EP2352736A1 - Verfahren zur herstellung von mono-aminofunktionalisierten dialkylphosphinsäuren, deren salze und ester und ihre verwendung - Google Patents

Verfahren zur herstellung von mono-aminofunktionalisierten dialkylphosphinsäuren, deren salze und ester und ihre verwendung

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Publication number
EP2352736A1
EP2352736A1 EP09778829A EP09778829A EP2352736A1 EP 2352736 A1 EP2352736 A1 EP 2352736A1 EP 09778829 A EP09778829 A EP 09778829A EP 09778829 A EP09778829 A EP 09778829A EP 2352736 A1 EP2352736 A1 EP 2352736A1
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EP
European Patent Office
Prior art keywords
acid
bis
mono
salts
catalyst
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Application number
EP09778829A
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German (de)
English (en)
French (fr)
Inventor
Michael Hill
Werner Krause
Martin Sicken
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Clariant International Ltd
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Clariant International Ltd
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Publication of EP2352736A1 publication Critical patent/EP2352736A1/de
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • 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
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
    • 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
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'

Definitions

  • the invention relates to a process for the preparation of monoamino-functionalized dialkylphosphinic acids, their salts and esters and their use.
  • the invention therefore relates to a process for preparing monomino-functionalized dialkylphosphinic acids, esters and salts, which comprises: a) a source of phosphinic acid (I)
  • the mono-amino-functionalized dialkylphosphinic acid obtained according to step d), its salt or ester (III) is preferably subsequently reacted in a step e) with metal compounds of Mg, Ca, Al 1 Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce 1 Bi, Sr, Mn, Li 1 Na, K and / or a protonated nitrogen base to give the corresponding monomino-functionalized dialkylphosphinic salts (III) of these metals and / or a nitrogen compound.
  • the alkylphosphonous acid obtained according to step a), its salt or ester (II) and / or the monofunctionalized dialkylphosphinic acid obtained according to step b), its salt or ester (VI) and / or the mono obtained according to step c) are preferred -functionalized dialkylphosphinic acid, its salt or ester (VII) and / or the mono-amino-functionalized dialkylphosphinic acid obtained according to step d), its salt or ester (III) and / or the respectively resulting reaction solution thereof with an alkylene oxide or an alcohol M-OH and or M'-OH esterified, and the respectively resulting Alkylphosphonigklasteder (II), monofunctionalized dialkylphosphinic (VI), monofunctionalized dialkylphosphinic (VII) and / or mono-amino-functionalized Dialkylphosphinklaester (III) the further reaction steps b), c), d) or e) subjected.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are preferably identical or different and are each independently H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and / or phenyl.
  • X is preferably H, Ca, Mg, Al, Zn, Ti, Fe, Ce, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert. Butyl, phenyl, ethylene glycol, propyl glycol, butyl glycol, pentyl glycol, hexyl glycol, allyl and / or glycerol.
  • Y is preferably hydrochloric, sulfuric, nitric or phosphoric, phosphonic, phosphinic, formic, acetic, propionic, butyric, lactic, palmitic, stearic, malonic, maleic, fumaric, tartaric, citric, ascorbic, trimethylborane, triethylborane, tributylborane and / or triphenylborane ,
  • N is preferably 0, V 4 , V 3 , V 2 , 1, 2, 3 and 4.
  • the catalyst systems A, B, C and D are preferably each formed by reaction of a transition metal and / or a transition metal compound with at least one ligand.
  • the transition metals and / or transition metal compounds of rhodium, ruthenium, nickel, palladium, platinum and / or copper are preferably acetylene, methylacetylene, 1-butyne, 1-hexyne, 2-hexyne, 1-octyne, 4-octyne, 1-butyne-4-ol, 2-butyne-1 ol, 3-butyn-1-ol, 5-hexyn-1-ol, 1-octyn-3-ol, 1-pentyne, phenylacetylene and / or trimethylsilylacetylene.
  • the hydrogen cyanide sources are preferably hydrogen cyanogen, acetone cyanohydrin, formamide and / or their alkali metal and / or alkaline earth metal salts.
  • the alcohol of the general formula M-OH is linear or branched, saturated and unsaturated, monohydric organic alcohols having a carbon chain length of Ci-Ci 8 and in the alcohol of the general formula M'-OH to linear or branched, saturated and unsaturated, polyhydric organic alcohols having a carbon chain length of C 1 -C 18 .
  • the invention also relates to the use of mono-amino-functionalized
  • the invention also relates to the use of mono-amino-functionalized dialkylphosphinic acids, salts and esters, which have been prepared according to one or more of claims 1 to 11, as flame retardants, in particular flame retardants for clearcoats and intumescent coatings, flame retardants for wood and other cellulosic products, as reactive and / or non-reactive flame retardant for polymers, for the production of flame-retardant polymer molding compositions, for the production of flame-retardant polymer moldings and / or for the flame retardant finishing of polyester and cellulose pure and mixed fabrics by impregnation.
  • flame retardants in particular flame retardants for clearcoats and intumescent coatings, flame retardants for wood and other cellulosic products, as reactive and / or non-reactive flame retardant for polymers, for the production of flame-retardant polymer molding compositions, for the production of flame-retardant polymer moldings and / or for the flame retardant finishing of polyester and cellulose pure
  • the invention also relates to a flame-retardant thermoplastic or thermosetting polymer molding composition
  • a flame-retardant thermoplastic or thermosetting polymer molding composition comprising 0.5 to 45% by weight of monoamino-functionalized dialkylphosphinic acids, salts or esters, which have been prepared according to one or more of claims 1 to 11, 0.5 to 95 %
  • thermoplastic or thermosetting polymer or mixtures thereof 0 to 55% by weight of additives and 0 to 55% by weight of filler or reinforcing materials, the sum of the components being 100% by weight.
  • the invention also relates to flameproofed thermoplastic or thermosetting polymer moldings, films, filaments and fibers containing from 0.5 to 45% by weight of monoamino-functionalized dialkylphosphinic acids, salts or esters, which are according to one or more of the claims 1 to 11, 0.5 to 95 wt .-% thermoplastic or thermosetting polymer or mixtures thereof, 0 to 55 wt .-% additives and 0 to 55 wt .-% filler or reinforcing materials, wherein the sum of the components 100 Wt .-% is.
  • step d) If the monomino-functionalized dialkylphosphinic acid (III) after step d) is an ester, acidic or basic hydrolysis may preferably be carried out in order to obtain the free monomino-functionalized dialkylphosphinic acid or its salt.
  • the target compounds to be prepared d. H. the mono-amino-functionalized dialkylphosphinic acids by 3-
  • the amino functionality of the abovementioned monoamino-functionalized dialkylphosphinic acids, their salts and esters of the formula (III) is preferably a "free" amine or forms ammonium salts with mineral acids, carboxylic acids, Lewis acids, organic acids or mixtures of these acids.
  • Preferred mineral acids are hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, phosphonic acid and phosphinic acid.
  • Preferred carboxylic acids are formic, acetic, propionic, butyric, lactic, palmitic, stearic, malonic, maleic, fumaric, tartaric, citric and ascorbic acids.
  • Preferred Lewis acids are boranes, such as diborane; Trialkylboranes such as trimethylborane, triethylborane, tributylborane and triarylboranes such as triphenylborane.
  • the transition metals for the catalyst A are preferably elements of the seventh and eighth subgroups (according to modern nomenclature a metal of group 7, 8, 9 or 10), such as rhenium, ruthenium, cobalt, rhodium, iridium, nickel, palladium and platinum.
  • the metal salts used as the source of the transition metals and transition metal compounds are those of mineral acids containing the anions fluoride, chloride, bromide, iodide, fluorate, chlorate, bromate, iodate, fluorite, chlorite, bromite, iodite, hypofluorite, hypochlorite, hypobromite, hypoiodite, perfluorate, perchlorate, perbromate, periodate, Cyanide, cyanate, nitrate, nitride, nitrite, oxide, hydroxide, borate, sulfate, sulfite, sulfide, persulfate, thiosulfate,
  • Sulfamate, phosphate, phosphite, hypophosphite, phosphide, carbonate and sulfonate such as methanesulfonate, chlorosulfonate, fluorosulfonate, trifluoromethanesulfonate, benzenesulfonate, naphthylsulfonate, toluenesulfonate, t-butylsulfonate, 2-hydroxypropanesulfonate and sulfonated ion exchange resins; and / or organic salts, such as acetylacetonates and salts of a carboxylic acid having up to 20 carbon atoms, such as formate, acetate, propionate, butyrate, oxalate, stearate and citrate, including halogenated carboxylic acids having up to 20 carbon atoms, such as trifluoroacetate, trichloroacetate ,
  • transition metals and transition metal compounds are metal salts of the transition metals with tetraphenylborate and halogenated tetraphenylborate anions, such as perfluorophenylborate.
  • Suitable salts also include double salts and complex salts consisting of one or more transition metal ions and independently one or more alkali metal, alkaline earth metal, ammonium, organic ammonium, phosphonium and organic phosphonium ions and independently one or more of the above anions.
  • Suitable double salts provide z.
  • a source of the transition metals is the transition metal as an element and / or a transition metal compound in its zero-valent state.
  • the transition metal is used metallically or used as an alloy with other metals, in which case boron, zirconium, tantalum, tungsten, rhenium, cobalt, iridium, nickel, palladium, platinum and / or gold is preferred.
  • the transition metal content in the alloy used is preferably 45-99.95% by weight.
  • the transition metal is microdispersed (particle size 0.1 mm - 100 microns) used.
  • the transition metal on a metal oxide such as alumina, silica, titania, zirconia, zinc oxide, nickel oxide, vanadium oxide, chromium oxide, magnesium oxide, Celite ®, diatomaceous earth, on a metal carbonate such as barium carbonate, calcium carbonate, strontium carbonate, on a metal sulfate such as barium sulfate, it is preferred Calcium sulfate, strontium sulfate, on a metal phosphate such as aluminum phosphate, vanadium phosphate, on a metal carbide such as silicon carbide, on a metal aluminate such as calcium aluminate, on a metal silicate such as aluminum silicate, chalks, zeolites, bentonite, montmorillonite, hectorite, on functionalized silicates, functionalized silica gels such as Silia Bond ®, QuadraSil TM, on functionalized polysiloxanes such as Deloxan ®,
  • Suitable sources of the metal salts and / or transition metals are preferably also their complex compounds.
  • Complex compounds of the metal salts and / or transition metals are composed of the metal salts or transition metals and one or more complexing agents. Suitable complexing agents are, for. For example, olefins, diolefins, nitriles, dinitriles, carbon monoxide, phosphines, diphosphines, phosphites, diphosphites, dibenzylideneacetone, cyclopentadienyl, indenyl or styrene. Suitable complex compounds of the metal salts and / or transition metals may be supported on the abovementioned support materials.
  • the content of said supported transition metals 0.01 to 20 wt .-%, preferably 0.1 to 10 wt .-%, in particular 0.2 to 5 wt .-%, based on the total mass of the support material.
  • Suitable sources of transition metals and transition metal compounds are, for example
  • the ligands are preferably phosphines of the formula (VIII)
  • kylsulfonyl -C 20 alkylsulfinyl, silyl and / or their derivatives and / or by at least one R 9 phenyl substituted by at least one R 9 are substituted naphthyl.
  • phosphines (VIII) are trimethyl, triethyl, tripropyl, triisopropyl, tributyl, triisobutyl, triisopentyl, trihexyl, tricyclohexyl, trioctyl, tridecyl, triphenyl, diphenylmethyl, phenyldimethyl, tri (o-tolyl), tri (p-tolyl), ethyldiphenyl, dicyclohexylphenyl, 2-pyridyldiphenyl, bis (6-methyl-2-pyridyl) phenyl, tri (p-chlorophenyl), tri ( p-methoxyphenyl), diphenyl (2-sulfonatophenyl) phosphine; Potassium, sodium and ammonium salts of diphenyl (3-sulfonatophenyl) phosphine, bis (4,6-dimethyl-3-s
  • the ligands are bidentate ligands of the general formula R 8 2 M "-ZM” R 8 2 (IX).
  • M independently represent N, P, As or Sb.
  • both M are the same and more preferably M "is a phosphorus atom.
  • Each group R 8 independently represents the radicals described under formula (VIII). Preferably, all groups R 8 are identical.
  • Z preferably represents a divalent bridging group which contains at least 1 bridging atom, preferably containing 2 to 6 bridging atoms.
  • Bridging atoms can be selected from C, N, O, Si, and S atoms.
  • Z is preferably an organic bridging group which is at least one
  • Z is an organic bridging group containing from 1 to 6 bridging atoms of which at least two are carbon atoms which may be unsubstituted or substituted.
  • Preferred Z groups are -CH 2 -, -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -,
  • Suitable bidentate phosphine ligands are, for example, 1, 2-bis (dimethyl), 1, 2-bis (diethyl), 1, 2-bis (dipropyl), 1, 2-bis (diisopropyl), 1, 2-bis (dibutyl), 1, 2-bis (di-tert-butyl), 1, 2-bis (dicyclohexyl) and 1, 2-bis (diphenylphosphino) ethane; 1,3-bis (dicyclohexyl), 1,3-bis (diisopropyl), 1,3-bis (di-tert-butyl) and 1,3-bis (diphenylphosphino) propane; 1,4-bis (diisopropyl) and 1,4-bis (diphenylphosphino) butane; 1, 5-bis (dicyclohexylphosphino) pentane; 1, 2-bis (di-tert-butyl), 1, 2-bis (di-phenyl), 1, 2-
  • the ligands of the formula (VIII) and (IX) can be bonded to a suitable polymer or inorganic substrate by the radicals R 8 and / or the bridging group.
  • the catalyst system has a transition metal-to-ligand molar ratio of from 1: 0.01 to 1: 100, preferably from 1: 0.05 to 1:10, and more preferably from 1: 1 to 1: 4.
  • the reactions in process stages a), b) c), d) and e) are preferably carried out optionally in an atmosphere which contains further gaseous constituents such as, for example, nitrogen, oxygen, argon, carbon dioxide; the temperature is -20 to 340 0 C, in particular 20 to 180 0 C and the total pressure 1 to 100 bar.
  • the isolation of the products and / or the transition metal compound and / or the transition metal compound and / or catalyst system and / or the ligand and / or the educts according to process steps a), b) c), d) and e) is optionally carried out by distillation or rectification , by crystallization or precipitation, by filtration or centrifugation, by adsorption or chromatography or other known methods. According to the invention, solvents, adjuvants and optionally other volatile components are replaced by, for. As distillation, filtration and / or extraction.
  • the reactions in the process stages a), b) c), d) and e) optionally in absorption columns, spray towers, bubble columns, stirred tanks, trickle bed reactor, Strömumgsrohren, loop reactors and / or kneaders.
  • Suitable mixing devices are z. As anchor, blade, MIG, propeller, impeller, turbine, cross-stirrer, dispersing, hollow (gassing) - stirrer, rotor-stator mixers, static mixers, Venturi nozzles and / or lift pumps.
  • reaction solutions / mixtures preferably have a mixing intensity which corresponds to a rotational Reynolds number of from 1 to 1,000,000, preferably from 100 to 100,000.
  • an intensive mixing of the respective reactants, etc. takes place under an energy input of 0.080 to 10 kW / m 3 , preferably 0.30 to 1.65 kW / m 3 .
  • the particular catalyst A, B, C or D preferably acts homogeneously and / or heterogeneously during the reaction. Therefore, the heterogeneous catalyst acts during the reaction as a suspension or bound to a solid phase.
  • the respective catalyst A, B, C or D before, generated in situ at the beginning and / or during the reaction.
  • the particular reaction is preferably carried out in a solvent as a one-phase system in homogeneous or heterogeneous mixture and / or in the gas phase.
  • phase transfer catalyst can additionally be used.
  • the reactions according to the invention can be carried out in the liquid phase, in the gas phase or else in the supercritical phase.
  • the particular catalyst A, B, C or D is preferably used for liquids in a homogeneous or suspension, while in gas-phase or supercritical driving a fixed bed arrangement is advantageous.
  • Suitable solvents are water, alcohols such. Methanol, ethanol, i-propanol, n-propanol, n-butanol, i-butanol, t-butanol, n-amyl alcohol, i-amyl alcohol, t-amyl alcohol, n-hexanol, n-octanol, i-octanol, n-tridecanol, benzyl alcohol, etc.
  • Preference is furthermore given to glycols such as. For example, ethylene glycol,
  • aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and petroleum ether, petroleum benzine, kerosene, petroleum, paraffin oil, etc .
  • aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, etc .
  • Halogenated hydrocarbons such as methylene chloride, chloroform, 1, 2-dichloroethane, chlorobenzene, carbon tetrachloride, tetrabromoethylene, etc .
  • alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, etc .
  • Ethers such as ani
  • Diethylene glycol diethyl ether diethylene glycol dimethyl ether (diglyme), diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 1,2-dimethoxyethane (DME monoglyme), ethylene glycol monobutyl ether, triethylene glycol dimethyl ether (triglyme), triethylene glycol monomethyl ether, etc .; Ketones such as acetone, diisobutyl ketone, methyl n-propyl ketone; Methyl ethyl ketone, methyl i-butyl ketone, etc .; Esters such as methyl formate, methyl acetate, ethyl acetate, n-propyl acetate and n-butyl acetate, etc .; Carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, etc .; individually or in combination with each other.
  • Suitable solvents are also the olefins and phosphinic acid sources used. These offer advantages in terms of a higher space-time yield.
  • the reaction is carried out under its own vapor pressure of the olefin and / or the solvent.
  • R 1 , R 2 , R 3 , R 4 of the olefin (IV) are the same or different and are independently H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and / or phenyl.
  • olefins such as allyl isothiocyanate, allyl methacrylate, 2-allylphenol, N-allylthiourea, 2- (allylthio) -2-thiazoline, allyltrimethylsilane, allyl acetate, allylacetoacetate, allyl alcohol, allylamine, allylbenzene, allyl cyanide, allyl (cyanoacetate), allylanisole, trans-2-pentenal, cis-2-pentenenitrile, 1-penten-3-ol, 4-penten-1-ol, 4-penten-2-ol, trans-2-hexenal, trans-2-hexene-i ol, cis-3-hexene-1-ol, 5-hexene-1-ol, styrene, methylstyrene, 4-methylstyrene, vinyl acetate, 9-vinylanthracene, 2-vinylpyr
  • the reaction preferably takes place at a partial pressure of the olefin of 0.01-100 bar, more preferably at a partial pressure of the olefin of 0.1-10 bar.
  • the reaction is carried out in a phosphinic-olefin molar ratio of 1: 10,000 to 1: 0.001, more preferably in the ratio of 1: 30 to 1: 0.01.
  • the reaction preferably takes place in a phosphinic acid catalyst molar ratio of 1: 1 to 1: 0.00000001, more preferably 1: 0.01 to 1: 0.000001.
  • the reaction preferably takes place in a phosphinic acid / solvent molar ratio of 1: 10,000 to 1: 0, more preferably 1:50 to 1: 1.
  • a process according to the invention for the preparation of compounds of the formula (II) is characterized in that a phosphinic acid source is reacted with olefins in the presence of a catalyst and the resulting alkylphosphonous acid, esters or salts (II) of catalyst, transition metal, Transition metal compound, ligand, complexing agent, salts and by-products is released.
  • the catalyst, the catalyst system, the transition metal and / or the transition metal compound is separated by adding an adjuvant 1 and removing the catalyst, the catalyst system, the transition metal and / or the transition metal compound by extraction and / or filtration.
  • the ligand and / or complexing agent is separated by extraction with an adjuvant 2 and / or distillation with an adjuvant 2.
  • Auxiliary 1 is preferably water and / or at least one member of the family of metal scavengers.
  • Preferred metal scavengers are metal oxides such as alumina, silica, titania, zirconia, zinc oxide, nickel oxide, vanadium oxide, chromium oxide, magnesium oxide, Celite ®, diatomaceous earth;
  • Metal carbonates such as barium carbonate, calcium carbonate, strontium carbonate; Metal sulfates such as barium sulfate, calcium sulfate, strontium sulfate; Metal phosphates such as aluminum phosphate, vanadium phosphate, metal carbides such as silicon carbide; Metal aluminates such as calcium aluminate; Metal silicates such as aluminum silicate, chalks, zeolites, bentonite, montmorillonite, hectorite; functionalized silicates, functionalized silica gels, such as Silia Bond ®, QuadraSil TM; Polysiloxanes such as Deloxan ®; Metal nitrides, carbon, activated carbon, mullites, bauxites, antimonyites, scheelites, perovskites, hydrotalcites, functionalized and unfunctionalized cellulose, chitosan, keratin, heteropolyanions, ion exchangers such as Amberlite TM
  • auxiliary agent 1 is preferably added in
  • the auxiliary 1 is preferably used at temperatures of 20-90 ° C.
  • the residence time of adjuvant 1 is preferably 0.5 to 360 minutes.
  • Auxiliaries 2 are preferably the abovementioned solvents according to the invention, as are preferably used in process step a).
  • esterification of the mono-amino-functionalized dialkylphosphinic acid (III) or the monofunctionalized dialkylphosphinic acid (VII) or the monofunctionalized dialkylphosphinic acid (VI) or the alkylphosphonous acid derivatives (II) and the phosphinic acid source (I) to give the corresponding esters can be carried out, for example Reaction with higher boiling alcohols with removal of the water formed by azeotropic distillation or by reaction with epoxides (alkylene oxides) can be achieved.
  • the alkylphosphonous acid (II) is directly esterified with an alcohol of the general formula M-OH and / or M'-OH or by reaction with alkylene oxides, as indicated below.
  • M-OH are primary, secondary or tertiary alcohols having a carbon chain length of CrCl 8 .
  • M'-OH ethylene glycol 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 2,2-dimethylpropane-1, 3-diol, neopentyl glycol, 1, 6-hexanediol, 1, 4-cyclohexane-dimethanol, glycerol, trishydroxymethylethane, trishydroxymethylpropane, pentaerythritol, sorbitol, mannitol, ⁇ -naphthol,
  • Polyethylene glycols, polypropylene glycols and / or EO-PO block polymers are also suitable as M-OH and M'-OH.
  • mono- or polyhydric, unsaturated alcohols having a carbon chain length of C 1 -C 18 such as n-buten-2-ol-1, 1, 4-butenediol and allyl alcohol.
  • M-OH and M'-OH are reaction products of monohydric alcohols with one or more molecules of alkylene oxides, preferably with ethylene oxide and / or 1, 2-propylene oxide.
  • reaction products of monohydric alcohols with one or more molecules of alkylene oxides preferably with ethylene oxide and / or 1, 2-propylene oxide.
  • M-OH and M'-OH are also preferably reaction products of polyhydric alcohols with one or more molecules of alkylene oxide, in particular diglycol and triglycol, and adducts of 1 to 6 molecules of ethylene oxide or propylene oxide with glycerol, trishydroxymethylpropane or pentaerythritol.
  • reaction products of water with one or more molecules of alkylene oxide Preference is given to polyethylene glycols and poly-1, 2-propylene glycols of various molecular sizes having an average molecular weight of 100-1000 g / mol, more preferably of 150-350 g / mol.
  • M-OH and M'-OH are reaction products of ethylene oxide with poly-1, 2-propylene glycols or fatty alcohol propylene glycols; also reaction products of 1,2-propylene oxide with polyethylene glycols or
  • Fatty alcohol ethoxylates Preference is given to those reaction products having an average molecular weight of 100-1000 g / mol, more preferably of 150-450 g / mol.
  • reaction products of alkylene oxides with ammonia, primary or secondary amines, hydrogen sulfide, mercaptans, oxygen acids of phosphorus and C 2 -C 6 -dicarboxylic acids are also suitable as M-OH and M'-OH.
  • reaction products of ethylene oxide with Nitrogen compounds are triethanolamine, methyldiethanolamine, n-butyldiethanolamine, n-dodecyl-diethanolamine, dimethylethanolamine, n-butyl-methyl-ethanolamine, di-n-butyl-ethanolamine, n-dodecylmethyl-ethanolamine, tetrahydroxyethyl-ethylenediamine or pentahydroxyethyl-diethylenetriamine.
  • Preferred alkylene oxides are ethylene oxide, 1, 2-propylene oxide, 1, 2-epoxybutane,
  • Suitable solvents are the solvents mentioned in process step a) and also the alcohols M-OH, M'-OH and the alkylene oxides used. These offer advantages in terms of a higher space-time yield.
  • the reaction is preferably carried out under its own vapor pressure of the alcohol M-OH, M'-OH and alkylene oxide used and / or of the solvent.
  • the reaction preferably takes place at a partial pressure of the alcohol M-OH, M'-OH and alkylene oxide used of 0.01 to 100 bar, more preferably at a partial pressure of the alcohol of 0.1 to 10 bar.
  • the reaction is preferably carried out at a temperature of -20 to 340 ° C., more preferably at a temperature of 20 to 180 ° C.
  • the reaction takes place at a total pressure of 1 to 100 bar.
  • the reaction preferably takes place in a molar ratio of the alcohol or alkylene oxide component to the phosphinic acid source (I) or alkylphosphonous acid (II) or monofunctionalized dialkylphosphinic acid (VI) or monofunctionalized dialkylphosphinic acid (VII) or monomino-functionalized dialkylphosphinic acid (II).
  • III of 10,000: 1 to 0.001: 1, more preferably in the ratio of 1000: 1 to 0.01: 1.
  • the reaction preferably takes place in a molar ratio of the phosphinic acid source (I) or alkylphosphonous acid (II) or monofunctionalized dialkylphosphinic acid (VI) or monofunctionalized dialkylphosphinic acid (VII) or monoamino-functionalized dialkylphosphinic acid (III) Solvent of 1: 10,000 to 1: 0, more preferably in a phosphinic solvent molar ratio of 1:50 to 1: 1.
  • Catalyst B as used for process step b) for the reaction of alkylphosphonous acid, its salts or esters (II) with an acetylenic compound (V) to give monofunctionalized dialkylphosphinic acid, its salts and esters (VI), may preferably be Catalyst A be.
  • R 5 and R 6 are preferably independently of each other and represent H and / or CrC ⁇ -alkyl, C 6 -C 8 -aryl and / or C 7 -C 2 o-alkylaryl (optionally substituted).
  • R 5 and R 6 are H, methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, phenyl, naphthyl , ToIyI, 2-phenylethyl, 1-phenylethyl, 3-phenyl-propyl and / or 2-phenylpropyl.
  • acetylenic compounds preference is given to acetylene, methylacetylene, 1-butyne, 1-hexyne, 2-hexyne, 1-octyne, 4-octyne, 1-butyne-4-ol, 2-butyne-1-ol, 3-butyne-1 -ol, 5-hexyn-1-ol, 1-octyn-3-ol, 1-pentyne, phenylacetylene and / or trimethylsilylacetylene used.
  • the reaction is preferably carried out in the presence of a phosphinic acid of the formula (X),
  • R 11 and R 12 are each independently of the other CrC 2 o-alkyl, C 7 -C 2 o-aryl or C 7 -C 2 o-alkaryl, optionally substituted.
  • R 11 and R 12 are each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, ToIyI or XyIyI (substituted if necessary).
  • the proportion of phosphinic acid (X), based on the alkylphosphonous acid (II) used, is preferably from 0.01 to 100 mol%, particularly preferably from 0.1 to 10 mol%.
  • the reaction takes place at temperatures of 30 to 120 0 C and particularly preferably at 50 to 90 0 C; the reaction time is 0.1 to 20 hours.
  • the reaction is carried out under its own vapor pressure of the acetylenic compound (V) and / or the solvent.
  • Suitable solvents for process step b) are those which are used further in process step a).
  • the reaction preferably takes place at a partial pressure of the acetylenic compound of 0.01-100 bar, more preferably 0.1-10 bar.
  • the ratio of acetylenic compound (V) to alkylphosphonous acid (II) is 10,000: 1 to 0.001: 1, more preferably 30: 1 to 0.01: 1.
  • the reaction preferably takes place in an alkylphosphonous acid catalyst molar ratio of 1: 1 to 1: 0.00000001, more preferably in an alkylphosphonous acid catalyst molar ratio of 1: 0.01 to 1: 0.000001.
  • the reaction preferably takes place in an alkylphosphonous acid solvent molar ratio of 1: 10,000 to 1: 0, more preferably in an alkylphosphonous acid solvent molar ratio of 1:50 to 1: 1.
  • the reaction described in step c) is achieved by hydrocyanation of the monofunctionalized dialkylphosphinic acid (VI) by hydrogen cyanide or a hydrogen cyanide source in the presence of a catalyst C.
  • Catalyst C as it is for process step c) for the reaction of the monofunctionalized dialkylphosphinic acid derivative (VI) with hydrogen cyanide or a hydrogen cyanide source to give the monofunctionalized dialkylphosphinic acid derivative (VII), may preferably be catalyst A or derived from a metal from the first subgroup.
  • the transition metal for the catalyst C is preferably palladium, copper or nickel.
  • transition metals and transition metal compounds listed under Catalyst A, the following transition metals and transition metal compounds can also be used:
  • Diisopropylphenylphosphonit Dimethylphenyl, diisopropylphenyl, ethyldiphenyl and methyldiphenylphosphinite.
  • the transition metals are used in their zerovalent state.
  • transition metal salts can be used in the presence of a reducing agent as a catalyst.
  • a reducing agent is borohydrides, metal borohydrides, aluminum hydrides, metal aluminum hydrides, metal alkyls, zinc, iron, aluminum, sodium and hydrogen.
  • the hydrocyanation reaction is carried out in the presence of a promoter I.
  • Preferred promoters I are Lewis acids.
  • metal salts preferably metal halides, such as fluorides, chlorides, bromides, iodides; sulfates, Sulfonates, haloalkylsulfonates, perhaloalkylsulfonates such as fluoroalkylsulfonates or perfluoroalkylsulfonates; Haloacetates, perhaloacetates, carboxylates and phosphates such as PO 4 3 " , HPO 4 2 ' , H 2 PO 4 ' , CF 3 COO " , C 7 Hi 5 OSO 2 " or SO 4 2" preferred.
  • Suitable Lewis acids are preferably inorganic or organic metal compounds in which the cation is selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium , Zirconium, niobium, molybdenum, cadmium, rhenium, beryllium, gallium, indium, thallium, hafnium, erbium, germanium, tungsten, palladium, thorium, and tin.
  • Examples include ZnBr 2 , ZnI 2 , ZnCb, ZnSO 4 , CuCl 2 , CuCl, CU (O 3 SCF 3 ) 2 , CoCl 2 , CoI 2 , FeI 2 , FeCl 3 , FeCl 2 , FeCl 2 (THF) 2 , TiCl 4 (THF) 2 , TiCl 4 , TiCl 3 , CITi (Oi-propyl) 3 , Ti (OMe) 4 , Ti (OEt) 4 , Ti (OJ-Pr) 4 , Ti (On-Pr) 4 , MnCl 2 , ScCl 3 , AICI 3 , (C 8 Hi 7 ) AICI 2 , (C 8 H 17 ) 2 AICI, (i -C 4 Hg) 2 AICI, (C 6 Hs) 2 AICI, (C 6 H 5 ) AICI 2 , Al (OMe) 3 , Al (OEt) 3 ,
  • organometallic compounds such as (C 6 Hs) 3 SnX 2 with X being CF 3 SO 3 , CH 3 C 6 H 4 SO 3 ; RAICI 2 , R 2 AICI, R 3 Al, (RO) 3 Al, R 3 TiCl, (RO) 4 Ti, RSnO 3 SCF 3 , R 3 B and B (OR) 3 , wherein R is selected from H 1 C 1 -Ci 2 -
  • the ratio of promoter I to catalyst C is preferably about 0.1: 1 to 50: 1, more preferably about 0.5: 1 to 1.2: 1.
  • Suitable alkali salts of hydrogen cyanide sources are, for. B. NaCN, KCN, etc.
  • Suitable solvents are those as used further in process step a).
  • the proportion of catalyst C based on the monofunctionalized dialkylphosphinic acid used is preferably 0.00001 to 20 mol%, more preferably 0.00001 to 5 mol%.
  • the reaction takes place at temperatures of 30 to 200 0 C and more preferably at 50 to 120 0 C.
  • the reaction time is preferably 0.1 to 20 hours.
  • the process step c) is preferably carried out at an absolute pressure of 0.1 to 100 bar, preferably at 0.5 to 10 bar, in particular at 0.8 to 1, 5 bar.
  • the reaction is carried out under the vapor pressure of the cyanogen hydrogen and / or the solvent.
  • the reaction preferably takes place at a partial pressure of the hydrogen cyanide of 0.01 to 20 bar, more preferably 0.1 to 1.5 bar.
  • the ratio of hydrogen cyanide to dialkylphosphinic acid (II) is preferably from 10,000: 1 to 0.001: 1, more preferably from 30: 1 to 0.01: 1.
  • the reaction preferably takes place in a dialkylphosphinic acid catalyst molar ratio of 1: 1 to 1: 0.00000001, more preferably in a dialkylphosphinic acid catalyst molar ratio of 1: 0.01 to 1: 0.000001.
  • the reaction preferably takes place in a dialkylphosphinic acid solvent molar ratio of 1: 10,000 to 1:10, particularly preferably in a dialkylphosphinic acid solvent molar ratio of 1:50 to 1: 1.
  • the hydrocyanation according to the invention can be carried out in the liquid phase, in the gas phase or in the supercritical phase, wherein the catalyst at Liquid is used homogeneously or as a suspension, while in gas-phase or supercritical driving a fixed bed arrangement is advantageous.
  • the process according to the invention is carried out continuously.
  • the process according to the invention is carried out in the liquid phase. Therefore, the pressure in the reactor is preferably adjusted so that the reactants are in liquid form under the reaction temperature used. Furthermore, it is preferred that the hydrogen cyanide is used in liquid form.
  • one or more reactors may be used, which are preferably connected in series using multiple reactors.
  • step d) is carried out by hydrogenating the monofunctionalized dialkylphosphinic acid, its salts and esters (VII) by means of selective hydrogenation by a reducing agent or catalytically by hydrogen in the presence of a catalyst D and optionally an amine and a promoter (II). reached.
  • Preferred reducing agents are metal hydrides, borohydrides, metal borohydrides, aluminum hydrides and metal aluminum hydrides.
  • Examples of preferred reducing agents are decaborane, diborane, diisobutylaluminum hydride,
  • the reaction preferably takes place in a dialkylphosphinic acid reducing agent molar ratio of from 1:10 to 1: 0.1, particularly preferably in a dialkylphosphinic acid reducing agent molar ratio of from 1: 2 to 1: 0.25.
  • the preferred catalytic hydrogenation is carried out by means of hydrogen in the presence of a catalyst D and optionally an amine and / or a promoter (II).
  • the catalyst D as it is for the process step d) for the reaction of the monofunctionalized dialkylphosphinic acid derivative (VII) with hydrogen and optionally a promoter to the mono-amino-functionalized dialkylphosphinic acid derivative (III), may preferably be the catalyst A.
  • the ligands and bidentate ligands listed under Catalyst C can also be used.
  • the proportion of catalyst D based on the monofunctionalized dialkylphosphinic acid (VII) used is preferably 0.00001 to 20 mol%, more preferably 0.0001 to 10 mol%.
  • the hydrogenation reaction preferably takes place in the presence of an amine.
  • Preferred amines are ammonia, monoamines, diamines, higher amines and the mono-amino-functionalized dialkylphosphinic acid, its salt or ester itself.
  • Preferred monoamines are, for example, amines of the formula R '- NH 2 , where R' is Cr 2 o-alkyl, linear or branched.
  • Preferred monoamines are methylamine, ethylamine, propylamine, i-propylamine, butylamine, i-butylamine, pentylamine and 2-ethylhexylamine.
  • Preferred diamines are amines of the formula H 2 NR "-NH 2 , where R" is ci- 2 o-alkyl, linear or branched. Preference is given to ethylenediamine, propylenediamine, diaminobutane, pentamethylenediamine and hexamethylenediamine.
  • the partial pressure of the ammonia is preferably 0.01 to 100 bar, more preferably 0.05 to 50 bar, in particular 0.1 to 20 bar.
  • the concentration of ammonia in the reaction mixture is 1 to 30 wt .-%, particularly preferably 5 to 25 wt .-%.
  • the concentration of monoamine and / or diamine in the reaction mixture is 1 to 80 wt .-%, particularly preferably 5 to 60 wt .-%.
  • the hydrogenation reaction is preferably carried out in the presence of a promoter (II), preference being given as promoters (II) to alkali metal and alkaline earth metal hydroxides and alcoholates.
  • promoters (II) are NaOH, KOH, Mg (OH) 2 , Ca (OH) 2 , Ba (OH) 2 and sodium or potassium methoxide,
  • the ratio of promoter (II) to catalyst is about 0.001: 1 to 0.5: 1, preferably about 0.01: 1 to 0.2: 1, more preferably 0.04: 1 to 0.1: 1.
  • At least part of the promoter and, secondly, the amine are added to the catalyst and / or the solution / suspension containing the catalyst.
  • at least 10 wt .-%, preferably 20 wt .-% and particularly preferably 50 wt .-% of the promoter (II) is added first.
  • the transition metals are used in their zerovalent state.
  • the heterogeneous catalyst D acts during the reaction as a suspension or bound to a solid phase.
  • the reaction is preferably carried out in a solvent as a one-phase system in homogeneous or heterogeneous mixture and / or in the gas phase.
  • Suitable solvents are those as used further in process step a).
  • the reaction preferably takes place in a dialkylphosphinic acid solvent molar ratio of 1: 10,000 to 1: 0, more preferably in a dialkylphosphinic acid solvent molar ratio of 1:50 to 1: 1.
  • the reaction is carried out at temperatures of 20 to 200 0 C and more preferably from 40 to 150 0 C, in particular from 60 to 100 0 C.
  • the reaction time is preferably 0.1 to 20 hours.
  • the reaction is preferably carried out under the partial pressure of the hydrogen and / or of the solvent.
  • the process step of the process according to the invention is preferably carried out at a partial pressure of the hydrogen of 0.1 to 100 bar, particularly preferably 0.5 to 50 bar, in particular 1 to 20 bar.
  • the process step of the process according to the invention is preferably carried out at an absolute pressure of 0.1 to 150 bar, more preferably 0.5 to 70 bar, in particular 1 to 30 bar.
  • the hydrogenation according to the invention can be carried out in the liquid phase, in the gas phase or else in the supercritical phase.
  • the catalyst is preferably used homogeneously or as a suspension, while a fixed-bed arrangement is advantageous in the case of gas-phase or supercritical operation.
  • the mono-amino-functionalized dialkylphosphinic acid or its salt (III) can be subsequently converted into further metal salts.
  • the metal compounds used in process step e) are preferably compounds of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr 1 Zn, Ce, Bi, Sr, Mn, Li, Na, K particularly preferably Ca, Al, Ti, Zn, Sn, Ce, Fe.
  • Suitable solvents for process step e) are those which are used further up in process step a).
  • the reaction preferably takes place in process stage e) in an aqueous medium.
  • process stage e) the obtained according to process stage d) obtained mono-amino-functionalized dialkylphosphinic acids, their esters and / or alkali metal salts (III) with metal compounds of Mg, Ca, Al, Zn, Ti, Sn 1 Zr, Ce or Fe to the mono-amino-functionalized dialkylphosphinic salts (III) of these metals.
  • the reaction takes place in a molar ratio of monomino-functionalized dialkylphosphinic acid / ester / salt (III) to metal of 8: 1 to 1: 3 (for tetravalent metal ions or metals having a stable tetravalent oxidation state) of from 6: 1 to 1 3 (for trivalent metal ions or metals with stable trivalent oxidation state), from 4 to 1 to 1 to 3 (for divalent
  • Metal ions or metals with stable divalent oxidation state and from 3 to 1 to 1 to 4 (for monovalent metal ions or metals with stable monovalent oxidation state).
  • process stage d) obtained mono-amino-functionalized DialkylphosphinklarAsalz (III) in the corresponding dialkylphosphinic and sets in process stage e) with metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe to the mono -amino-functionalized dialkylphosphinic salts (III) of these metals.
  • the monomino-functionalized dialkylphosphinic acid ester (III) obtained in process step d) is preferably converted into a dialkylphosphinic alkali metal salt and used in process stage e) with this Metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe to the mono-amino-functionalized dialkylphosphinic (IM) salts of these metals.
  • the metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe for process stage e) are preferably metals, metal oxides, hydroxides,
  • the metal compounds are preferably aluminum chloride, aluminum hydroxide, aluminum nitrate, aluminum sulfate, titanyl sulfate, zinc nitrate, zinc oxide, zinc hydroxide and / or zinc sulfate.
  • metallic aluminum aluminum fluoride, hydroxychloride, bromide, iodide, sulfide, selenide; phosphide, hypophosphite, antimonide, nitride; carbide, hexafluorosilicate; hydride, calcium hydride, borohydride; chlorate; Sodium aluminum sulfate, aluminum potassium sulfate, aluminum ammonium sulfate, nitrate, metaphosphate, phosphate, silicate, magnesium silicate, carbonate, hydrotalcite, sodium carbonate, borate; thiocyanate; oxide, oxyhydroxide, their corresponding hydrates and / or polyaluminum hydroxy compounds, which preferably have an aluminum content of 9 to 40 wt .-%.
  • Aluminum salts of mono-, di-, oligo-, polycarboxylic acids such as. Aluminum diacetate, acetoacetate, formate, lactate, oxalate, tartrate, oleate, palmitate, stearate, trifluoromethanesulfonate, benzoate, salicylate, 8-oxyquinolate.
  • zinc halides zinc fluoride, zinc chlorides, zinc bromide, zinc iodide
  • zinc borate carbonate, hydroxide carbonate, silicate, hexafluorosilicate, stannate, hydroxide stannate, magnesium aluminum hydroxide carbonate; nitrate, nitrite, phosphate, pyrophosphate; sulphate, phosphide, selenide, telluride and zinc salts of the oxo acids of the seventh main group (hypohalites, halides, halogenates, eg zinc iodate, perhalates, eg zinc perchlorate); Zinc salts of pseudohalides (zinc thiocyanate, cyanate, cyanide); Zinc oxides, peroxides, hydroxides or mixed zinc oxide hydroxides.
  • zinc salts of the oxo acids of the transition metals for example zinc chromate (VI) hydroxide, chromite, molybdate, permanganate, molybdate.
  • zinc salts of mono-, di-, oligo-, polycarboxylic acids such as. B. zinc formate, acetate, trifluoroacetate, propionate, butyrate, valerate, caprylate, oleate, stearate, oxalate, tartrate, citrate, benzoate, salicylate, lactate, acrylate, maleate, succinate, salts of amino acids (glycine), acidic hydroxy functions (zinc phenolate, etc.), zinc p-phenolsulfonate, acetylacetonate, stannate, dimethyldithiocarbamate, trifluoromethanesulfonate.
  • Titanium compounds include metallic titanium as well as titanium (III) and / or (IV) chloride, nitrate, sulfate, formate, acetate, bromide, fluoride, oxychloride,
  • oxysulfate oxide, n-propoxide, n-butoxide, isopropoxide, ethoxide, 2-ethylhexyl oxide.
  • metallic tin and the tin salts tin (II) and / or (IV) chloride
  • Tin oxides and tin alkoxide such.
  • Tin (IV) tert-butoxide is also suitable.
  • cerium (III) fluoride is also suitable.
  • chloride is also suitable.
  • nitrate is also suitable.
  • zirconium compounds metallic zirconium and zirconium salts such as zirconium chloride, sulfate, zirconyl acetate, zirconyl chloride are preferred. Further preferred are zirconium oxides and zirconium (IV) tert-butoxide.
  • the reaction in process stage e) preferably takes place at a solids content of the monomino-functionalized dialkylphosphinic salts (III) of from 0.1 to 70% by weight, preferably from 5 to 40% by weight.
  • the reaction is carried out in process stage e) at a temperature of 20 to 250 0 C, preferably at a temperature of 80 to 120 0 C.
  • the reaction preferably takes place in process stage e) at a pressure between 0.01 and 1000 bar, preferably 0.1 to 100 bar.
  • the reaction preferably takes place in process stage e) during a reaction time of 1 * 10 -7 to 1 * 10 2 h.
  • the monomino-functionalized dialkylphosphinic acid salt (III) removed by filtration and / or centrifuging from the reaction mixture is preferably dried after process stage e).
  • the product mixture obtained after process step d) is reacted with the metal compounds without further purification.
  • Preferred solvents are the solvents mentioned in process step a).
  • reaction in process stage d) and / or e) is preferably in the solvent system given by stage a), b) and / or c).
  • reaction in process stage e) is preferably in a modified solvent system.
  • acidic components, solubilizers, foam inhibitors, etc. are added.
  • the product mixture obtained after process stage a), b), c) and / or d) is worked up.
  • the product mixture obtained after process stage d) is worked up and then the mono-amino-functionalized dialkylphosphinic acids and / or their salts or esters (III) obtained in process stage d) are reacted with the metal compounds in process stage e).
  • the product mixture is worked up according to process stage d) by isolating the mono-amino-functionalized dialkylphosphinic acids and / or their salts or esters (III) by removing the solvent system, for. B. by evaporation.
  • the monomino-functionalized dialkylphosphinic acid salt (III) of the metals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe preferably has a residual moisture content of from 0.01 to 10% by weight, preferably from 0.1 to 1 wt .-%; an average particle size of 0.1 to 2000 microns, preferably from 10 to 500 microns; a bulk density of 80 to 800 g / l, preferably from 200 to 700 g / l and a pourability of Pfrengle from 0.5 to 10, preferably from 1 to 5, on.
  • the amino functionality of the mono-amino-functionalized dialkylphosphinic acids, their salts and esters of the formula (III) can be reacted with mineral acids, carboxylic acids, Lewis acids, organic acids or mixtures of these acids to form further ammonium salts.
  • the reaction preferably takes place at a temperature of 0 to 150 ° C., more preferably at a temperature of 20 to 70 ° C.
  • Suitable solvents are those as used further in process step a).
  • Preferred mineral acids are hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid and phosphinic acid.
  • Preferred carboxylic acids are formic, acetic, propionic, butyric, lactic, palmitic, stearic, malonic, maleic, fumaric, tartaric, citric and ascorbic acids.
  • Preferred Lewis acids are boranes such as diborane, trialkylboranes such as trimethylborane, triethylborane, tributylborane, triarylboranes such as triphenylborane.
  • ammonium salts are particularly preferably salts of the abovementioned monoamino-functionalized dialkylphosphinic acids (IM), their salts and esters with hydrochloric acid, phosphoric acid, phosphonic acid, phosphinic acid, acetic acid, citric acid, ascorbic acid or triphenylborane.
  • IM monoamino-functionalized dialkylphosphinic acids
  • the shaped bodies, films, threads and fibers particularly preferably contain 5 to 30% by weight of the monomino-functionalized dialkylphosphinic acid / ester / salts prepared according to one or more of claims 1 to 11, 5 to 90% by weight.
  • the additives are preferably antioxidants, antistatics, blowing agents, other flame retardants, heat stabilizers, impact modifiers, process aids, lubricants, light stabilizers, anti-dripping agents, compatibilizers, reinforcing agents, fillers, nucleating agents, nucleating agents, additives for laser marking,
  • Hydrolysis stabilizers Hydrolysis stabilizers, chain extenders, color pigments, plasticizers and / or plasticizers.
  • a flame retardant containing from 0.1 to 90% by weight of the monomino-functionalized dialkylphosphinic acids, esters and salts (III) and from 0.1 to 50% by weight of further additives, particularly preferably diols.
  • Preferred additives are also aluminum trihydrate, antimony oxide, brominated aromatic or cycloaliphatic hydrocarbons, phenols, ethers, chloroparaffin, hexachlorocyclopentadiene adducts, red phosphorus, melamine derivatives, melamine cyanurates, ammonium polyphosphates and magnesium hydroxide.
  • Preferred additives are also other flame retardants, in particular salts of dialkylphosphinic acids.
  • the invention relates to the use of the inventive mono-amino-functionalized dialkylphosphinic acids, esters and salts (III) as flame retardants or as an intermediate for the preparation of
  • thermoplastic polymers such as polyester, polystyrene or polyamide
  • thermosetting polymers such as unsaturated polyester resins, epoxy resins, polyurethanes or acrylates.
  • Suitable polyesters are derived from dicarboxylic acids and their esters and diols and / or from hydroxycarboxylic acids or the corresponding lactones. Particularly preferred are terephthalic acid and ethylene glycol, propane-1, 3-diol, butane-1, 3-diol used.
  • Suitable polyesters include polyethylene terephthalate, polybutylene terephthalate (Celanex ® 2500, Celanex ® 2002, from Celanese;. Ultradur ®, BASF), poly-1, 4- dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and also block polyether esters derived from polyethers having hydroxyl end groups; also with polycarbonates or MBS (methyl methacrylate-butadiene-styrene) modified polyester.
  • Dicarboxylic acid and diols initially esterified directly and then polycondensed.
  • dicarboxylic acid esters in particular dimethyl esters, it is first transesterified and then polycondensed using the customary catalysts.
  • conventional additives crosslinking agents, matting and stabilizing agents, nucleating agents, dyes and fillers, etc. may preferably be added during polyester production.
  • the esterification and / or transesterification takes place in the polyester production at temperatures of 100-300 ° C., more preferably 150-250 ° C.
  • the polycondensation takes place in the polyester production at pressures between 0.1 to 1, 5 mbar and temperatures of 150 to 450 0 C, more preferably at 200 - 300 0 C.
  • the flame-retardant polyester molding compositions prepared according to the invention are preferably used in polyester moldings.
  • Preferred polyester moldings are threads, fibers, films and moldings which contain as the dicarboxylic acid component mainly terephthalic acid and as the diol component mainly ethylene glycol.
  • the resulting phosphorus content in threads and fibers produced from flame-retardant polyester is preferably 0.1-18% by weight, preferably 0.5-15% by weight, and in the case of films 0.2-15% by weight, preferably 0.9 - 12 wt .-%.
  • Suitable polystyrenes are polystyrene, poly (p-methylstyrene) and / or poly (alphamethylstyrene).
  • the suitable polystyrenes are copolymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, such as. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Blends of high impact strength of styrene copolymers and another polymer, such as.
  • styrene such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.
  • the suitable polystyrenes are also graft copolymers of styrene or alpha-methylstyrene, such as. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile
  • Copolymers styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof, such as they z. B. as so-called ABS, MBS, ASA or AES
  • the polymers are preferably polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 2,12, polyamide 4, polyamide 4,6, polyamide 6, polyamide 6,6 , Polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 6,66, polyamide 7,7, polyamide 8,8, polyamide 9,9, polyamide 10,9, polyamide 10,10, polyamide 11, polyamide 12, etc.
  • Such polyamides are z. B under the tradename Nylon ®, DuPont, Ultramid ®, BASF, Akulon ® K122, from DSM, Zytel ® 7301, from DuPont....; Durethan ® B 29, Messrs. Bayer and Grillamid® ®, Fa. Ems Chemie.
  • aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally an elastomer as a modifier, for.
  • the mono-amino-functionalized dialkylphosphinic acid / ester / salts prepared according to one or more of claims 1 to 11 are preferably used in
  • Molding compounds used which are further used for the production of polymer moldings.
  • the flame-retardant molding composition particularly preferably contains from 5 to 30% by weight of monomino-functionalized dialkylphosphinic acids, salts or esters prepared according to one or more of claims 1 to 11, from 5 to 90% by weight of polymer or mixtures thereof to 40 wt .-% of additives and 5 to 40 wt .-% filler, wherein the sum of the components is always 100 wt .-%.
  • the invention also relates to flame retardants containing the mono-amino-functionalized dialkylphosphinic acids, salts or esters prepared according to one or more of claims 1 to 11.
  • the invention relates to polymer molding compositions and polymer moldings, films, filaments and fibers containing the monomino-functionalized dialkylphosphinic salts (IM) according to the invention of the metals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe ,
  • the flame retardant components are mixed with the polymer granules and any additives and on a twin-screw extruder (type Leistritz LSM ® 30/34) at temperatures of 230 to 260 0 C (PBT-GV) or from 260 to 280 0 C (PA 66 -GV) incorporated.
  • PBT-GV twin-screw extruder
  • PA 66 -GV twin-screw extruder
  • the molding compositions were processed in an injection molding machine (Aarburg Allrounder) at melt temperatures of 240-270 0 C (PBT-GV) and 260-290 0 C (PA 66-GV) into test specimens.
  • the specimens are tested and classified for flame retardance (flame retardance) using the UL 94 (Underwriter Laboratories) test.
  • V-O no afterburning longer than 10 sec, sum of afterburning times at
  • V-1 no afterburning longer than 30 sec after end of flaming, sum of afterburning times with 10 flame treatments not bigger than 250 sec, no afterglow of the samples longer than 60 sec after flaming end, other criteria as for V-O.
  • V-2 Ignition of the cotton by burning dripping, other criteria as in V-1. Not classifiable (nkl) does not meet fire class V-2.
  • the LOI value (Limiting Oxygen Index) is determined according to ISO 4589. According to ISO 4589, the LOI corresponds to the lowest concentration by volume of oxygen which, in a mixture of oxygen and nitrogen, is just the combustion of the Plastic entertains. The higher the LOI value, the harder the flammability of the tested material. LOI 23 flammable
  • ethylphosphonous acid prepared as in Example 1
  • ethylene oxide is introduced into a 500 ml five-necked flask with gas inlet tube, thermometer, intensive stirrer and reflux condenser with gas combustion.
  • ethylene oxide is introduced.
  • a reaction temperature of 70 0 C is set and post-reacted at 80 0 C for one hour.
  • the ethylene oxide uptake is 65.7 g.
  • the acid number of the product is less than 1 mg KOH / g. It will be 129 g (94% of theory)
  • Ethylphosphonous acid 2-hydroxyethyl ester obtained as a colorless, water-clear product.
  • Example 5 At room temperature, in a three-necked flask with stirrer and
  • reaction solution is passed through a charged with Deloxan ® THP II column and the THF removed in vacuo.
  • the product is purified by distillation at reduced pressure. There are obtained 32.7 g (93% of theory) Ethylvinylphosphin Acidbutylester as a colorless oil.
  • reaction solution is passed through a charged with Deloxan ® THP II column and the acetic acid removed in vacuo.
  • the product is purified by chromatography. There are obtained 20.9 g (87% of theory) of ethylvinylphosphinic acid as a colorless oil.
  • Example 7 At room temperature, in a three-necked flask with stirrer and
  • reaction solution is passed through a charged with Deloxan ® THP II column and the butanol removed in vacuo. There are obtained 33.4 g (95% of theory) Ethylvinylphosphin Acidbutylester as a colorless oil.
  • Example 9 360 g (3 mol) of ethylvinylphosphinic acid (prepared as in Example 6) are dissolved at 85 ° C. in 400 ml of toluene and admixed with 888 g (12 mol) of butanol. At a reaction temperature of about 100 0 C, the water formed is removed by azeotropic distillation. The product is purified by distillation at reduced pressure. There are obtained 496 g (95% of theory) Ethylvinylphosphin Acid Bathrebutylester as a colorless oil.
  • Example 12 At room temperature, in a three-necked flask with stirrer and
  • Argon carrier stream passed through the reaction solution. After a reaction time of 3 hours, the hydrogen cyanide is expelled from the apparatus with argon.
  • Example 16 441 g of (3.0 mol) of ethyl (2-cyanoethyl) phosphinic acid (prepared as in Example 12) of toluene are dissolved at 85 0 C in 400 ml and with 248 g (4 mol) of ethylene glycol and analogous to Example 15 esterified, then the toluene and excess ethyl glycol separated in vacuo. There are obtained 510 g (89% of theory) of ethyl (2-cyanoethyl) -phosphinic acid 2-hydroxyethyl ester as a colorless oil
  • Example 20 414 g (2 mol) of ethyl (3-aminopropyl) -phosphinic acid butyl ester (prepared as in Example 18) are placed in a five-necked flask with thermometer, reflux condenser, intensive stirrer and dropping funnel. At 160 0 C 500 ml of water is metered in over 4 h and a butanol-water mixture is distilled off. The solid residue is recrystallized from acetone. There are obtained 296 g (98% of theory) of ethyl (3-aminopropyl) -phosphinic acid as a colorless solid.
  • Example 21 414 g (2 mol) of ethyl (3-aminopropyl) -phosphinic acid butyl ester (prepared as in Example 18) are placed in a five-necked flask with thermometer, reflux condenser, intensive stirrer and dropping funnel. At 160 0 C 500 ml of water is metered
  • Example 22 906 g (6 mol) of ethyl (3-aminopropyl) -phosphinic acid (prepared as in Example 20) are dissolved in 860 g of water and introduced into a five-necked flask with thermometer, reflux condenser, intensive stirrer and dropping funnel and charged with about 480 g ( 6 mol) neutralized 50% sodium hydroxide solution.
  • Example 23 227 g (1 mol) of ethyl (3-amino-1-phenylpropyl) -phosphinic acid (prepared analogously to Example 20) and 85 g of titanium tetrabutoxide are refluxed in 500 ml of toluene for 40 hours. Resulting butanol is distilled off with portions of toluene from time to time. The resulting solution is then freed from the solvent. 233 g (98% of theory) of ethyl (3-amino-1-phenylpropyl) -phosphinic titanium salt are obtained.
  • a mixture of 50% by weight of polybutylene terephthalate, 20% by weight of ethyl-3-aminopropyl-phosphinic aluminum (III) salt (prepared as in Example 22) and 30% by weight of glass fibers are coated on a twin-screw extruder (Leistritz LSM 30/34) at temperatures of 230 to 260 0 C to form a polymer molding compound.
  • the homogenized polymer strand was stripped off, cooled in a water bath and then granulated. After drying, the molding materials are processed on an injection molding machine (type Aarburg Allrounder) at 240 to 270 0 C to form polymer molding and a UL-94 classification of VO determined.
  • a mixture of 53% by weight of polyamide 6.6, 30% by weight of glass fibers, 17% by weight of ethyl (3-amino-1-phenylpropyl) -phosphinic titanium salt (prepared as in Example 23) are used on a twin-screw extruder (Type Leistritz LSM 30/34) compounded into polymer molding compounds.
  • the homogenized polymer strand was stripped off, cooled in a water bath and then granulated.
  • ADJUSTED SHEET (RULE 91) ISA / EP
  • the molding compositions are processed on an injection molding machine (type Aarburg Allrounder) at 260 to 290 0 C to form polymer moldings and obtained a UL-94 classification of VO.
  • a 75% suspension of 15.1 g of ethyl (3-aminopropyl) -phosphinic acid (prepared as in Example 20) and 372.4 g of adipic acid hexamethylenediamine salt in water are placed under nitrogen in a steel autoclave and slowly to a temperature of 220 0 C. and brought a pressure of 20 bar. Then the temperature is increased to about 270 0 C while maintaining the pressure, formed water continuously removed from the autoclave and slowly reduced to atmospheric pressure.
  • the polymer (335 g) contains 0.9% phosphorus, the LOI is 32.

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DE102008055914A1 (de) * 2008-11-05 2010-05-06 Clariant International Limited Verfahren zur Herstellung von mono-hydroxyfunktionalisierten Dialkylphosphinsäuren, -estern und -salzen mittels Acroleinen und ihre Verwendung
DE102008055916A1 (de) * 2008-11-05 2010-05-06 Clariant International Limited Verfahren zur Herstellung von mono-hydroxyfunktionalisierten Dialkylphosphinsäuren, -estern und -salzen mittels Allylalkoholen und ihre Verwendung
EP2352740B1 (de) * 2008-11-07 2014-09-24 Clariant Finance (BVI) Limited Verfahren zur herstellung von dialkylphosphinsäuren, -estern und -salzen mittels acrylsäurederivaten und ihre verwendung
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EP2367835B1 (de) * 2008-11-11 2013-12-11 Clariant Finance (BVI) Limited Verfahren zur herstellung von mono-allylfunktionalisierten dialkylphosphinsäuren, deren salze und ester mit allylischen verbindungen und ihre verwendung
DE102008060035A1 (de) * 2008-12-02 2010-06-10 Clariant International Limited Verfahren zur Herstellung von mono-hydroxyfunktionalisierten Dialkylphosphinsäuren, -estern und -salzen mittels Vinylester einer Carbonsäure und ihre Verwendung
DE102008060036A1 (de) * 2008-12-02 2010-06-10 Clariant International Limited Verfahren zur Herstellung von mono-carboxyfunktionalisierten Dialkylphosphinsäuren, -estern und -salzen mittels Vinylester einer Carbonsäure und ihre Verwendung
DE102008060535A1 (de) 2008-12-04 2010-06-10 Clariant International Limited Verfahren zur Herstellung von mono-carboxyfunktionalisierten Dialkylphosphinsäuren, -estern und -salzen mittels Vinylether und ihre Verwendung
DE102008063627A1 (de) 2008-12-18 2010-06-24 Clariant International Limited Verfahren zur Herstellung von monohydroxyfunktionalisierten Dialkylphosphinsäuren,-estern und -salzen mittels Ethylenoxid und ihre Verwendung
DE102008063668A1 (de) 2008-12-18 2010-07-01 Clariant International Limited Verfahren zur Herstellung von Alkylphosponsäuren, -estern und -salzen mittels Oxidation von Alkylphosphonigsäuren und ihre Verwendung
DE102008063642A1 (de) 2008-12-18 2010-06-24 Clariant International Limited Verfahren zur Herstellung von monocarboxyfunktionalisierten Dialkylphosphinsäuren, -estern und -salzen mittels Alkylenoxiden und ihre Verwendung
KR101697948B1 (ko) 2008-12-18 2017-01-19 클라리언트 파이넌스 (비브이아이)리미티드 아세틸렌을 사용하는 에틸렌디알킬포스핀산, 에틸렌디알킬포스핀산 에스테르 및 에틸렌디알킬포스핀산 염의 제조방법 및 이의 용도
DE102008064012A1 (de) 2008-12-19 2010-06-24 Clariant International Limited Halogenfreie Addukte von Alkylphosphonigsäurederivaten und diesterbildenden Olefinen, halogenfreie Verfahren zu deren Herstellung und ihre Verwendung
DE102008064003A1 (de) 2008-12-19 2010-06-24 Clariant International Limited Verfahren zur Herstellung von mono-funktionalisierten Dialkylphosphinsäuren, -estern und -salzen und ihre Verwendung
CN104262620B (zh) * 2014-09-30 2016-06-01 成都拓利科技股份有限公司 一种膨胀型抗熔滴阻燃剂及其制备方法
US10730968B2 (en) * 2015-12-18 2020-08-04 Lg Chem, Ltd. Method for preparing modified conjugate diene polymer
JP7767333B2 (ja) * 2021-02-09 2025-11-11 丸善石油化学株式会社 リン化合物の精製方法および再利用方法

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