EP2563797A2 - Procédé de production de mélanges de sels d'acides alkylphosphoniques et de sels d'acides dialkylphosphiniques - Google Patents

Procédé de production de mélanges de sels d'acides alkylphosphoniques et de sels d'acides dialkylphosphiniques

Info

Publication number
EP2563797A2
EP2563797A2 EP11715668A EP11715668A EP2563797A2 EP 2563797 A2 EP2563797 A2 EP 2563797A2 EP 11715668 A EP11715668 A EP 11715668A EP 11715668 A EP11715668 A EP 11715668A EP 2563797 A2 EP2563797 A2 EP 2563797A2
Authority
EP
European Patent Office
Prior art keywords
acid
aluminum
salts
mixture
alkylphosphonous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11715668A
Other languages
German (de)
English (en)
Inventor
Michael Hill
Sebastian HÖROLD
Werner Krause
Martin Sicken
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Finance BVI Ltd
Original Assignee
Clariant Finance BVI Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant Finance BVI Ltd filed Critical Clariant Finance BVI Ltd
Publication of EP2563797A2 publication Critical patent/EP2563797A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—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
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
    • C07F9/4816—Acyclic saturated acids or derivatices which can have further substituents on alkyl

Definitions

  • the invention relates to a process for the preparation of mixtures
  • the flame-retardant finish of, for example, polyesters and polyamides can be achieved by adding various additives.
  • Phosphorus based products are the replacement for halogenated flame retardants.
  • the phosphorus-based additives show as high a flame resistance as their halogenated representatives.
  • the salts of phosphinic acids For thermoplastic polymers, the salts of phosphinic acids
  • PCT / US2006 / 045770 describes flame retardant thermoplastic polymers comprising a mixture of metal salts of dialkylphosphinic acids and
  • the invention is therefore based on the object, a process for the preparation of mixtures of Alkylphosphonigklakland- and Dialkylphosphinkladalzen for
  • Dialkylphosphinic salts with short side chains should be reproducibly produced without interfering halogen compounds as starting materials and with good yields.
  • R 1 , R 2 , R 3 , R 4 independently of one another are H, C 1 -C 8 -alkyl, C 6 -C 8 -aryl, C 7 -C 8 -arylalkyl and / or C 7 -Ci 8 alkylaryl and A and B are the same or different and are independently C 2 -C 2 o-alkyl and / or C 8 -C 2 o-alkylaryl and XH, CrCi 8 alkyl, C 6 -C 8 -Aryl, C 7 -C 18 -arylalkyl, C 7 -C 8 -alkylaryl,
  • V (V) (VI), where A and B have the same meaning as in a) and Y is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or one
  • R 1 , R 2 , R 3 , R 4 are the same or different and are independently H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert. Butyl, trimethylene and / or tetramethylene.
  • the olefins (II) are preferably ethylene, 1-propylene, 1-butene, 1-pentene, cylopentene, 1-hexene and / or cyclohexene.
  • the phosphinic acid source (I) is phosphinic acid, its sodium, potassium, calcium, magnesium, aluminum, ammonium salt and / or methyl, ethyl, propyl, i-propyl, butyl, t Butyl, glycol ester.
  • a and B are the same or different and are independently ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, isopentyl, cyclopentyl, hexyl, isohexyl, cyclohexyl.
  • the mixtures to be prepared are salts of alkylphosphonous acid (V), such as aluminum (III), calcium (II), magnesium (II), cerium (III), Ti (IV) and / or zinc (II) salts of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, isopentyl, cylopentyl, hexyl, isohexyl and / or
  • V alkylphosphonous acid
  • V such as aluminum (III), calcium (II), magnesium (II), cerium (III), Ti (IV) and / or zinc (II) salts of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, isopentyl, cylopentyl, hexyl, isohexyl and / or
  • Dialkylphosphinic acid salt (VI) 0.5 to 35% by weight of alkylphosphonous acid salt (V) and 65 to 99.5% by weight of dialkylphosphinic acid salt (VI).
  • Dialkylphosphinic salts (VI) 3 to 30% by weight of alkylphosphonous acid salt (V) and 70 to 97% by weight of dialkylphosphinic acid salt (VI).
  • Dialkylphosphinkladz (VI) based on the total weight of the mixture, 0 to 5 wt .-% of other ingredients such as alkylphosphonic and / or telomere Dialkylphosphinkladze.
  • the invention also relates to the use of the mixtures of
  • thermoplastic polymers for thermosetting polymers, for clearcoats, for thermoplastic polymers
  • Intumescent coatings for wood and other cellulosic products, for the production of flame-retardant polymer molding compounds, 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.
  • thermoplastic polymers are preferably polyesters, polystyrene and / or polyamide and the thermosetting polymers are unsaturated polyester resins, epoxy resins, polyurethanes and / or acrylates.
  • the invention further relates to a flame-retardant thermoplastic or thermosetting polymer molding composition containing 2 to 50% by weight of the mixtures of alkylphosphonous acid salt (V) and dialkylphosphinic acid salt (VI) prepared according to one or more of claims 1 to 9, based on the thermoplastic or thermosetting polymer.
  • the invention also relates to flame-retardant thermoplastic or
  • thermosetting polymer moldings, films, filaments and fibers containing from 2 to 50% by weight of the mixtures of alkylphosphonous acid salt (V) and
  • Dialkylphosphinic acid salt (VI) prepared according to one or more of claims 1 to 9, based on the thermoplastic or thermosetting polymer.
  • the flame-retardant thermoplastic or thermoset polymer moldings, films, threads and fibers preferably contain 3 to
  • Dialkylphosphinic acid salt (VI) prepared according to one or more of claims 1 to 9, based on the thermoplastic or thermosetting polymer.
  • reaction steps a) and b) are preferably carried out in a solvent or solvent system and in an atmosphere containing further gaseous constituents such as, for example, nitrogen, oxygen, argon,
  • 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 be used.
  • Suitable solvents of process steps a) and b) are water, alcohols, glycols, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alicyclic hydrocarbons, ethers, glycol ethers, ketones, esters and / or carboxylic acids.
  • the solvent system contains solvent system additives and water.
  • the solvent system preferably contains from 50 to 100% by weight of water and from 0 to 50% by weight of solvent system additives, particularly preferably from 80 to
  • the solvent system contains 95 to 100% by weight of water and 0 to 5% by weight of solvent system additives.
  • the solvent system additives are preferably mineral acids, acid salts, carboxylic acids, alkalis and / or electrolytes.
  • the acidic salts are preferably sodium bisulfate,
  • the carboxylic acids are preferably formic acid, acetic acid, propionic acid, butyric acid and / or longer-chain carboxylic acids and / or their dimers, oligomers and / or polymers.
  • Preferred solution system additives are mineral acids such.
  • Particularly preferred mineral acids are hydrofluoric acid, hydrochloric acid, perchloric acid, sulfurous acid, sulfuric acid, peroxomonosulfuric acid (Caro's acid), peroxodisulfuric acid, nitrous acid, nitric acid, phosphorous acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid,
  • Peroxomonophosphoric acid peroxodiphosphoric acid
  • carbonic acid silicic acid
  • boric acid peroxoboric acid
  • Process steps a) and b) optionally take place by distillation or rectification, by crystallization or precipitation, by filtration or centrifugation, by adsorption or chromatography or other known methods.
  • reaction stages a) and b) are preferably carried out optionally in absorption columns, spray towers, bubble columns, stirred kettles,
  • the reaction solutions mixtures preferably have a mixing intensity corresponding to a rotation Reynolds number of 1 to 1,000,000, preferably 100 to 100,000, and there is intensive mixing of the respective reaction partners, etc. under an energy input of 0.080 to
  • reaction in process step a) preferably takes place in one
  • the phosphinic acid source (I) is phosphinic acid (hypophosphorous acid, H 3 PO 2 ), a salt of phosphinic acid, an ester of phosphinic acid or mixtures thereof.
  • the salt of phosphinic acid (I) is preferably alkali salts, alkaline earth salts and / or ammonium salts.
  • esters of phosphinic acid (I) are preferably alkyl, hydroxyalkyl, alkylaryl, aryl and / or alkenyl esters.
  • esters of alkylphosphonous acid (II) are the corresponding methyl, ethyl, propyl, i-propyl, butyl, t-butyl, glycol esters.
  • Y is preferably Mg, Ca, Al, Ti, Fe, Zr, Zn, Ce and / or a nitrogen compound.
  • esterification may be carried out to obtain its ester (I).
  • step a) When the phosphinic acid source (I) in step a) is a salt, acidic hydrolysis may be carried out to obtain the free phosphinic acid (I). If the mixture of alkylphosphonous acid (III) and dialkylphosphinic acid (IV) according to step a) is an ester, acidic or basic hydrolysis can be carried out to give the free alkylphosphonous acid (III) and dialkylphosphinic acid (IV) or its salt receive.
  • the phosphinic acid is prepared in situ from salts of phosphinic acid and at least one mineral acid, wherein the ratio of additive acid to hypophosphite (on an equivalent basis) is 0: 1 to 2: 1. Equivalent to this is the fraction of the number of moles of acid divided by the number of acidic protons.
  • R 1 , R 2 , R 3 , R 4 of the olefin (II) in process step a) are preferably identical or different and are, independently of one another, H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
  • Suitable solvents of process steps a) and b) are water, alcohols, glycols, aliphatic hydrocarbons, aromatic hydrocarbons,
  • Halogenated hydrocarbons alicyclic hydrocarbons, ethers, glycol ethers, ketones, esters and / or carboxylic acids.
  • Suitable solvents in process step a) are also the olefins and phosphinic acid sources used. These offer advantages in terms of a higher space-time yield.
  • the reaction in process step a) is carried out under its own vapor pressure of the olefin and / or the solvent.
  • the reaction in the process step a) 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 atmosphere contains gaseous components that do not participate in the reaction.
  • the gaseous components are preferably oxygen, nitrogen, carbon dioxide, noble gases, hydrogen and / or alkanes.
  • the atmosphere in step a) in the reaction to 50 to 99.9 wt .-% of components of the solvent system and olefin, preferably 70 to 95 wt .-%.
  • reaction in process step a) preferably takes place in one
  • radical initiators all systems which generate free radicals are suitable as radical initiators.
  • the addition of the olefin can be initiated by an anionic initiator, radical initiator or photochemically.
  • Particularly preferred free-radical initiators are peroxo compounds such as peroxomonosulphuric acid, potassium peroxomonosulphate, peroxodisulphuric acid, potassium peroxodisulphate,
  • Particularly preferred radical initiators are compounds which are known in the
  • Solvent system can form peroxides such as lithium, sodium, potassium, calcium, strontium, barium, magnesium and zinc peroxide, sodium, potassium, Calcium, barium, strontium and magnesium peroxoborate and their hydrates and peroxohydrates, peroxomonophosphoric acid, peroxodiphosphoric acid, potassium, ammonium peroxodiphosphate, potassium ammonium peroxodiphosphate,
  • peroxides such as lithium, sodium, potassium, calcium, strontium, barium, magnesium and zinc peroxide, sodium, potassium, Calcium, barium, strontium and magnesium peroxoborate and their hydrates and peroxohydrates, peroxomonophosphoric acid, peroxodiphosphoric acid, potassium, ammonium peroxodiphosphate, potassium ammonium peroxodiphosphate,
  • Ammonium triphosphate peroxophosphate hydrate sodium carbonate peroxohydrate, urea peroxohydrate, ammonium oxalate peroxide,
  • Preferred free-radical initiators are hydrogen peroxide, performic acid,
  • Peracetic acid benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide,
  • Preferred free-radical initiators are water-soluble azo initiators such as 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate , 2,2'-Azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methyl-propionamidine] hydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (1-imino-1-pyrrolidino 2-ethylpropane) dihydrochloride, 2,2'-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyeth
  • azo initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile), azo-bis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (4-methoxy-2 , 4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate),
  • alkyl perketals such as 2,2-bis (tert-butylperoxy) butane, ethyl 3,3-bis (tert-butylperoxy) butyrate, 1,1-di- (tert-butylperoxy) cyclohexane.
  • the radical initiator is used in amounts of 0.05 to 5 mol% relative to the respective olefin (II).
  • the free-radical initiator is preferably used in amounts of from 0.001 to 10 mol%, based on the phosphinic acid source.
  • the radical initiator is at a rate of 0.01 to
  • reaction steps a) and b) are preferably carried out in a solvent or solvent system and in an atmosphere containing further gaseous constituents such as, for example, nitrogen, oxygen, argon,
  • 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. If a multi-phase system is used in addition one can
  • Phase transfer catalyst can be used.
  • the mixture of alkylphosphonous acid (III) and dialkylphosphinic acid (IV) may contain from 0 to 10% by weight, based on the total weight, of further phosphorus-containing constituents, such as alkylphosphonic acid salts and / or telomers.
  • the mixture of alkylphosphonous acid (III) and dialkylphosphinic acid (IV) is subsequently reacted in process stage b) to give mixtures of other metal salts of alkylphosphonous acid (V) and dialkylphosphinic acid (VI).
  • the metal compounds used are preferably the
  • the reaction takes place in a molar ratio of phosphorus to metal of 8 to 1 to 1 to 3.
  • the product mixture obtained after process stage a) is preferably reacted with the metal compounds without further purification.
  • the product mixture obtained after process stage a) is worked up.
  • the product mixture is worked up by the mixture of alkylphosphonous acid (III) and dialkylphosphinic acid (IV) and / or their
  • the insulating step is carried out by removing the solvent system, for. B. by evaporation.
  • the insulating step is carried out by removing the solvent system and the minor components dissolved therein, e.g. B. by solid / liquid separation process.
  • the product mixture is worked up by insoluble by-products are separated z. B. by solid / liquid separation process.
  • the reaction in process step b) is in a modified given solvent system.
  • acidic components for this purpose, acidic components
  • Dialkylphosphinic acid (IV) after step a) to a mixture of the esters so may preferably be carried out an acidic or basic hydrolysis to obtain the mixture of alkylphosphonous acid (III) and dialkylphosphinic acid (IV) or salts thereof.
  • the mixture obtained in process step a) is carried out
  • the mixture obtained in process step a) is converted
  • Alkali salt and sets in process step b) this with metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe to the mixtures of
  • the metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe for process step b) are metals, metal oxides, hydroxides,
  • acetate, formate, oxalate, tartrate, benzoate, and / or alkoxides such as.
  • n-propoxide, n-butoxide, tert-butoxide isopropoxide, ethoxide and their hydrates.
  • aluminum compounds metallic aluminum and aluminum salts with anions of the seventh main group such.
  • aluminum salts with anions of the sixth main group such as.
  • aluminum sulfide, aluminum selenide such as.
  • Aluminum salts with anions of the fifth main group such as.
  • Aluminum nitride and aluminum salts with anions of the fourth main group such.
  • aluminum hydride aluminum-calcium hydride, aluminum borohydride or aluminum salts of the oxo acids of the seventh main group such.
  • aluminum salts of the oxo acids of the sixth main group such as.
  • aluminum sulfate aluminum sulfate hydrate, aluminum sulfate hexahydrate,
  • Aluminum salts of the oxo acids of the fifth main group such as Aluminum nitrate nonahydrate, aluminum metaphosphate, aluminum phosphate, light aluminum phosphate hydrate, aluminum monobasic phosphate, monobasic aluminum phosphate solution; as well as aluminum salts of
  • Oxo acids of the fourth main group such.
  • Dihydroxyaluminum sodium carbonate, NaAl (OH) 2CO 3 and aluminum salts of the oxo acids of the third main group such as. B. aluminum borate or else
  • Aluminum salts of pseudohalides such.
  • aluminum oxide purum, purissum, technical, basic, neutral, acidic
  • aluminum oxide hydrate aluminum hydroxide or mixed
  • Aluminum oxide hydroxide and / or polyaluminum hydroxy compounds which preferably have an aluminum content of 9 to 40 wt .-%.
  • Preferred aluminum salts are those with organic anions z.
  • Aluminum salts of mono-, di-, oligo-, polycarboxylic acids such.
  • zinc compounds is elemental, metallic zinc and zinc salts with inorganic anions such.
  • zinc halides zinc fluoride, zinc fluoride tetrahydrate, zinc chlorides (zinc butter), bromides zinc iodide
  • anhydrous zinc carbonate basic zinc carbonate hydrate, (basic) zinc silicate, zinc hexafluorosilicate, zinc hexafluorosilicate hexahydrate, zinc stannate,
  • Zinc salts of oxo acids of the fifth main group (zinc nitrate,
  • Zinc salts of oxo acids of the sixth main group (zinc sulfate,
  • Zinc sulphate monohydrate, zinc sulphate heptahydrate) and zinc salts of the oxo acids of the seventh main group hypohalites, halogenites, halogenates, eg zinc iodate, perhalates, eg zinc perchlorate.
  • zinc oxides Preference is given to zinc oxides, zinc peroxides (for example zinc peroxide), zinc hydroxides or mixed zinc oxide hydroxides (standard zinc oxide, for example from Grillo, activated zinc oxide from, for example, Rheinchemie, zincite, calamine).
  • Zinc salts of the oxo acids of the transition metals are preferred
  • Preferred zinc salts are those with organic anions, these include zinc salts of mono-, Di-, oligo-, polycarboxylic acids, salts of formic acid (zinc formates), acetic acid (zinc acetates, zinc acetate dihydrate, galazine), trifluoroacetic acid (zinc trifluoroacetate hydrate), zinc propionate, zinc butyrate,
  • Zinc valerate zinc caprylate, zinc oleate, zinc stearate, oxalic acid (zinc oxalate), tartaric acid (zinc tartrate), citric acid (tribasic zinc dihydrate),
  • Benzoic acid (benzoate), zinc salicylate, lactic acid (zinc lactate, zinc lactate trihydrate), acrylic acid, maleic acid, succinic acid, amino acids (glycine), acidic hydroxo-functionals (zinc phenolate etc), zinc para-phenolsulfonate, zinc para- Phenolsulfonate hydrate, zinc acetylacetonate hydrate, zinc tannate,
  • titanium compounds metallic titanium as well as titanium salts with inorganic anions such.
  • chloride nitrate or sulfate ions and organic anions such.
  • Particularly preferred are titanium dichloride, titanium sesquisulfate, titanium (IV) bromide, titanium (IV) fluoride,
  • Preferred titanium alkoxides are titanium (IV) n-propoxide (Tilcom ® NPT, Vertec ® NPT), titanium (IV) - n-butoxide, Titanchloridtriisopropoxid, titanium (IV) ethoxide, titanium (IV) - 2-ethylhexyloxide (Tilcom EHT ®, ® Vertetec EHT)
  • metallic tin and tin salts tin (II) chloride, tin (II) chloride dihydrate, tin (IV) chloride
  • tin oxides and preferred tin alkoxide tin (IV) tert-butoxide are preferred, as well as tin oxides and preferred tin alkoxide tin (IV) tert-butoxide.
  • the zirconium compounds include metallic zirconium and zirconium salts such as zirconium (IV) chloride, zirconium sulfate, zirconium sulfate tetrahydrate,
  • the metal compounds are aluminum chloride, aluminum hydroxide, aluminum nitrate, aluminum sulfate, titanyl sulfate,
  • Titanium tetrabutylate, zinc nitrate, zinc oxide, zinc hydroxide and / or zinc sulfate Titanium tetrabutylate, zinc nitrate, zinc oxide, zinc hydroxide and / or zinc sulfate.
  • the reaction in process step b) takes place at a solids content of the mixture of alkylphosphonous salt (V) and dialkylphosphinic acid salt (VI) of 0.1 to 70% by weight, preferably 5 to 40% by weight.
  • the reaction in process step b) preferably takes place at a temperature of 20 to 250.degree. C., preferably at a temperature of 80 to 120.degree.
  • the reaction in process step b) preferably takes place at a pressure of between 0.01 and 1000 bar, preferably 0.1 to 100 bar.
  • reaction takes place in process stage b) during a
  • Alkylphosphonigkladresalz (V) and Dialkylphosphin Acidsalz (VI) of these metals from 1 * 10 "7 to 1 * 10 2 h., Preferably after the process step b) by filtration and / or
  • Chamber / Frame Filter Presses Automatic Chamber Filter Presses, Vacuum Drum Cell Filters, Vacuum Disc Cell Filters, Vacuum Inner Cell Filters, Vacuum Planetary Cell Filters, Rotary Pressure Filters, Vacuum Band Filter Separated.
  • the filtration pressure is 5 * 10 "6 to 60 bar, the filtration temperature 0 to 400 ° C, the specific filter capacity 10 to 200 kg * h " 1 * m "2 and the
  • Residual moisture of the filter cake obtained 5 to 60%.
  • Dialkylphosphinic acid salt (VI) in process step b) with solid bowl centrifuges such as overflow centrifuges, peeler centrifuges, chamber centrifuges, Screw discharge centrifuges, plate centrifuges, tube centrifuges,
  • the acceleration ratio is 300 to 15,000, the
  • Suitable aggregates for drying are chamber dryers, channel dryers, belt dryers (air speed 2 - 3 m / s), plate dryers (temperature 20 to 400 ° C), drum dryers (100 - 250 ° C hot gas temperature), paddle dryers (50 - 300 ° C Temperature), current dryer (10 - 60 m / s air velocity, 50 - 300 ° C exhaust air temperature), fluid bed dryer (0.2 - 0.5 m / s
  • Vacuum drying ovens (20 to 300 ° C temperature, 0.001-0.016 MPa pressure), vacuum roller dryer (20 to 300 ° C temperature, 0.004-0.014 MPa pressure, vacuum paddle dryer (20 to 300 ° C temperature, 0.003-0.02 MPa pressure), vacuum condenser dryer (20 to 300 ° C temperature, 0.003-0.02 MPa pressure).
  • Dialkylphosphinklasalz (VI) of the metals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe optionally a residual moisture content of 0.01 to 10 wt .-%, preferably from 0.1 to 1 wt .-%, a average particle size from 0.1 to 2000 .mu.m, preferably from 10 to 500 [im, 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.
  • alkylphosphonous salt (V) and dialkylphosphinic acid salt (VI) of the metals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe can be used here as
  • the mixtures of alkylphosphonous salt (V) and dialkylphosphinic acid salt (VI) of the metals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe can here be based on the total weight of the mixture 0 to 5 wt .-% further ingredients such as
  • the invention also relates to a solution of mixtures
  • Alkylphosphonous acid (III) and dialkylphosphinic acid (IV) and / or their esters and / or alkali metal salts which contain 10 to 100% by weight of alkylphosphonous acid (III) and dialkylphosphinic acid (IV) and / or their esters and / or alkali metal salts 10 to 100% by weight.
  • % Solvent system the sum being 100% by weight.
  • Dialkylphosphinklad (VI) of these metals were obtained.
  • the subject of the present invention also comprises a process comprising adding sodium hypophosphite with ethylene in the presence of sodium peroxodisulfate in water to the sodium salt of the mixture
  • alkylphosphonous acid (III) and dialkylphosphinic acid (IV) as the main product, this product is then reacted with aluminum sulfate to the aluminum salt of the mixture of alkylphosphonous (V) and dialkylphosphinic (VI).
  • the subject of the present invention also includes in particular a process in which phosphinic acid with ethylene in the presence of Sodium peroxodisulfate in water to the mixture of alkylphosphonous acid (III) and dialkylphosphinic acid (IV) as the main product, this product is then reacted with aluminum hydroxide to the aluminum salt of the mixture
  • Dialkylphosphinic acid (IV) and / or their alkali metal or alkaline earth metal salts which by reaction of phosphinic acid and / or their salts with olefins in the presence of a catalyst to mixtures of alkylphosphonous (III) and dialkylphosphinic (IV) and / or their alkali metal or alkaline earth metal salts a solvent system.
  • mixtures of alkylphosphonous salts (V) and dialkylphosphinic salts (VI) which have been obtained by reacting a) phosphinic acid and / or their alkali metal or alkaline earth metal salts with olefins in the presence of a catalyst to give mixtures of alkylphosphonous acid (III) and dialkylphosphinic acid (IV) and / or their alkali or
  • mixtures of alkylphosphonous salts (V) and dialkylphosphinic salts (VI) obtained by converting mixtures of alkylphosphonous acid salt (III) and dialkylphosphinic acid salt (IV) obtained in process step a) into the mixtures of alkylphosphonous acid (III) and dialkylphosphinic acid (IV). and subsequent implementation of this
  • alkylphosphonous acid (III) and dialkylphosphinic acid (IV) with metal compounds of Mg, Ca, Al, Zn, Sn, Ti, Ce, Zr or Fe to the mixtures of Alkylphosphonigklaresalze (V) and Dialkylphosphin Acidsalze (VI) of these metals.
  • the subject of the present invention also comprises a process in which sodium hypophosphite with ethylene in the presence of Natnumperoxodisulfat in water to the sodium salt of the mixture
  • the subject of the present invention also includes in particular a process in which phosphinic acid with ethylene in the presence of
  • dialkylphosphinic acid also preferred are mixtures of alkylphosphonous salts (V) and dialkylphosphinic salts (VI) obtained by converting mixtures of alkylphosphonous acid (III) and dialkylphosphinic acid (IV) obtained in process step a) into mixtures of alkylphosphonous salt (III) and dialkylphosphinic acid salt (IV) and subsequent reaction of these mixtures of Alkylphosphonigklaklasalz (III) and Dialkylphosphinklasalz (IV) with
  • alkylphosphonous salt (V) and dialkylphosphinic acid salt (VI) prepared by the process according to the invention can be used in particular as flame retardants or as intermediates for the preparation of flame retardants.
  • Dialkylphosphinic acid salt (VI) 0.5 to 35% by weight of alkylphosphonous acid salt (V) and 65 to 99.5% by weight of dialkylphosphinic acid salt (VI).
  • Dialkylphosphinic salts (VI) 3 to 30% by weight of alkylphosphonous acid salt and 70 to 97% by weight of dialkylphosphinic acid salt.
  • Dialkylphosphinic acid salt (VI) based on the total weight of the mixture 0 to 5 wt .-% of other ingredients such as alkylphosphonic and / or telomere Dialkylphosphinklaresalze.
  • the mixture according to the invention of alkylphosphonous acid salt (V) and dialkylphosphinic acid salt (VI) contains 0.5 to 30% by weight of ethylphosphonous acid aluminum salt and 70 to 99.5% by weight.
  • Diethylphosphinic aluminum salt Furthermore, from 0 to 50% by weight of at least one further flame retardant based on the flameproofed thermoplastic or thermosetting polymer molding composition or the flameproofed thermoplastic or thermoset polymer molding may be added to the flameproofed thermoplastic or thermoset polymer molding compound or the flameproofed thermoplastic or thermoset polymer molding.
  • At least one synergist or phosphorus-nitrogen flame retardant can be added to the flameproofed thermoplastic or thermosetting polymer molding composition or to the flameproofed thermoplastic or thermoset polymer molding.
  • synergist or phosphorus-nitrogen flame retardant based on the flame-retardant thermoplastic or thermosetting polymer molding composition or the flame-retardant are preferably the flame-retardant thermoplastic or thermosetting polymer molding composition or the flameproofed thermoplastic or thermoset polymer molding
  • thermoplastic or thermosetting polymer molding added thermoplastic or thermosetting polymer molding added.
  • synergists or phosphorus-nitrogen flame retardants are preferably condensation products of the melamine and / or
  • the synergist or phosphorus-nitrogen flame retardant is preferably melam, Meiern, melon, dimelamine pyrophosphate, Melamine polyphosphate, melampolyphosphate, melon polyphosphate and melem polyphosphate or mixed polysalts thereof.
  • the phosphorus-nitrogen flame retardants are preferably also nitrogen-containing phosphates of the formulas (NH 4 ) y H 3 -y PO 4 or (NH 4 PO 3 ) z , where y is 1 to 3 and z is 1 to 10,000.
  • Ammonium dihydrogen phosphate and / or ammonium polyphosphate are examples of ammonium dihydrogen phosphate and / or ammonium polyphosphate.
  • the nitrogenous synergists are also present.
  • Benzoguanamine tris (hydroxyethyl) isocyanurate, allantoin, glycouril, melamine, melamine cyanurate, dicyandiamide and / or guanidine.
  • synergistic combinations of said phosphinates with nitrogen-containing compounds (DE-A-96 14424,
  • Suitable synergists are i.a. also carbodiimides, zinc borate,
  • the flame-retardant thermoplastic or thermosetting polymer molding composition or the flame-retardant thermoplastic or thermoset polymer molding at least one stabilizer such as zinc salts, basic or amphoteric oxides, hydroxides, carbonates, silicates, borates, stannates, mixed oxide hydroxides, oxide-hydroxide carbonates, hydroxide Silicates or hydroxide borates, phosphonite, phosphite or a stabilizer such as zinc salts, basic or amphoteric oxides, hydroxides, carbonates, silicates, borates, stannates, mixed oxide hydroxides, oxide-hydroxide carbonates, hydroxide Silicates or hydroxide borates, phosphonite, phosphite or a
  • stabilizer such as zinc salts, basic or amphoteric oxides, hydroxides, carbonates, silicates, borates, stannates, mixed oxide hydroxides, oxide-hydroxide carbonates, hydroxide Silicates or hydroxide
  • Phosphonite / phosphite mixture or an ester or salt of long chain aliphatic carboxylic acids (fatty acids), which typically have chain lengths of Cu to C40 added.
  • thermoplastic or thermosetting polymer molding composition Preference is given to the flame-retardant thermoplastic or thermosetting polymer molding composition or the flame-retardant thermoplastic or thermoset polymer molding 0 to 15 wt .-% stabilizer based on the flame-retardant thermoplastic or thermosetting polymer molding composition or the flame-retardant thermoplastic or thermosetting
  • the stabilizers are preferably also alkali, alkaline earth, aluminum and / or zinc salts of long-chain fatty acids with 14 to
  • esters or salts of stearic acid such as.
  • glycerol or calcium stearate or to reaction products of Montanwachsklaren with ethylene glycol such as a mixture of ethylene glycol mono-Montanwachsklareester, ethylene glycol dimontanwachsklareester, Montanwachsklaren and ethylene glycol or reaction products of Montanwachsklaren with a calcium salt.
  • reaction products are preferably a mixture of 3-budanediol mono-montan wax acid esters, 3-budanediol di-montan wax acid esters, montan wax acids, 1, 3-butanediol, calcium montanate and the calcium salt.
  • Polymer molding compound or the flame-retardant thermoplastic or thermoset polymer molding other additives may be added, such.
  • antioxidants UV absorbers and light stabilizers, metal deactivators, peroxide-destroying compounds, polyamide stabilizers, basic
  • Co-stabilizers nucleating agents and other additives.
  • thermoplastic or thermosetting polymer molding composition or the flameproofed thermoplastic or thermoset polymer are preferred
  • Suitable antioxidants include alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol; 1, 2-Alkylthiomethylphenole, z. B. 2,4-dioctylthiomethyl-6-tert-butylphenol; Hydroquinones and alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol; Tocopherols, e.g. B. ⁇ -tocopherol, ⁇ -tocopherol,
  • ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E); Hydroxylated thiodiphenyl ethers, e.g. B. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert- butyl-3-methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis (2,6-di-methyl-4-hydroxyphenyl) -disulfic acid; Alkylidene Bisphenols, e.g. B. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol;
  • O, N and S benzyl compounds e.g. BSSS ⁇ '- tetra-tert-butyl ⁇ ' - dihydroxybenzyl ether; Hydroxybenzylated malonates, e.g. Dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydrorybenzyl) -malonate; Hydroxybenzyl aromatics, e.g. B.
  • Triazine compounds e.g. B. 2,4-bis-octylmercapto-6 (3,5-di-tert-butylm-hydroxyanilino) -I.S.
  • Suitable UV absorbers and light stabilizers are, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole; 2-hydroxybenzophenones, such as. For example, 4-hydroxy, 4-methoxy, 4-octoxy,
  • Esters of optionally substituted benzoic acids such as.
  • nickel compounds such as. Example, nickel complexes of 2,2'-thio-bis [4 (1, 1, 3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands, such as n Butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonklare monoalkyl esters, as of Methyl or ethyl esters, nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands; Sterically hindered amines, such as.
  • additional ligands such as n Butylamine, triethanolamine or N-cyclohexyl-diethanolamine
  • Suitable metal deactivators are, for. B. ⁇ , ⁇ '-Diphenyloxalklarediamid, N-salicylal-N'-salicyloylhydrazin, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4 -hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) -oxalic dihydrazide, oxanilide, isophthalic dihydrazide, sebacic acid bis-phenylhydrazide, ⁇ , ⁇ '-diacetyl-adipic acid dihydrazide, N , N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic di
  • Mercaptobenzimidazole the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis ( ⁇ -dodecylmercapto) propionate.
  • Suitable basic co-stabilizers are melamine, polyvinylpyrrolidone,
  • Suitable nucleating agents are for. For example, 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid. To the other additives counts z.
  • plasticizers expandable graphite, lubricants, emulsifiers, pigments, optical brighteners, antistatic agents, blowing agents,
  • Heat stabilizers impact modifiers, process auxiliaries, anti-dripping agents, Compatibilizers, nucleating agents, laser marking additives, hydrolysis stabilizers, chain extenders, and / or plasticizers.
  • Polymer molding compound or the flame-retardant thermoplastic or thermoset polymer molding may further fillers and
  • the fillers and reinforcing agents include, for. As calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite and others.
  • thermoplastic or thermosetting polymer molding composition Preference is given to the flame-retardant thermoplastic or thermosetting polymer molding composition or the flame-retardant thermoplastic or thermoset polymer molding 0 to 70 wt .-% filler and / or
  • Reinforcing agents based on the flame-retardant thermoplastic or thermosetting polymer molding composition or the flame-retardant thermoplastic or thermoset polymer molding added.
  • the metal oxides are preferably magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide and / or tin oxide.
  • the hydroxides are preferably aluminum hydroxide, boehmite, magnesium hydroxide, hydrotalcite, hydrocalumite, calcium hydroxide, zinc hydroxide, tin oxide hydrate and / or manganese hydroxide.
  • the flame-retardant thermoplastic or thermosetting polymer molding compositions and bodies are preferred.
  • the flame-retardant thermoplastic or thermosetting polymer molding compositions and bodies are preferred.
  • the flame-retardant thermoplastic or thermosetting polymer molding compositions and bodies are preferred.
  • the flame-retardant thermoplastic or thermosetting polymer molding compositions and bodies are preferred.
  • the flame-retardant thermoplastic or thermosetting polymer molding compositions and bodies are particularly preferred.
  • the flame-retardant thermoplastic or thermosetting polymer molding compositions and bodies are particularly preferred.
  • the flame-retardant thermoplastic or contain
  • the flame-retardant thermoplastic or contain
  • Dosing can be carried out as a solid, in solution or melt, as well as in the form of solid or liquid mixtures or as masterbatches / concentrates.
  • the abovementioned further flame retardants, synergists, phosphorus-nitrogen flame retardants, stabilizers, further additives, fillers and the mixture of alkylphosphonous salt (V) and dialkylphosphinic acid salt (VI) can be introduced into the plastic in a wide variety of process steps. So it is possible with polyamides or polyesters, already at the beginning or at the end of the polymerization / polycondensation or in a following
  • Dialkylphosphinic acid salt (VI) as granules, flakes, fine particles, powders and / or micronisate.
  • Dialkylphosphinkladz (VI) also as a physical mixture of solids, as a melt mixture, as Kompaktat, as an extrudate or in the form of a masterbatch.
  • 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.
  • 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 containing as the dicarboxylic acid component mainly terephthalic acid and as
  • Diol component mainly contain ethylene glycol.
  • the resulting phosphorus content in threads and fibers produced from flame-retardant polyester is preferably 0.1-8, preferably 0.5-5, 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 such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.
  • the suitable polystyrenes are also um
  • 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
  • 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. These are z. B under the tradename Nylon ®, Fa. DuPont, Ultramid ®, Fa. BASF, Akulon ® K122,
  • 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.
  • poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide block copolymers of the above polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted
  • Polypropylene glycol or polytetramethylene glycol Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM polyamide systems").
  • RIM polyamide systems condensed polyamides
  • flame-retardant polymer moldings characterized in that flame-retardant polymer molding compositions according to the invention are produced by injection molding (for example, Aarburg Allrounder injection molding machine) and presses,
  • Foam injection molding, internal gas pressure injection molding, blow molding, film casting, calendering, lamination or coating at higher temperatures to the flame-retardant polymer molding is processed.
  • thermosetting polymers are preferably unsaturated polyester resins (UP resins) which are more saturated and more stable to copolyesters
  • UP resins are cured by free-radical polymerization with initiators (eg peroxides) and accelerators.
  • Preferred unsaturated dicarboxylic acids and derivatives for the preparation of the polyester resins are maleic anhydride and fumaric acid.
  • Preferred saturated dicarboxylic acids are phthalic acid, isophthalic acid,
  • Terephthalic acid Terephthalic acid, tetrahydrophthalic acid, adipic acid.
  • Preferred diols are 1, 2 propanediol, ethylene glycol, diethylene glycol and
  • Preferred vinyl compound for crosslinking is styrene.
  • Preferred hardener systems are peroxides and Metallcoinitiatoren z.
  • Preferred hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permalate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-chlorobenzoyl peroxide, dicyclohexyl peroxide dicarbonate.
  • initiators are used in amounts of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight, calculated on the mass of all comonomers.
  • Preferred metal co-initiators are cobalt, manganese, iron, vanadium, nickel or lead compounds. Preference is given to using metal co-initiators in amounts of from 0.05 to 1% by weight, calculated on the mass of all comonomers.
  • Preferred aromatic amines are dimethylaniline, dimethyl-p-toluene, diethylaniline and phenyldiethanolamine.
  • Dicarboxylic anhydride derived from at least one C-rC ß- dicarboxylic acid, copolymerized at least one vinyl aromatic compound and a polyol and reacted with inventive adducts of Alkylphosphonigklakladon and diester-forming olefins.
  • thermosetting resin with inventive mixture of Alkylphosphonigklasalz (V) and
  • the polymers are preferably crosslinked epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic
  • Suitable glycidyl compounds are bisphenol A diglycidyl esters, bisphenol F diglycidyl esters, polyglycidyl esters of phenol-formaldehyde resins and cresol-formaldehyde resins, polyglycidyl esters of pthalthalene, isophthalic and
  • Suitable hardeners are aliphatic, cycloaliphatic, aromatic and
  • heterocyclic amines or polyamines such as ethylenediamine, diethylenetriamine triethylenetetramine, propan-1,3-diamine, hexamethylenediamine, aminoethylpiperazine, isophoronediamine, polyamidoamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenol sulfones, aniline-formaldehyde resins, 2,2,4-trimethylhexane-1,6 diamine, m-xylylenediamine, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 3-aminomethyl-3,55-trimethylcyclohexylamine
  • Methylhexahydrophthal Acidanhydrid and phenols such.
  • Phenol arylalkyl resin Phenol arylalkyl resin, phenoltrimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol-kocondensate resin, naphthol-cresol-kocondensate resin, biphenol-modified phenol resin and aminotriazine modified phenolic resin. All hardeners can be used alone or in combination with each other.
  • Polymerization are tertiary amines, benzyldimethylamine, N-alkylpyridines, imidazole, 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, metal salts of organic acids, Lewis Acids and amine complex salts.
  • the formulation of the invention may also contain other additives conventionally used in epoxy resin formulations, such as pigments, dyes and stabilizers.
  • Epoxy resins are suitable for encapsulation of electrical or electronic components and for impregnation and impregnation processes. In electrical engineering, epoxy resins are predominantly rendered flame retardant and used for circuit boards and insulators.
  • the polymers are preferably crosslinked polymers which are derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.
  • the polymers are crosslinkable acrylic resins derived from substituted acrylic acid esters, such as. As of epoxy acrylates, urethane acrylates or polyester acrylates.
  • the polymers are preferably alkyd resins, polyester resins and acrylate resins which are blended with melamine resins, urea resins, isocyanates,
  • Isocyanurates, polyisocyanates or epoxy resins are crosslinked.
  • Preferred polyols are alkene oxide adducts of ethylene glycol, 1,2-propanediol, bisphenol A, trimethylolpropane, glycerol, pentaerythrol, sorbitol, sugar,
  • the preferred oxyalkylating agents 7 preferably contain 2 to
  • Preferred polyester polyols are obtained by polycondensation of a
  • Polyalcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, glucose and / or sorbitol with a dibasic acid such as oxalic acid, malonic acid, Succinic, tartaric, adipic, sebacic, maleic, fumaric, phthalic and / or terephthalic acid. These polyester polyols may be used alone or in combination.
  • Suitable polyisocyanates are aromatic, alicyclic or aliphatic
  • Polyisocyanates containing not less than two isocyanate groups and mixtures thereof Preference is given to aromatic polyisocyanates such as tolyl diisocyanate,
  • Suitable polyisocyanates are modified products obtained by reaction of polyisocyanate with polyol, urea, carbodiimide and / or biuret.
  • Suitable catalysts for the production of polyurethane are strong bases, alkali metal salts of carboxylic acids or aliphatic tertiary amines. Preference is given to quaternary ammonium hydroxide, alkali metal hydroxide or alkoxide, sodium or potassium acetate, potassium octoate, sodium benzoate, 1,4-diazabicyclo [2.2.2] octane, NNN'.N'-tetramethylhexamethylene-diamine, N, N, N ⁇ N'- Tetramethylpropylenediamine, NNN'.N'.N'-pentamethyldiethylenetriamine, N, N'-di- (C 1 -C 2) -alkylpiperazine,
  • Trimethylaminoethylpiperazine N, N-dimethylcyclohexylamine, ⁇ , ⁇ -dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, trimethylamine, triethylamine, tributylamine, triethylenediamine, bis (dimethylaminoalkyl) piperazines, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine, ⁇ , ⁇ - Diethylbenzylamine, bis (N, N-diethylaminoethyl) adipate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-butanediamine, N, N-diethyl- [beta] -phenylethylamine, 1, 2-dimethyl-imidazole, 2-methylimidazole, etc.
  • the weight ratio of the polyisocyanate to polyol is 170 to
  • the weight ratio of the catalyst is preferably 0.1 to 4 parts by weight, more preferably 1 to 2 parts by weight, based on 100 parts by weight of the polyol.
  • Preferred blowing agents for polyurethanes are water, hydrocarbons, chlorofluorohydrocarbon, fluorohydrocarbon etc. The amount of
  • Blowing agent for polyurethanes is 0.1 to 1, 8 parts by weight, preferably 0.3 to 1, 6 parts by weight and in particular 0.8 to 1, 6 parts by weight based on
  • Ethylphosphonous acid aluminum (III) salt in a ratio of 88.6% by weight diethylphosphinic acid aluminum (III) salt and 11.4% by weight ethylphosphonous acid aluminum (III) salt (yield 92.6%).
  • a solution of 636 g (6 mol) of sodium hypophosphite monohydrate in 3 kg of water is placed in a 10 L double-pressure reactor. After heating the reaction solution to 100 ° C, ethylene is passed through a set to 6 bar reducing valve to saturation in the reactor. The reaction solution is uniformly metered at an ethylene pressure of 6 bar and a temperature of 100 - 110 ° C with constant stirring, a 0.4 molar sodium peroxodisulfate solution at a metering rate of 25 ml / h. If a certain conversion of ethylene is reached, the dosage of sodium peroxodisulfate solution is stopped and the reactor is depressurized.
  • Ethylphosphonous acid aluminum (III) salt in a ratio of 87.3% by weight diethylphosphinic acid aluminum (III) salt and 12.7% by weight ethylphosphonous acid aluminum (III) salt (yield 96.3%).
  • the resulting mixture contains diethylphosphinic acid and ethylphosphonous acid aluminum (III) salt in a ratio of 83.3% by weight of diethylphosphinic acid aluminum (III) salt and 16.7% by weight of ethylphosphonous acid aluminum (III) salt (yield 95.9%). ).
  • Sulfuric acid are dissolved in 7.5 kg of water and placed in a 16-L jacketed pressure reactor made of steel enamel. After the reaction mixture has been heated to 100 ° C., ethylene is introduced into the reactor up to saturation via a reducing valve set to 6 bar. With constant stirring, a solution of 22 g (1 mol%) of sodium percarbonate in 300 g of water is added uniformly at an ethylene pressure of 6 bar and a temperature of 100 - 110 ° C. At a conversion of ethylene of 83.5%, the dosage of sodium percarbonate is stopped and the reactor is expanded.
  • Ethylphosphonous acid aluminum (III) salt in a ratio of 76.4% by weight diethylphosphinic acid A! Uminium (III) salt and 23.6% by weight ethylphosphonous acid aluminum (III) salt (yield 95.0%).
  • Example 6 Ethylphosphonous acid aluminum (III) salt in a ratio of 76.4% by weight diethylphosphinic acid A! Uminium (III) salt and 23.6% by weight ethylphosphonous acid aluminum (III) salt (yield 95.0%).
  • Aluminum (III) salt in a ratio of 93.0% by weight of diethylphosphinic acid Aluminum (III) salt and 7.0% by weight ethylphosphonous acid aluminum (III) salt (yield 96.4%).
  • Ethylphosphonous acid aluminum (III) salt in a ratio of 79.6% by weight diethylphosphinic acid aluminum (III) salt and 20.4% by weight ethylphosphonous acid aluminum (III) salt (yield 89.7%).
  • the resulting mixture contains diethylphosphinic acid and ethylphosphonous titanium (IV) salt in a ratio of 76.3% by weight.
  • Mixture contains diethylphosphinic and Ethylphosphonigklare zinc (II) salt in a ratio of 81, 3 wt .-% diethylphosphinic zinc (II) salt and
  • Polyamide 6.6 (PA 6.6 GV): Ultramid ® A27 (BASF AG, D.) ⁇
  • DEPAL diethylphosphinic acid
  • Dialkylphosphinic aluminum salt in a ratio of 25.0 to 75.0 wt.%, Hereinafter referred to as EPAL / DEPAL
  • Melamine polyphosphate MPP as hereinafter
  • Melapur ® 200 Melapur ® 200 (Messrs. Ciba SC, CH) Melamine cyanurate (MC as hereinafter) Melapur ® MC50 (Messrs. Ciba SC, CH)
  • Wax components (component F):
  • Licowax E ® from Clariant, D (ester of montan wax acid) production, processing and testing of flame-retardant plastic molding composition:
  • the flame retardant components were mixed in the ratio indicated in the table with the phosphonite, the lubricants and stabilizers and via the side feeder of a twin-screw extruder (Leistritz ZSE 27 / 44D type) at temperatures of 260 to 310 ° C in PA 6.6 or at 250 - 275 ° C incorporated in PBT.
  • the glass fibers were added via a second side feed.
  • the homogenized polymer strand was stripped off, cooled in a water bath and then granulated. After sufficient drying, the molding materials were on a twin-screw extruder (Leistritz ZSE 27 / 44D type) at temperatures of 260 to 310 ° C in PA 6.6 or at 250 - 275 ° C incorporated in PBT.
  • the glass fibers were added via a second side feed.
  • the homogenized polymer strand was stripped off, cooled in a water bath and then granulated. After sufficient drying, the molding materials were on a
  • Injection molding machine (type Arburg 320 C Allrounder) processed to test specimens at melt temperatures of 250 to 300 ° C and based on the UL 94 test
  • MVR Melt volume index
  • the formulations V-1 to V-3 are comparative examples in which a
  • MCP Melamine polyphosphate
  • Table 1 PA 66 GF 30 test results.
  • Hydrotalcite can prevent the gray discoloration and the efflorescence goes back significantly (V-2, V-3).
  • inventive combination of DEPAL with EPAL and optionally the Further additives reduce the polymer degradation almost completely, the fire class V-0 is achieved and the mechanical values are improved.
  • Reinforcing material such as a textile glass endless mat of
  • Basis weight 200 g / m 2 with a homogenized mixture (UP 1, EP 1) of resin, accelerator, the flame retardant component (s), hardener and possibly solvent impregnated, cured for 24 hours at room temperature and an additional 3 hours at 80 ° C. annealed.
  • UP 1, EP 1 homogenized mixture
  • the fire behavior test was carried out according to the instructions of Underwriters Laboratories "Test for Flammability of Plastics Materials - UL 94" in the version of 02.05.1975 on specimens of the above-described laminates of 127 mm length, 12.7 mm width and a thickness of 1, 6 mm performed.
  • the laminates obtained from blends UP 1, UP 2, EP 1 and EP 2 have a UL-94 classification determined to be V-0.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production de mélanges de sels d'acides alkylphosphoniques et de sels d'acides dialkylphosphiniques, caractérisé en ce que a) l'on fait réagir une source d'acide phosphinique (I) avec des oléfines (II) en présence d'un catalyseur A pour obtenir un mélange d'acide alkylphosphonique (III) et d'acide dialkylphosphinique (IV) ou de leurs sels ou de leurs esters, et b) l'on fait réagir le mélange ainsi obtenu, contenant de l'acide alkylphosphonique (III) et de l'acide dialkylphosphinique (IV) ou leurs sels ou esters, avec des composés métalliques de Mg, Ca, AI, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K et/ou une base azotée protonée pour obtenir les mélanges correspondants de sel d'acide alkylphosphonique (V) et de sel d'acide dialkylphosphinique (VI) de ces métaux et/ou un composé azoté, (V) (VI), Y représentant Mg, Ca, AI, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K et/ou un composé azoté et n valant ¼, ⅓, ½, 1.
EP11715668A 2010-04-29 2011-04-20 Procédé de production de mélanges de sels d'acides alkylphosphoniques et de sels d'acides dialkylphosphiniques Withdrawn EP2563797A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010018684A DE102010018684A1 (de) 2010-04-29 2010-04-29 Verfahren zur Herstellung von Mischungen aus Alkylphosphonigsäuresalzen und Dialkylphosphinsäuresalzen
PCT/EP2011/002014 WO2011134620A2 (fr) 2010-04-29 2011-04-20 Procédé de production de mélanges de sels d'acides alkylphosphoniques et de sels d'acides dialkylphosphiniques

Publications (1)

Publication Number Publication Date
EP2563797A2 true EP2563797A2 (fr) 2013-03-06

Family

ID=44146877

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11715668A Withdrawn EP2563797A2 (fr) 2010-04-29 2011-04-20 Procédé de production de mélanges de sels d'acides alkylphosphoniques et de sels d'acides dialkylphosphiniques

Country Status (5)

Country Link
US (1) US8889772B2 (fr)
EP (1) EP2563797A2 (fr)
JP (2) JP2013529191A (fr)
DE (1) DE102010018684A1 (fr)
WO (1) WO2011134620A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251523A (zh) * 2017-07-14 2019-01-22 科莱恩塑料和涂料有限公司 阻燃的灰色聚酰胺组合物及其用途

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010018680A1 (de) 2010-04-29 2011-11-03 Clariant International Limited Flammschutzmittel-Stabilisator-Kombination für thermoplastische und duroplastische Polymere
DE102010018682A1 (de) * 2010-04-29 2011-11-03 Clariant International Ltd. Verfahren zur Herstellung von Alkylphosphonigsäuresalzen
DE102010018681A1 (de) 2010-04-29 2011-11-03 Clariant International Ltd. Flammschutzmittel-Stabilisator-Kombination für thermoplastische und duroplastische Polymere
CN103788125B (zh) * 2013-12-31 2015-02-11 邓娟 一种用于聚合物的添加剂及其制备方法
ES2851624T3 (es) * 2014-09-24 2021-09-08 Clariant Int Ltd Composición de catalizador para un procedimiento de fabricación de poliéster
JP6151678B2 (ja) * 2014-10-15 2017-06-21 大和化学工業株式会社 難燃性ポリウレタン樹脂および難燃性合成皮革
DE102015004662A1 (de) * 2015-04-13 2016-10-13 Clariant International Ltd. Verfahren zur Herstellung flammwidriger, nicht korrosiver und stabiler Polyamidformmassen
DE102015223432A1 (de) * 2015-11-26 2017-06-01 Clariant International Ltd Polymere Flammschutzmittelmischungen
DE102016213281A1 (de) * 2016-07-20 2018-01-25 Clariant Plastics & Coatings Ltd Flammschutzmittelmischungen, ihre Herstellung und ihre Verwendung
DE102016213282A1 (de) * 2016-07-20 2018-01-25 Clariant Plastics & Coatings Ltd Flammschutzmittelmischungen, ihre Herstellung und ihre Verwendung
JP6897063B2 (ja) 2016-11-04 2021-06-30 日立金属株式会社 電流センサ
CN111662323A (zh) * 2019-03-07 2020-09-15 黎杰 二烷基次膦酸-烷基亚磷酸金属复合盐,其制备方法和用途
CN111116988B (zh) * 2020-01-07 2020-11-20 威海海润新材料科技有限公司 一种有机磷化物阻燃剂及其制备方法与应用
CN111748203B (zh) * 2020-07-03 2021-11-19 金旸（厦门）新材料科技有限公司 一种己内酰胺原位改性勃姆石协效阻燃增强高温尼龙材料及其制备方法
EP4086302A1 (fr) 2021-05-07 2022-11-09 Clariant International Ltd Combinaison ignifugeant-stabilisant pour polymères thermoplastiques
WO2022236322A1 (fr) * 2021-05-07 2022-11-10 Dupont Polymers, Inc. Composition polymère améliorée
CN115974915A (zh) * 2021-10-15 2023-04-18 中国科学院宁波材料技术与工程研究所 二烷基次膦酸杂化盐及其制备方法、应用
CN115819844B (zh) * 2022-12-05 2024-07-12 金发科技股份有限公司 一种烷基亚膦酸复合盐及其制备方法和应用
WO2024168827A1 (fr) * 2023-02-17 2024-08-22 中国科学院宁波材料技术与工程研究所 Composition de dialkylphosphinate, son procédé de préparation et son utilisation
CN117534702B (zh) * 2024-01-10 2024-04-05 太仓维龙化工有限公司 一种二烷基-单烷基复合次膦酸盐及其快速制备方法

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA738245B (en) 1972-10-25 1974-09-25 Hoechst Ag Flame resistant thermoplastic polyesters
DE2447727A1 (de) 1974-10-07 1976-04-08 Hoechst Ag Schwerentflammbare polyamidformmassen
DE4430932A1 (de) 1994-08-31 1996-03-07 Hoechst Ag Flammgeschützte Polyesterformmasse
BE1008947A3 (nl) 1994-12-01 1996-10-01 Dsm Nv Werkwijze voor de bereiding van condensatieproducten van melamine.
DE19608006A1 (de) 1996-03-04 1997-09-11 Hoechst Ag Salze von phosphonigen Säuren und deren Verwendung als Flammschutzmittel in Kunststoffen
DE19614424A1 (de) 1996-04-12 1997-10-16 Hoechst Ag Synergistische Flammschutzmittel-Kombination für Polymere
TW491843B (en) 1997-03-04 2002-06-21 Nissan Chemical Ind Ltd 1,3,5-triazine derivative salts of polyacids comprising phosphorus, sulfur, and oxygen and process for producing the same
DE19734437A1 (de) 1997-08-08 1999-02-11 Clariant Gmbh Synergistische Flammschutzmittel-Kombination für Polymere
DE19737727A1 (de) 1997-08-29 1999-07-08 Clariant Gmbh Synergistische Flammschutzmittel-Kombination für Kunststoffe
WO1999028328A1 (fr) * 1997-11-28 1999-06-10 Clariant Gmbh Procede pour la preparation d'acides dialkylphosphiniques
DE59809884D1 (de) * 1997-11-28 2003-11-13 Clariant Gmbh Verfahren zur herstellung von salzen der dialkylphosphinsäuren
DE19923743C2 (de) 1999-05-25 2002-03-07 Clariant Gmbh Verfahren zur Herstellung von (Metall)salzen von Alkylphosphonigen Säuren II
DE10241126A1 (de) 2002-09-03 2004-03-25 Clariant Gmbh Flammschutzmittel-Stabilisator-Kombination für thermoplastische Polymere
DE10359815A1 (de) * 2003-12-19 2005-07-28 Clariant Gmbh Verfahren zur Herstellung von Dialkylphosphinsäure-Salzen
DE10359814A1 (de) * 2003-12-19 2005-07-28 Clariant Gmbh Dialkylphosphinsäure-Salze
WO2005105818A1 (fr) 2004-04-23 2005-11-10 Supresta Llc Procede d’alkylation de composes contenant du phosphore
US20060045770A1 (en) 2004-08-24 2006-03-02 Fei-Tyh Chuang Piston rod for oil-less air compressor
US7049463B2 (en) 2004-10-25 2006-05-23 Rhodia Inc. Process for the preparation of highly purified, dialkyl phosphinic acids
CN101218305B (zh) * 2005-07-08 2011-03-23 宝理塑料株式会社 阻燃性树脂组合物
TWI410453B (zh) * 2005-12-01 2013-10-01 Supresta Llc 含二取代膦酸鹽與單取代膦酸鹽之混合物的阻焰性組成物
WO2008051584A2 (fr) 2006-10-25 2008-05-02 Rhodia Inc. Processus pour la préparation de composés dialkyldithiophosphiniques hautement purifiés
DE102007032669A1 (de) * 2007-07-13 2009-01-15 Clariant International Limited Alkylphosphonigsäuren, -salze und -ester, Verfahren zu deren Herstellung und ihre Verwendung
DE102010018682A1 (de) 2010-04-29 2011-11-03 Clariant International Ltd. Verfahren zur Herstellung von Alkylphosphonigsäuresalzen
DE102010018680A1 (de) 2010-04-29 2011-11-03 Clariant International Limited Flammschutzmittel-Stabilisator-Kombination für thermoplastische und duroplastische Polymere
DE102010018681A1 (de) 2010-04-29 2011-11-03 Clariant International Ltd. Flammschutzmittel-Stabilisator-Kombination für thermoplastische und duroplastische Polymere

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011134620A2 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251523A (zh) * 2017-07-14 2019-01-22 科莱恩塑料和涂料有限公司 阻燃的灰色聚酰胺组合物及其用途

Also Published As

Publication number Publication date
WO2011134620A2 (fr) 2011-11-03
US8889772B2 (en) 2014-11-18
JP2016216463A (ja) 2016-12-22
JP2013529191A (ja) 2013-07-18
JP6410759B2 (ja) 2018-10-24
US20130131239A1 (en) 2013-05-23
DE102010018684A1 (de) 2011-11-03
WO2011134620A3 (fr) 2012-03-29

Similar Documents

Publication Publication Date Title
EP2563797A2 (fr) Procédé de production de mélanges de sels d'acides alkylphosphoniques et de sels d'acides dialkylphosphiniques
EP2625220B1 (fr) Combinaisons de stabilisateurs ingnifugeants pour les polymères thermoplastiques
EP2563876B1 (fr) Association agent ignifuge-stabilisateur pour polymères thermoplastiques et thermodurcissables
EP2563877B1 (fr) Association agent ignifuge-stabilisateur pour polymères thermoplastiques et thermodurcissables
US9534109B2 (en) Flame retardant-stabilizer combination for thermoplastic polymers
EP1544205B1 (fr) Procédé pour la préparation de sels d'acides dialkylphosphiniques
EP1832595B1 (fr) Mélanges en sels d'acides dialkyl phosphiniques fonctionnalisés par monocarboxyle et composants complémentaires, un procédé destiné à sa fabrication et à son utilisation
EP2379573B1 (fr) Procédé de production d'acides éthylène-dialkylphosphiniques, de leurs esters et de leurs sels au moyen d'acétylène et leur utilisation
EP2563798A2 (fr) Procédé de production de sels d'acides alkylphosphoniques
DE102004023085A1 (de) Dialkylphosphinsäure-Salze, ein Verfahren zu ihrer Herstellung und ihre Verwendung
WO2018015253A1 (fr) Mélanges ignifuges, leur préparation et leur utilisation
DE102008064012A1 (de) Halogenfreie Addukte von Alkylphosphonigsäurederivaten und diesterbildenden Olefinen, halogenfreie Verfahren zu deren Herstellung und ihre Verwendung
EP3487956A1 (fr) Mélanges ignifuges, leur préparation et leur utilisation

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20121129

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20131024

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

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20140702