphate ester composition.
  • Phosphorus oxychloride (78.3 grams) was added gradually to the sodium phenate solution in a stirred and cooled reactor, the rate of addition being adjusted to maintain the temperature of the reactants at 20-25°C. The 2-ethylhexyl phosphorodichloridate was then added, again keeping the temperature at 20-25°C., and stirring (without cooling) was continued for 45 minutes after the addition of the phosphorodichloridate was complete. Water (300 grams) was then added and stirring was continued for a further 15 minutes and during subsequent cooling to 150C. Stirring was then stopped, and the mixture was allowed to settle for 60 minutes, forming two layers, an upper aqueous layer and a lower organic layer.
  • The two layers were separated, and the organic layer was washed twice at 90°C, with an equal volume of 2% by weight sodium hydroxide solution containing a small amount of a sequestering agent, and a further four times with an equal volume of water at a temperature of 70-80°C. After the final wash the phosphate ester product was steam stripped under vacuum to remove any residual low-boiling material, and then filtered.
  • The phosphate ester composition prepared as described above contained about 66% by weight of 2-ethylhexyl diphenyl phosphate, about 4% by weight of di(2-ethylhexyl) phenyl phosphate and 30% by weight of triphenyl phosphate. The composition showed no signs of crystallization during 6 weeks storage at -13°C. or at -20°C. In comparison, a composition containing the same proportions of phosphate ester ingredients but prepared by dissolving triphenyl phosphate in the other component showed turbidity after one week and an extensive deposit after two weeks at -13°C.
    • EXAMPLES 2-4
  • Other compositions within the scope of the invention were prepared by the same procedure as that described in Example 1, but with different amounts of reactants in stages b) and c). The amounts of reactants, together with the proportions of 2-ethylhexyl diphenyl phosphate (EDP), di(2-ethylhexyl) phenyl phosphate (DPP) and triphenyl phosphate (TPP) in the products, are shown in the table below.
    Figure imgb0001

Claims (10)

1. A liquid phosphate ester composition comprising (i) a first phosphate ester component consisting of at least one C6-12 alkyl diphenyl phosphate or a mixture of at least one C6-12 alkyl diphenyl phosphate and at least one di(C6-12 alkyl) phenyl phosphate in which mixture the amount of the di(C6-12 alkyl) phenyl phosphate or phosphates is not more than 10 molar percent of the mixture, and (ii) triphenyl phosphate; characterised in that the ratio by weight of the first phosphate ester component to the triphenyl phosphate in the composition is from 1.8:1 to 5.5:1, and the phosphate ester composition has a low temperature storage stability such that no crystallisation of triphenyl phosphate occurs during storage of the composition during 10 days at -5°C. -
2. A composition according to Claim 1 characterised in that the storage stability is such that no crystallisation of triphenyl phosphate occurs during storage of the composition during 10 days at -13°C.
3. A composition according to Claim 1 characterised in that the first phosphate ester component is a mixture of 2-ethylhexyl diphenyl phosphate and di(2-ethylhexyl) phenyl phosphate containing not more than 10 molar percent of the mixture of di(2-ethylhexyl) phenyl phosphate.
4. A composition according to any of Claims 1 to 3 characterised in that the ratio by weight of the first phosphate ester component to the triphenyl phosphate in the composition is within the range 2:1 to 2.5:1.
5. A composition according to any of Claims 1 to 3 characterised in that the ratio by weight of the first phosphate ester component to the triphenyl phosphate in the composition is within the range 3:1 to 5:1.
6. A process for the production of a phosphate ester by the reaction of a phosphorus oxyhalide or an alkyl phosphorodihalidate with an alkali metal phenate., characterised in that, for the production of a liquid phosphate ester composition as defined in Claim 1, phosphorus oxyhalide is reacted with a stoichiometric excess (relative to the phosphorus oxyhalide) of an alkali metal phenate to form a mixture containing triphenyl phosphate and alkali metal phenate, and the alkali metal phenate in that mixture is reacted with a dihalidate reactant comprising at least one C6-12 alkyl phosphorodihalidate, the proportions of the reactants being selected to give a liquid phosphate ester composition containing the required proportions of the first phosphate ester component and triphenyl phosphate.
7. A process according to Claim 6, characterised in that an amount of phosphorus oxyhalide corresponding to the required amount of triphenyl phosphate is added with agitation and cooling to an aqueous solution of alkali metal phenate containing sufficient alkali metal phenate to react with the whole of the phosphorus oxyhalide and with the dihalidate reactant to be added subsequently and when the addition of the phosphorus oxyhalide is complete, the dihalidate reactant is added to the aqueous reaction mixture with agitation and cooling.
8. A process according to Claim 7, characterised in that the original amount of alkali metal phenate is from 2 to 10% more than the stoichiometric amount relative to the phosphorus oxyhalide and dihalidate reactant together.
9. A process according to either of Claims 7 and 8, characterised in that the reaction temperature during the reaction of the phosphorus oxyhalide with the alkali metal phenate and during the reaction of the dihalidate reactant with the alkali metal phenate is maintained in the range 15-30°C.
10. A process according to any of Claims 6 to 9, characterised in that the phosphorus oxyhalide is phosphorus oxychloride, the alkali metal phenate is sodium phenate, and the alkyl phosphorodihalidate is an alkyl phosphorodichloridate.
EP78300009A 1977-06-17 1978-06-01 Phosphate ester compositions and process for preparing them Expired EP0000240B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB2541677 1977-06-17
GB2541677 1977-06-17
AU37745/78A AU520571B2 (en) 1977-06-17 1978-07-04 Phosphate ester compositions

Publications (2)

Publication Number Publication Date
EP0000240A1 true EP0000240A1 (en) 1979-01-10
EP0000240B1 EP0000240B1 (en) 1983-01-12

Family

ID=25624088

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78300009A Expired EP0000240B1 (en) 1977-06-17 1978-06-01 Phosphate ester compositions and process for preparing them

Country Status (2)

Country Link
EP (1) EP0000240B1 (en)
AU (1) AU520571B2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0025720A1 (en) * 1979-09-17 1981-03-25 FMC Corporation Process for the manufacture of mixed phosphoric acid ester compositions and plasticised polymers containing them
EP4431517A1 (en) 2023-03-15 2024-09-18 LANXESS Deutschland GmbH Phosphoric acid ester compositions for flame retardant soft pvc with low volatility

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2596141A (en) * 1950-02-17 1952-05-13 Monsanto Chemicals Monoalkyl diphenyl phosphate esters
GB837680A (en) * 1955-11-08 1960-06-15 Celanese Corp Triaryl phosphate mixtures
FR1262302A (en) * 1960-07-15 1961-05-26 Socony Mobil Oll Company Process for the preparation of aryl phosphate esters
FR1502426A (en) * 1965-12-01 1967-11-18 Bush Boake Allen Ltd Resinous compositions containing triaryl phosphate
FR1567435A (en) * 1967-05-16 1969-05-16
FR2211491A1 (en) * 1972-12-20 1974-07-19 Monsanto Co

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2596141A (en) * 1950-02-17 1952-05-13 Monsanto Chemicals Monoalkyl diphenyl phosphate esters
GB837680A (en) * 1955-11-08 1960-06-15 Celanese Corp Triaryl phosphate mixtures
FR1262302A (en) * 1960-07-15 1961-05-26 Socony Mobil Oll Company Process for the preparation of aryl phosphate esters
FR1502426A (en) * 1965-12-01 1967-11-18 Bush Boake Allen Ltd Resinous compositions containing triaryl phosphate
FR1567435A (en) * 1967-05-16 1969-05-16
FR2211491A1 (en) * 1972-12-20 1974-07-19 Monsanto Co

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0025720A1 (en) * 1979-09-17 1981-03-25 FMC Corporation Process for the manufacture of mixed phosphoric acid ester compositions and plasticised polymers containing them
EP4431517A1 (en) 2023-03-15 2024-09-18 LANXESS Deutschland GmbH Phosphoric acid ester compositions for flame retardant soft pvc with low volatility
WO2024188687A1 (en) 2023-03-15 2024-09-19 Lanxess Deutschland Gmbh Phosphoric acid ester compositions for flame-retardant soft pvc with low volatility

Also Published As

Publication number Publication date
EP0000240B1 (en) 1983-01-12
AU3774578A (en) 1980-01-10
AU520571B2 (en) 1982-02-11

Similar Documents

Publication Publication Date Title
US2610978A (en) Production of halogen containing organic compounds of phosphorus
US3937765A (en) Process for preparing 0,0-diaryl n,n-dialkyl phosphoramidates
DE2329400A1 (en) ORGANIC PHOSPHATES AND THEIR USES
US3781388A (en) Phosphates
US2157164A (en) Manufacture of esters of phosphoric acid
US2728790A (en) Catalyzed process for preparation of phosphates and phosphites
JPS5822159B2 (en) Process for producing aryl esters of alkanephosphonic acids and phosphinic acids
EP0000240B1 (en) Phosphate ester compositions and process for preparing them
US3131207A (en) Derivatives of phosphonitrilic acidorthophosphoric acid anhydride and process for preparing them
US3019249A (en) Synthesis of partial esters of phosphorus acids and salts thereof
US2071017A (en) Aryl phosphoric acid halides
EP1026191A1 (en) Flame retardant compounds, process for their production and flame-retarded organic polymer materials
US2033918A (en) Liquid organo derivatives of phosphoric acid
EP0735039B1 (en) A process for preparing tribromoneopentyl chloroalkyl phosphates
US2883411A (en) Production of heterocyclic phosphoruscontaining compounds
US2875230A (en) Preparation of neutral mixed phosphates from trialkyl phosphates and alcohols
US2851476A (en) Process of making phosphates
US2852549A (en) Preparation of neutral mixed phosphates by interaction of phosphates
US2407279A (en) Method for the preparation of neutral esters of phosphoric acid
US2877260A (en) Manufacture of beta-halo-alkyl phosphites
US4288392A (en) Process for the preparation of dialkyl phosphoric acids
US2739978A (en) Dialkyl monoaryl esters of orthophosphoric acid
US4034023A (en) Process for preparing mixed phosphate ester compositions
US2650935A (en) Monoalkyl dinaphthyl phosphate esters
US2612514A (en) Production of esters of relatively strong organic and inorganic acids with aliphatic compounds having more than one carbon atom

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB SE

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB SE

ET Fr: translation filed
REF Corresponds to:

Ref document number: 2862148

Country of ref document: DE

Date of ref document: 19830217

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19840331

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19840425

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19840628

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19840630

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19890601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19890602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19890630

BERE Be: lapsed

Owner name: MONSANTO EUROPE S.A.

Effective date: 19890630

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19900228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19900301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 78300009.4

Effective date: 19900412

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT