Classifications

• • 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 monohydroxy-functionalized dialkylphosphinic acids, esters and salts by means of vinyl esters of a carboxylic acid and their use.
• This object is achieved by a process for the preparation of monohydroxy-functionalized dialkylphosphinic acids, esters and salts, which comprises: a) a source of phosphinic acid (I)
• 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-hydroxy-functionalized compound obtained according to step c) are preferred Dialkylphosphinic, whose 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 Alkylphosphonigklakladreester (II), mono-functionalized dialkylphosphinic (VI ) and / or monohydroxy-functionalized dialkylphosphinic esters (III) are subjected to the further reaction steps b), c) or d).
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are the same or different and are independently H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , tert. Butyl and / or phenyl.
• XH Ca, Mg, Al, Zn, Ti, Fe, Ce, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, ethylene glycol, propyl glycol, butylglycol, pentylglycol, hexylglycol is preferred , Allyl and / or glycerin.
• the catalyst system A is preferably formed by reaction of a transition metal and / or a transition metal compound and at least one ligand.
• transition metals and / or transition metal compounds are preferably those from the seventh and eighth subgroups.
• the transition metals and / or transition metal compounds are preferably rhodium, nickel, palladium, platinum, ruthenium.
• Catalyst B is preferably hydrogen peroxide, sodium peroxide, lithium peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, sodium peroxodisulfate, potassium peroxoborate, peracetic acid, benzoyl peroxide, di-t-butyl peroxide and / or peroxodisulfuric acid and / or azodiisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride and / or 2,2'-azobis (N, N'-dimethylene-isobutyramidine) dihydrochloride.
• the catalyst C is preferably metals, metal hydrides, metal hydroxides and metal alcoholates and mineral acids, for example sulfuric, nitric, hydrochloric, phosphoric acid or mixtures thereof.
• the vinyl esters of a carboxylic acid (V) are preferably vinyl, 1-propenyl, 1-butenyl acetate, propionate, butyrate, pivalate, benzoate, cinnamate, stearate and laurate ,
• 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-C- ⁇ 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 Ci-Ci ⁇ -
• the invention also relates to the use of mono-hydroxy-functionalized dialkylphosphinic acids, esters and salts (III) prepared according to one or more of claims 1 to 12 as an intermediate for further syntheses, as a binder, as a crosslinker or accelerator in the curing of epoxy resins, polyurethanes , unsaturated polyester resins, as polymer stabilizers, as crop protection agents, as a therapeutic or additive in therapeutics for humans and animals, as sequestering agents, as a mineral oil additive, as corrosion inhibitors, in detergents and cleaners, in electronics applications.
• mono-hydroxy-functionalized dialkylphosphinic acids, esters and salts (III) prepared according to one or more of claims 1 to 12 as an intermediate for further syntheses, as a binder, as a crosslinker or accelerator in the curing of epoxy resins, polyurethanes , unsaturated polyester resins, as polymer stabilizers, as crop protection agents, as a therapeutic or additive in therapeutics for humans and animals, as
• the invention also relates to the use of monohydroxy-functionalized dialkylphosphinic acids, salts and esters, which have been prepared according to one or more of claims 1 to 12, 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.
• the invention additionally relates to a flame-retardant thermoplastic or thermosetting polymer molding composition
• a flame-retardant thermoplastic or thermosetting polymer molding composition comprising from 0.5 to 45% by weight of monohydroxy-functionalized dialkylphosphinic acids, salts or esters which have been prepared according to one or more of claims 1 to 12, from 0.5 to 95 % By weight of 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 flame-retardant thermoplastic or thermosetting polymer moldings, films, filaments and fibers containing from 0.5 to 45% by weight of mono-hydroxyfunctionalized dialkylphosphinic acids, salts or esters (III), which are prepared according to a or more of claims 1 to 12, 0.5 to 95% by weight of 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, respectively Sum of components 100 wt .-% is.
• the mono-hydroxy-functionalized dialkylphosphinic acid is 2- (ethylhydroxyphosphinyl) -1-hydroxyethane, 2- (propylhydroxyphosphinyl) -1-hydroxyethane, 2- (i-propylhydroxyphosphinyl) -1-hydroxyethane, 2- (butylhydroxyphosphinyl) 1-hydroxyethane, 2- (sec-butylhydroxy-phosphinyl) -1-hydroxyethane, 2- (i-butyl-hydroxy-phosphinyl) -1-hydroxyethane,
• the mono-hydroxy-functionalized dialkylphosphinic ester is preferably methyl, ethyl; i-propyl; butyl; Phenyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl and / or 2,3-dihydroxypropyl esters of the abovementioned mono-hydroxy-functionalized dialkylphosphinic acids.
• the mono-hydroxy-functionalized dialkylphosphinic acid salt is preferably an aluminum (III), calcium (II), magnesium (II), cerium (III), Ti (IV) and / or zinc ( II) salt of the aforementioned mono-hydroxy-functionalized dialkylphosphinic acids.
• 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 , 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,
• transition metals and transition metal compounds are 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 abovementioned 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.
• 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 is preferred, on a metal oxide such as alumina, silica, titania, zirconia, zinc oxide, nickel oxide, vanadium oxide, chromium oxide, magnesium oxide, Celite ®, diatomaceous earth is preferred, on a metal oxide such as alumina, silica, titania, zirconia, zinc oxide, nickel oxide, vanadium oxide, chromium oxide, magnesium oxide, Celite ®, diatomaceous earth is preferred, on a metal oxide such as alumina, silica, titania, zirconia, zinc oxide, nickel oxide, vanadium oxide, chromium oxide, magnesium oxide, Celite ®, diatomaceous earth is preferred, on a metal oxide such as alumina, silica, titania, zirconia,
• Metal carbonate such as barium carbonate, calcium carbonate, strontium carbonate, on a metal sulfate such as barium sulfate, calcium sulfate, strontium sulfate, on a metal phosphate such as aluminum phosphate, vanadium phosphate a metal carbide such as silicon carbide, on a metal aluminate such as calcium aluminate, on a metal silicate such as aluminum silicate, chalk, zeolites, bentonite, montmorillonite, hectorite, on functionalized silicates, functionalized silica gels such as Silia Bond ®, QuadraSil TM, on functionalized polysiloxanes such as Deloxan ® , on a metal nitride, on carbon, activated carbon, mullites, bauxites, antimonyites, scheelites, perovskites, hydrotalcites, heteropolyanions, on functionalized and unfunctionalized cellulose, chito
• 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 are, for.
• Suitable complexing agents are, for.
• 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, palladium, platinum, nickel, rhodium; Palladium platinum, nickel or rhodium on alumina, on silica, on barium carbonate, on barium sulfate, on calcium carbonate, on strontium carbonate, on carbon, on activated charcoal; Platinum-palladium-gold, aluminum-nickel, iron-nickel, lanthanoid-nickel, zirconium-nickel, platinum-iridium, platinum-rhodium; Raney ® nickel, nickel-zinc-iron oxide; Palladium (II), nickel (II), platinum (II), rhodium chloride, bromide, iodide, fluoride, hydride, oxide, peroxide, cyanide, sulfate, nitrate, phosphide, boride, chromium oxide, cobalt oxide, carbonate hydroxide, cyclohexanebutyrate, hydroxide
• Ethylenebis (triphenylphosphine) platinum (0) platinum (0).
• the ligands are preferably phosphines of the formula (VII)
• Suitable phosphines are, for example, 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
• M independently represent N, P, As or Sb.
• the two M are the same and more preferably M "is a phosphorus atom.
• Each group R 10 independently represents the radicals described under formula (VII). Preferably, all groups R 10 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, 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 (VII) and (VIII) can be bonded to a suitable polymer or inorganic substrate by the radicals R 10 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) and d) 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 1, in particular 20 to 180 0 C and the total pressure of 1 to 100 bar.
• the isolation of the products and / or the transition metal 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) and d) is carried out optionally by distillation or rectification, by crystallization or precipitation, by filtration or centrifugation, by adsorption or chromatography or other known methods.
• solvents, auxiliaries and optionally other volatile constituents are replaced by e.g. Distillation, filtration and / or extraction separated.
• the reactions in the process stages a), b) c) and d) preferably take place optionally in absorption columns, spray towers, bubble columns, stirred tanks, Reiselbettreaktor, 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 undergo one
• 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 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 particular catalyst A is preferably generated in situ before the reaction and / or at the beginning of the reaction 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 is preferably used homogeneously or as a suspension, while a fixed-bed arrangement is advantageous in the case of gas-phase or supercritical operation.
• Suitable solvents are water, alcohols, such as. 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.
• alcohols such as. Methanol, ethanol, i-propanol, n-propanol, n-butanol, i-butanol, t-butanol, n-amyl alcohol, i-amyl alcohol, n-hexanol, n-octanol, i-octanol, n-tridecanol, benzyl alcohol, etc.
• glycols such as Ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, diethylene glycol, etc .
• 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 anisole (methyl phenyl ether), t-butyl methyl ether, dibenzyl ether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether, tetrahydrofuran, triisopropyl ether, etc .; Glycol ethers like Diethylene glycol diethyl ether, diethylene glycol dimethyl ether (diglyme), diethylene glycol monobutyl ether, diethylene glycol mono methyl 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-buty
• Suitable solvents are also the olefins used and
• 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-1 ol, cis-3-hexene-1-ol, 5-hexen-1-ol, styrene, methylstyrene, 4-methylstyrene, vinyl acetate, 9-vinylanthracene, 2-vinylpyridine, 4-
• the reaction preferably takes place at a partial pressure of the olefin of 0.01-100 bar, particularly 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 product II (alkylphosphonous acid or salts, esters) of catalyst, transition metal or transition metal compound, ligand, complexing agent , Salts and by-products is released.
• a phosphinic acid source is reacted with olefins in the presence of a catalyst and the product II (alkylphosphonous acid or salts, esters) of catalyst, transition metal or 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 auxiliaries 2 and / or distillation with auxiliaries 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, chalk, zeolites, bentonite, montmorillonite, hectorite, functionalized silicates, functionalized silica gels, such as Silia Bond ®, QuadraSil TM, Polysiloxanes such as Deloxan ®, metal nitrides, carbon, activated carbon, mullite, Bauxite, Antimonite, scheelite, perovskite, hydrotalcite, functionalized and unfunctionalized cellulose, chitosan, keratin, heteropolyanions, ion exchangers such as Amberlite TM
• Auxiliaries 1 are preferably added in quantities corresponding to a 0.1-40% by weight loading of the metal on the auxiliary 1.
• Aid 1 at temperatures of 20 is preferred - 90 0 C.
• the residence time of adjuvant 1 is preferably 0.5 to 360 minutes.
• Auxiliary 2 is preferably the abovementioned solvent according to the invention, as are preferably used in process step a).
• esterification of the mono-hydroxy-functionalized dialkylphosphinic acid (III) 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, by reaction with higher-boiling alcohols with removal of the water formed
• 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 C 1 -C 18 .
• Particularly preferred are methanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, amyl alcohol and / or hexanol.
• M-OH and M'-OH are monohydric or polyhydric, unsaturated alcohols having a carbon chain length of CM S , for example 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, particularly preferred are ethylene oxide and 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.
• M-OH and M'-OH it is also possible to use reaction products of water with one or more molecules of alkylene oxide.
• Preferred are Polyethylene glycols and poly-1, 2-propylene glycols of various molecular sizes having an average molecular weight of 100-1000 g / mol, particularly preferably from 150 to 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 from 100 to 1000 g / mol, more preferably from 150 to 450 g / mol.
• M-OH and M'-OH are 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.
• Suitable reaction products of ethylene oxide with ammonia, primary or secondary amines, hydrogen sulfide, mercaptans, oxygen acids of phosphorus and C 2 -C 6 -dicarboxylic acids are also usable as M-OH and M'-OH.
• Nitrogen compounds are triethanolamine, methyldiethanolamine, n-butyldiethanolamine, n-dodecyldiethanolamine, 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 used M-OH and M'-OH and alkylene oxides. 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 used and M'-OH and alkylene oxide and / or of the solvent.
• the reaction preferably takes place at a partial pressure of the alcohol M-OH and M'-OH and alkylene oxide used of 0.01 to 100 bar, particularly preferably at a partial pressure of the olefin of 0.1 to 10 bar.
• the reaction is preferably at a temperature from -20 to 340 0 C.
• sesonders preferably at a temperature from 20 to 180 0 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 monohydroxy-functionalized dialkylphosphinic acid (III) of 10,000: 1 to 0.001: 1, more preferably in the ratio of 1,000: 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 monohydroxy-functionalized dialkylphosphinic acid (III) to the solvent of 1: 10,000 to 1: 0, more preferably in a phosphinic acid solvent molar ratio of 1:50 to 1: 1.
• Preferred catalysts B as used for process step b) for the reaction of the alkylphosphonous acid, their salts or esters (II) with a vinyl ester of a carboxylic acid (V) to monofunctionalized dialkylphosphinic acid, their salts and esters (VI) are peroxo Compounds such as peroxomonosulfuric acid, potassium monopersulfate (potassium peroxomonosulfate), caroate TM, oxone TM, peroxodisulfuric acid, potassium persulfate (potassium peroxodisulfate), sodium persulfate (sodium peroxodisulfate), ammonium persulfate (ammonium peroxodisulfate).
• peroxomonosulfuric acid potassium monopersulfate (potassium peroxomonosulfate), caroate TM, oxone TM, peroxodisulfuric acid, potassium persul
• Preferred catalysts B are also compounds which can form peroxides in the solvent system, such as sodium peroxide, hydrates, Natriumperoxiddiperoxohydrat, hydrates, lithium peroxide, hydrates, Calcium peroxide, strontium peroxide, barium peroxide, magnesium peroxide, zinc peroxide, potassium hyperoxide, hydrates, sodium peroxoborate, hydrates, Kaliumperoxoboratperoxohydrat, Magnesiumperoxoborat, Calciumperoxoborat, Bariumperoxoborat, Strontiumperoxoborat, Kaliumperoxoborat, Peroxomonophosphorklare, peroxodiphosphoric, potassium peroxodiphosphate, ammonium peroxodiphosphate, Kaliumammoniumperoxodiphosphate, sodium carbonate peroxohydrate, urea peroxohydrate, Ammoniumoxalatperoxid, Bariumperoxidperoxohydrat, Barium peroxide peroxohydrate, calcium hydrogen
• Preferred catalysts B are also hydrogen peroxide, performic acid, peracetic acid, benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide, cumene hydroperoxide, pinene hydroperoxide, p-menthane hydroperoxide, tert-butyl hydroperoxide, acetylacetone peroxide, methyl ethyl ketone peroxide, succinic acid peroxide .
• Preferred catalysts B are also water-soluble azo compounds.
• Particularly preferred azo initiators as VAZO ® 52 2,2'-azobis (2,4-dimethyl valeronitrile), VAZO ® 64 (azo-bis (isobutyronitrile), AIBN), VAZO ® 67 2,2'-azobis (2 - methylbutyronitrile), VAZO ® 88 i-.i' AzobisCcyclohexane-i-carbonitrile), VAZO ® 68 from the company Dupont-Biesteritz, V-70 2.2 l-azobis (4-methoxy-2,4-dimethyl valeronitrile).
• azo initiators such as 2-tert-butylazo-2-cyanopropane, dimethylazo-diisobutyrate, azodiisobutyronitrile, 2-tert-butylazo-1-cyanocyclohexane, i-tert-amylazo-i-cyanocyclohexan.
• alkyl perketals such as 2,2-bis (tert-butylperoxy) butane, ethyl 3,3-bis (tert-butylperoxy) butyrate, 1,1-di- (tert-butylperoxy) cyclohexane.
• the catalyst B is used in amounts of 0.05 to 5 mol% relative to the respective vinyl ester of a carboxylic acid (V).
• the catalyst B is preferably used in amounts of from 0.001 to 10 mol%, based on the phosphorus-containing compound.
• the initiator B is preferably metered in at a rate of from 0.01 to 10 mol% of catalyst per hour, based on the phosphorus-containing compound.
• the catalyst B is added continuously during the reaction.
• the catalyst B is added continuously during the reaction in the form of a solution in the olefin (IV).
• the catalyst B is added continuously during the reaction in the form of a solution in the solvent used.
• Suitable solvents are those which are used further in process step a).
• the implementation of the alkylphosphonous acids (II) is preferably carried out with a Vinylester a carboxylic acid (V) at a temperature from 0 to 250 0 C, particularly preferably at 20 to 200 0 C and in particular at 50 to 150 0 C.
• the atmosphere in the reaction with a vinyl ester of a carboxylic acid (V) to 50 to 99.9 wt .-% of components of the solvent and vinyl ester of a carboxylic acid (V), preferably 70-95%.
• the reaction preferably takes place during the addition of the vinyl ester of a carboxylic acid (V) at a pressure of 1-20 bar.
• the product mixture obtained after process stage a) and / or b) is worked up.
• the product mixture obtained after process stage a) is worked up and then the monofunctionalized dialkylphosphinic acids obtained according to process stage b) and / or their esters and alkali metal salts are reacted in process stage c).
• step c) to give the monohydroxy-functionalized dialkylphosphinic acid, its salts and esters (III) is achieved by acidic or alkaline hydrolysis of the monofunctionalized dialkylphosphinic acid, its salts or esters (VI) using acids or bases in the presence of water ,
• a mono-hydroxy-functionalized dialkylphosphinic acid (III) is obtained, this can be reacted with a base to give a mono-hydroxy-functionalized dialkylphosphinic acid salt.
• Suitable mineral acids are, for example, hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid or mixtures of the acids.
• Suitable bases are metals, metal hydrides and metal alcoholates such as, for example, lithium, lithium hydride, lithium aluminum hydride, methyl lithium, butyl lithium, tert-butyllithium, lithium diisopropylamide, sodium, sodium hydride, sodium borohydride, sodium methoxide, sodium ethanolate or sodium butylate, potassium methoxide, potassium ethoxide or potassium butylate and also sodium hydroxide, potassium hydroxide, Lithium hydroxide, barium hydroxide,
• the acidic or alkaline hydrolysis can be carried out in the presence of water and an inert Harsmittles.
• Suitable inert solvents are the solvents mentioned in process step a), preference being given to low molecular weight alcohols having from 1 to 6 carbon atoms.
• the use of saturated aliphatic alcohols is particularly preferred.
• suitable alcohols are methanol, ethanol, propanol, i-propanol, butanol, 2-methyl-1-propanol, n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3-methyl-2-ol butanol, 2-methyl-3-butanol, 3-methyl-1-butanol or 2-methyl-1-butanol.
• Preferred bases (catalyst C) for carrying out the alkaline hydrolysis are metals, metal hydrides and metal alcoholates such as, for example, lithium, lithium hydride, lithium aluminum hydride, methyl lithium, butyl lithium, tert-butyl lithium, lithium diisopropylamide, sodium, sodium hydride, sodium borohydride, sodium methoxide, sodium ethanolate or sodium butylate, Potassium methoxide, potassium or potassium butoxide and also sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide and ammonium hydroxide. Preference is given to using sodium hydroxide, potassium hydroxide and barium hydroxide.
• Preferred mineral acids (catalyst C) for carrying out the acidic hydrolysis are, for example, sulfuric, nitric, hydrochloric, phosphoric acid or mixtures thereof. Sulfuric or hydrochloric acid are preferably used.
• the presence of water is essential. The amount of water can range from the stoichiometric requirement as a minimum amount to a surplus.
• the hydrolysis is preferably carried out in a phosphorus / water molar ratio of from 1: 1 to 1: 1000, more preferably from 1: 1 to 1:10.
• the hydrolysis is carried out in a phosphorus / base or acid molar ratio of 1: 1 to 1: 300, more preferably from 1, 1 to 1: 20.
• the amount of alcohol used is generally from 0.5 kg to 1, 5 kg per kg of monofunctionalized dialkylphosphinic acid, their salts or esters (VI), preferably from 0.6 kg to 1, 0 kg.
• the reaction temperature is preferably from 50 0 C to 140 0 C 1 preferably from 80 0 C to 130 0 C.
• the reaction is carried out at a total pressure of 1 to 100 bar, more preferably at a total pressure of 1 to 10 bar.
• the reaction time is preferably from 0.2 to 20 hours, more preferably from 1 to 12 hours.
• the mono-hydroxy-functionalized dialkylphosphinic acid or its salt (III) can be subsequently converted into further metal salts.
• the metal compounds used in process step d) are preferably compounds of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K. particularly preferably Mg, Ca, Al, Ti, Zn, Sn, Ce, Fe.
• Suitable solvents for process step d) are those which are used further in process step a).
• the reaction is carried out in process step d) in an aqueous medium.
• the reaction takes place in a molar ratio of monohydroxy-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).
• mono- hydroxy-functionalized dialkylphosphinic ester / salt (III) is carried out in process stage c) obtained in the corresponding dialkylphosphinic acid and sets this in process stage d) with metal compounds of Mg, Ca, Al, Zn, Ti, Sn 1 Zr, Ce or Fe to the monohydroxy-functionalized dialkylphosphinic salts (III) of these metals.
• the metal compounds of Mg, Ca, Al, Zn, Ti, Sn 1 Zr, Ce or Fe for process stage d) are metals, metal oxides, hydroxides, -oxide-hydroxide, borates, carbonates, -hydroxocarbonate , -hydroxocarbonate hydrates, mixed hydroxocarbonates, mixed hydroxocarbonate hydrates, phosphates, sulphates, sulphate hydrates, hydroxysulphate hydrates, mixed hydroxysulphate hydrates, oxysulphates, acetates, nitrates, fluorides, fluoride hydrates, chlorides, chloride hydrate, oxychloride, bromide, iodides, iodide hydrates, carboxylic acid derivatives and / or alkoxides.
• 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 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% by weight.
• aluminum salts of mono-, di-, oligo-, polycarboxylic acids such as.
• zinc halides zinc fluoride, zinc chlorides, zinc bromide, zinc iodide.
• Zinc salts of pseudohalides zinc thiocyanate, cyanate, cyanide
• Zinc oxides, peroxides, hydroxides or mixed zinc oxide hydroxides Preference is given to 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 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 step d) preferably takes place at a solids content of the monohydroxy-functionalized dialkylphosphinic acid salts 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 in process step d) preferably takes place at a pressure between 0.01 and 1000 bar, preferably 0.1 to 100 bar.
• the reaction takes place in process stage d) during a reaction time of 1 * 10 '7 to 1000 h.
• the monohydroxy-functionalized dialkylphosphinic acid salt (III) removed by filtration and / or centrifuging after process stage d) is preferably dried.
• the product mixture obtained after process step c) is reacted with the metal compounds without further purification.
• Preferred solvents are the solvents mentioned in process step a).
• reaction in process stage c) and / or d) is preferably in the solvent system given by stage a) and / or b).
• the reaction in process step d) is in a modified given solvent system.
• acidic components, solubilizers, foam inhibitors, etc. are added.
• the product mixture obtained after process stage a), b) and / or c) is worked up.
• the product mixture obtained after process stage c) is worked up and then the mono-hydroxy-functionalized dialkylphosphinic acids and / or their salts or esters (III) obtained in process stage c) are reacted with the metal compounds in process stage d).
• the product mixture is preferably worked up after process step c) by reacting the monohydroxy-functionalized dialkylphosphinic acids and / or salts thereof or ester (III) can be isolated by removing the solvent system, e.g. B. by evaporation.
• the monocarboxy-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 2,000 .mu.m, preferably from 10 to 500 .mu.m, a bulk density of 80 to 800 g / l, preferably from 200 to 700 g / l, a flowability of Pfrengle of 0.5 to 10, preferably from 1 to 5, on.
• the shaped bodies, films, threads and fibers particularly preferably contain 5 to 30% by weight of the monohydroxy-functionalized dialkylphosphinic acid / ester / salts prepared according to one or more of claims 1 to 12, 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, chain extenders, color pigments, plasticizers and / or plasticizers.
• a flame retardant containing 0.1 to 90 wt .-% of monohydroxy-functionalized dialkylphosphinic acid, esters and salts (III) and 0.1 to 50 wt .-% further additives, more preferably diols.
• Preferred additives are also aluminum trihydrate, antimony oxide, brominated aromatic or cycloaliphatic hydrocarbons, phenols, ethers, chlorinated paraffin, hexachloro-cyclopentadiene 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 monohydroxy-functionalized dialkylphosphinic acid, esters and salts (III) according to the invention as flame retardants or as intermediates for the preparation of flame retardants for thermoplastic polymers such as polyester, polystyrene or polyamide and for thermosetting polymers such as unsaturated polyester resins, Epoxy resins, polyurethanes or acrylates.
• 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. Terephthalic acid and ethylene glycol, propane-1, 3-diol and butane-1, 3-diol are particularly preferably 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 modified polyester.
• Synthetic linear polyesters with permanent flame retardancy are composed of dicarboxylic acid components, diol components of the monohydroxyfunctionalized dialkylphosphinic acids and esters according to the invention or of the monohydroxyfunctionalized dialkylphosphinic acids and esters prepared by the process according to the invention as phosphorus-containing chain members.
• the phosphorus-containing chain members make up 2-20% by weight of the dicarboxylic acid component of the polyester.
• the resulting phosphorus content in the polyester is preferably 0.1-5%, particularly preferably 0.5-3% by weight.
• the following steps can be carried out with or with the addition of the compounds according to the invention.
• the preparation of the molding composition starting from the free dicarboxylic acid and diols is first esterified directly and then polycondensed.
• 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 at 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, preferably 0.5-15, and for films 0.2-15, 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-butadiene-styrene styrene-isoprene-styrene
• styrene-ethylene / butylene-styrene styrene-ethylene / propylene-styrene.
• the suitable polystyrenes are preferably also graft copolymers of styrene or alpha-methylstyrene, such as, for example, 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
• 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.
• 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 monohydroxy-functionalized dialkylphosphinic acid / ester / salts prepared according to one or more of claims 1 to 12 are preferably used in molding compositions which are further used for the production of polymer moldings.
• the flame-retardant molding composition particularly preferably comprises from 5 to 30% by weight of mono-hydroxy-functionalized dialkylphosphinic acids, salts or esters prepared according to one or more of claims 1 to 12, 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 which contain the monohydroxy-functionalized dialkylphosphinic acids, salts or esters prepared according to one or more of claims 1 to 12.
• the invention relates to polymer molding compositions and polymer moldings, films, filaments and fibers containing the monohydroxy-functionalized dialkylphosphinic salts (III) 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 possibly.
• 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.
• the LOI value was also measured.
• the LOI value (Limiting Oxygen Index) is determined according to ISO 4589. According to ISO 4589, the LOI corresponds to the lowest concentration of oxygen in the volume in a mixture of oxygen and nitrogen just keeps burning the plastic. The higher the LOI value, the harder the flammability of the tested material.
• LOI 23 combustible LOI 24-28 partially combustible LOI 29-35 flame retardant LOI> 36 particularly flame-retardant
• Example 1 As in Example 1, 198 g of phosphinic acid, 198 g of water, 84 g of ethylene, 6.1 mg of palladium (II) sulfate, 25.8 mg of 9,9-dimethyl-4,5-bis (diphenylphosphino) -2,7- reacted sulfonato-xanthene disodium salt, then added to the purification over a charged with Deloxan ® THP II column and then added n-butanol. At a reaction temperature of 80-110 0 C, the water formed is removed by azeotropic distillation. The product (Ethylphosphonigklaklad) is purified by distillation at reduced pressure. 374 g (83% of theory) of butyl ethylphosphonite are thus obtained.
• Example 12 414 g (3 mol) of ethyl (2-hydroxyethyl) -phosphinic acid (prepared as in Example 8) 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. 500 g (86% of theory) of butyl ethyl (2-hydroxyethyl) phosphinate are purified by distillation under reduced pressure.
• ethyl (2-hydroxyethyl) -phosphinic acid prepared as in Example 8 are introduced into a 500 ml five-necked flask with gas inlet tube, thermometer, intensive stirrer and reflux condenser with gas combustion. At room temperature, ethylene oxide is introduced. Under cooling, a reaction temperature of 70 0 C is set and post-reacted at 80 0 C for one hour. The ethylene oxide uptake is 64.8 g. The acid number of the product is less than 1 mg KOH / g. 173 g (95% of theory) of ethyl (2-hydroxyethyl) -phosphinic acid 2-hydroxyethyl ester are obtained as a colorless, water-clear liquid.
• Trisodium phosphate anhydrate and 0.14 g of antimony (III) oxide was added, heated to 280 0 C and then evacuated.
• test specimens thus obtained gave an LOI of 40% O 2 and met the fire classification VO according to UL 94.
• Corresponding test specimens without ethyl (2-hydroxyethyl) -phosphinic acid 2-hydroxyethyl ester gave an LOI of only 31% O 2 and met according to UL 94 only the fire class V-2.
• the ethyl (2-hydroxyethyl) -phosphinic acid 2-hydroxyethyl ester-containing polyester molded body thus clearly shows flame retardant properties.
• Example 18 To 11.6 g of ethyl (2-hydroxyethyl) phosphinic acid (prepared as in Example 8) are added 367 g of dimethyl terephthalate, 170 g of 1,4-butanediol, 0.22 g of tetrabutyl titanate and 0.05 g of lithium acetate, and the The mixture is first heated for 2 hours with stirring to 130 to 180 0 C, then at reduced pressure to 270 0 C.
• the polymer (424 g) contains 0.6% phosphorus, the LOI is 34, that of untreated polybutylene terephthalate 23rd
• Nitrogen discharge is 100 g of a bisphenol A bisglycidethers having an epoxide value of 0.55 mol / 100 g (Beckopox EP 140, Solutia) and 17.9 g (0.13 mol) of ethyl (2-hydroxyethyl) phosphinic acid (prepared analogously to Example 8) with stirring to a maximum of 150 0 C heated. After 30 minutes, a clear melt results. After another hour of stirring at 150 0 C, the melt is cooled and crushed. This gives 116.4 g of a white powder having a phosphorus content of 3.3 wt .-%.
• a mixture of 50% by weight of polybutylene terephthalate, 20% by weight of ethyl (2-hydroxyethyl) -phosphinic aluminum (III) salt (prepared as in Example 10) and 30% by weight of glass fibers are coated on a twin-screw extruder ( Type Leistritz LSM 30/34) at temperatures of 230 to 260 0 C to a
• Polymer molding compound compounded 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.
• injection molding machine type Aarburg Allrounder
• Ethyl (2-hydroxyethyl) -phosphinic titanium salt (prepared as in Example 11) are compounded on a twin-screw extruder (Leistritz LSM 30/34 type) into polymer molding compositions.
• the homogenized polymer strand was stripped off, cooled in a water bath and then granulated. After drying, 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.

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