Mixtures Of At Least One Dialkylphosphinic Acid With At Least One Other Dialkylphosphinic Acid That Is Different Therefrom, Method For Production Thereof, And Use Thereof

Abstract

The invention relates to a mixture of at least one dialkylphosphinic acid of the formula (I) in which R 1 , R 2 are the same or different and are each C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl, C 7 -C 18 -alkylaryl, with at least one different dialkylphosphinic acid of the formula (II) in which R 3 , R 4 are the same or different and are each C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl and/or C 7 -C 18 -alkylaryl, with the proviso that at least one of the R 3 and R 4 radicals is different than R 1 and R 2 .

1 . A mixture of at least one dialkylphosphinic acid of the formula (I) 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with at least one different dialkylphosphinic acid of the formula (II) 
       
       
         
           
           
               
               
           
         
         wherein 
         R 3 , R 4  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with the proviso that at least one of the R 3  and R 4  radicals is different than R 1  and R 2 . 
       
     
     
         2 . The mixture as claimed in  claim 1 , wherein R 1  and R 2  are the same or different and are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl or phenyl. 
     
     
         3 . The mixture as claimed in  claim 1 , wherein R 3  and R 4  are the same or different and are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl or phenyl, with the proviso that at least one of the R 3  and R 4  radicals is different than R 1  and R 2 . 
     
     
         4 . The mixture as claimed in  claim 1 , comprising 0.1 to 99.9% by weight of the at least one dialkylphosphinic acid of the formula (I) and 99.9 to 0.1% by weight of the at least one different dialkylphosphinic acid of the formula (II). 
     
     
         5 . The mixture as claimed in  claim 1 , comprising 40 to 99.9% by weight of the at least one dialkylphosphinic acid of the formula (I) and 60 to 0.1% by weight of the at least one different dialkylphosphinic acid of the formula (II). 
     
     
         6 . The mixture as claimed in  claim 1 , comprising 60 to 99.9% by weight of the at least one dialkylphosphinic acid of the formula (I) and 40 to 0.1% by weight of the at least one different dialkylphosphinic acid of the formula (II). 
     
     
         7 . The mixture as claimed in  claim 1 , comprising 80 to 99.9% by weight of the at least one dialkylphosphinic acid of the formula (I) and 20 to 0.1% by weight of the at least one different dialkylphosphinic acid of the formula (II). 
     
     
         8 . The mixture as claimed in  claim 1 , comprising 90 to 99.9% by weight of the at least one dialkylphosphinic acid of the formula (I) and 10 to 0.1% by weight of the at least one different dialkylphosphinic acid of the formula (II). 
     
     
         9 . The mixture as claimed in  claim 1 , comprising 95 to 99.9% by weight of the at least one dialkylphosphinic acid of the formula (I) and 5 to 0.1% by weight of the at least one different dialkylphosphinic acid of the formula (II). 
     
     
         10 . The mixture as claimed in  claim 1 , comprising 98 to 99.9% by weight of the at least one dialkylphosphinic acid of the formula (I) and 2 to 0.1% by weight of the at least one different dialkylphosphinic acid of the formula (II). 
     
     
         11 . The mixture as claimed in  claim 1 , wherein the at least one dialkylphosphinic acid is diethylphosphinic acid, ethylpropylphosphinic acid, ethylbutylphosphinic acid, ethylpentylphosphinic acid, ethylhexylphosphinic acid, dipropylphosphinic acid, propylbutylphosphinic acid, propylpentylphosphinic acid, propylhexylphosphinic acid, dibutylphosphinic acid, butylpentylphosphinic acid, butylhexylphosphinic acid, dipentylphosphinic acid, pentylhexylphosphinic acid dihexylphosphinic acid or mixtures thereof. 
     
     
         12 . The mixture as claimed in  claim 1  wherein the at least one dialkylphosphinic acid is diethylphosphinic acid, wherein the at least one different dialkylphosphinic acid is butylethylphosphinic acid and wherein the mixture comprises 98 to 99.9% by weight of diethylphosphinic acid and 2 to 0.1% by weight of butylethylphosphinic acid. 
     
     
         13 . The mixture as claimed in  claim 1 , further comprising at least one synergist, wherein the at least one synergist is a nitrogen-containing compound, melem, melam, melon, melamine borate, melamine cyanurate, melamine phosphate, dimelamine phosphate, pentamelamine triphosphate, trimelamine diphosphate, tetrakismelamine triphosphate, hexakismelamine pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, melon polyphosphate or mixtures thereof;
 aluminum compounds, aluminum hydroxide, halloysite, sapphire products, boehmite, nanoboehmite;   magnesium compounds, magnesium hydroxide;   tin compounds, tin oxides;   antimony compounds, antimony oxides;   zinc compounds, zinc oxide, zinc hydroxide, zinc oxide hydrate, zinc carbonate, zinc stannate, zinc hydroxystannate, zinc silicate, zinc phosphate, zinc borophosphate, zinc borate, zinc molybdate or mixtures thereof;   silicon compounds, silicates, silicones or mixtures thereof;   phosphorus compounds, phosphinic acids and salts thereof, phosphonic acids and salts thereof, phosphine oxides, phosphazenes, piperazine (pyro)phosphates or mixtures thereof;   carbodiimides, piperazines, (poly)isocyanates, styrene-acrylic polymers;   carbonylbiscaprolactam or mixtures thereof;   nitrogen compounds selected from the group consisting of oligomeric esters of tris(hydroxyethyl) isocyanurate with aromatic polycarboxylic acids, or benzoguanamine, acetoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, cyanurates, cyanurate-epoxide compounds, urea cyanurate, dicyanamide, guanidine, guanidine phosphate, sulfate and mixtures thereof.   
     
     
         14 . The mixture as claimed in  claim 1 , comprising 99 to 1% by weight of the mixture of at least one dialkylphosphinic acid of the formula (I) and at least one different dialkylphosphinic acid of the formula (II) and 1 to 99% by weight of a synergist. 
     
     
         15 . A process for preparing a mixture of at least one dialkylphosphinic acid of the formula (I) 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with at least one different dialkylphosphinic acid of the formula (II) 
       
       
         
           
           
               
               
           
         
         wherein 
         R 3 , R 4  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with the proviso that at least one of the R 3  and R 4  radicals is different than R 1  and R 2 , comprising the steps of reacting a phosphorus source with an initiator and an olefin and treating the alkylated phosphorus compound thus obtained with a mineral acid and converting it, by concentration and workup, to a mixture of at least one dialkylphosphinic acid of the formula (I) and at least one different dialkylphosphinic acid of the formula (II). 
       
     
     
         16 . The process as claimed in  claim 15 , wherein the phosphorus source is a phosphinic salt, the olefin is ethylene and the mineral acid is sulfuric acid or hydrochloric acid, and the free-radical initiator is 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride, azobis(isobutyronitrile), 4,4′-azobis(4-cyanopentanoic acid) and/or 2,2′-azobis(2-methylbutyronitrile), hydrogen peroxide, ammonium peroxodisulfate, potassium peroxodisulfate, dibenzoyl peroxide, di-tert-butyl peroxide, peracetic acid, diisobutyryl peroxide, cumene peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-amyl peroxypivalate, dipropyl peroxydicarbonate, dibutyl peroxydicarbonate, dimyristyl peroxydicarbonate, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexylcarbonate, tert-butyl peroxyisobutyrate, 1,1-di(tert-butylperoxy)cyclohexane, tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxydiethylacetate, tert-butyl peroxyisopropylcarbonate, 2,2-di(tert-butylperoxy)butane, tert-amyl hydroperoxide and/er-2,5-dimethyl-2,5-di(tert-butylperoxy)hexane or mixtures thereof. 
     
     
         17 . The process as claimed in  claim 15  further comprising reacting sodium phosphinate with ethylene and then with dilute sulfuric acid, concentrated, filtered and distilled, in order to obtain a mixture of diethylphosphinic acid and butylethylphosphinic acid. 
     
     
         18 . The process as claimed in  claim 15 , wherein the reaction takes place in a solvent and the solvent is an alcohol, acid or water. 
     
     
         19 . The process as claimed in  claim 15 , wherein the reaction temperature is between 50 and 150° C. 
     
     
         20 . An intermediate for further syntheses, a binder, a crosslinker or accelerator in the curing of epoxy resins, polyurethanes and unsaturated polyester resins, a polymer stabilizer, a crop protection composition, a sequestrant, a mineral oil additive, an anticorrosive, a washing composition, a cleaning composition or an electronic composition comprising a mixture of at least one dialkylphosphinic acid of the formula (I) 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with at least one different dialkylphosphinic acid of the formula (II) 
       
       
         
           
           
               
               
           
         
         wherein 
         R 3 . R 4  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with the proviso that at least one of the R 3  and R 4  radicals is different than R 1  and R 2 . 
       
     
     
         21 . A flame retardant, as a flame retardant for clearcoats and intumescent coatings, a flame retardant for wood and other cellulosic products, a reactive and a nonreactive flame retardant for polymers, a flame-retardant polymer molding a flame-retardant for rendering polyester and pure and blended cellulose fabrics flame-retardant by impregnation, or a synergist comprising a mixture of at least one dialkylphosphinic acid of the formula (I) 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with at least one different dialkylphosphinic acid of the formula (II) 
       
       
         
           
           
               
               
           
         
         wherein 
         R 3 , R 4  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with the proviso that at least one of the R 3  and R 4  radicals is different than R 1  and R 2 . 
       
     
     
         22 . A flame-retardant thermoplastic or thermoset polymer molding composition or polymer molding, film, filament or fiber comprising 0.5 to 45% by weight of a mixture of at least one dialkylphosphinic acid of the formula (I) 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with at least one different dialklophosphinic acid of the formula (II) 
       
       
         
           
           
               
               
           
         
         wherein 
         R 3 , R 4  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with the proviso that at least one of the R 3  and R 4  radicals is different than R 1  and R 2 , 0.5 to 99.5% by weight of thermoplastic or thermoset polymer or mixtures thereof, 0 to 55% by weight of additives and 0 to 55% by weight of filler or a reinforcing material, where the sum of the components is 100% by weight. 
       
     
     
         23 . A flame-retardant thermoplastic or thermoset polymer molding composition or polymer molding, film, filament or fiber comprising 1 to 30% by weight of a mixture of at least one dialkylphosphinic acid of the formula (I) 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2  are the same or different and are C 1 -C 18 -alkyl. C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with at least one different dialkylphosphinic acid of the formula (II) 
       
       
         
           
           
               
               
           
         
         wherein 
         R 3 , R 4  are the same or different and are C 1 -C 18 -alkyl, C 2 -C 18 -alkenyl, C 6 -C 18 -aryl or C 7 -C 18 -alkylaryl, 
         with the proviso that at least one of the R 3  and R 4  radicals is different than R 1  and R 2 , 10 to 95% by weight of thermoplastic or thermoset polymer or mixtures thereof, 2 to 30% by weight of additives and 2 to 30% by weight of filler or a reinforcing material, where the sum of the components is 100% by weight.