Phosphoric ester preparations with reduced hygroscopicity

Abstract

The present invention relates to phosphoric ester preparations with reduced hygroscopicity, to use of these as flame retardants and hydraulic fluids, and to polyurethanes which comprise the phosphoric ester preparations of the invention.

What is claimed is: 
     
         1 . A phosphoric ester preparation which comprises
 i) an oligomer mixture a) comprising at least three poly(alkylene phosphates) corresponding to the formula (I)   
       
         
           
           
               
               
           
         
         
           in which 
         
         R 1 , R 2 , R 3  and R 4  are respectively mutually independently a straight-chain or branched C 1 - to C 8 -alkyl moiety or a straight-chain or branched C 1 - to C 4 -alkoxyethyl moiety, 
         A is a straight-chain, branched and/or cyclic C 4 - to C 20 -alkylene moiety, or 
         A is a moiety of the formula —CH 2 —CH═CH—CH 2 —, a moiety of the formula —CH 2 —C≡C—CH 2 —, a moiety of the formula —CHR 5 —CHR 6 —(O—CHR 7 —CHR 8 ) a —, a moiety of the formula —CHR 5 —CHR 6 —S(O) b —CHR 7 —CHR 8 — or a moiety of the formula —(CHR 5 —CHR 6 —O) c —R 9 —(O—CHR 7 —CHR 8 ) d —,
 in which 
 a is an integer from 1 to 5, 
 b is an integer from 0 to 2, 
 c and d are mutually independently an integer from 1 to 5, 
 
         R 5 , R 6 , R 7  and R 8  are mutually independently H or methyl, 
         R 9  is a moiety of the formula —CH 2 —CH═CH—CH 2 —, a moiety of the formula —CH 2 —C≡C—CH 2 —, a 1,2-phenylene moiety, a 1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the formula (II) 
       
       
         
           
           
               
               
           
         
         a moiety of the formula (III) 
       
       
         
           
           
               
               
           
         
         a moiety of the formula (IV) 
       
       
         
           
           
               
               
           
         
         or a moiety of the formula —C(═O)—R 12 —C(O)—, 
         where 
         R 10  and R 11  are respectively mutually independently H or C 1 - to C 4 -alkyl or R 10  and R 11  together are an optionally alkyl-substituted ring having from 4 to 8C atoms, 
         R 12  is a straight-chain, branched and/or cyclic C 2 - to C 8 -alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, or a 1,4-phenylene moiety, and 
         n is an integer from 0 to 100, 
         with the proviso that the at least three poly(alkylene phosphates) of the formula (I) differ from one another at least in the number n of the repeating units, and 
         the average value of the number of the repeating units  n  of the at least three poly(alkylene phosphates) of the formula (I) is greater than L10 and smaller than 2.00, 
         and 
         ii) at least one phosphoric ester b) with solubility of less than 3.0 g/l in water at 25° C. 
       
     
     
         2 . The phosphoric ester preparations according to  claim 1  in which the oligomer mixture
 a) comprises at least three poly(alkylene phosphates) of the formula (I), 
 in which 
 R 1 , R 2 , R 3  and R 4  are respectively mutually independently a straight-chain or branched C 1 - to C 4 -alkyl moiety or a C 1 - or C 2 -alkoxyethyl moiety, 
 A is a straight-chain or branched C 4 - to C 10 -alkylene moiety, or 
 A is a moiety of the formula —CH 2 —CH═CH—CH 2 —, a moiety of the formula —CH 2 —C≡C'CH 2 —, a moiety of the formula —CHR 5 —CHR 6 —(O—CHR 7 —CHR 8 ) a —, a moiety of the formula —CHR 5 —CHR 6 —S(O) b —CHR 7 —CHR 8 — or a moiety of the formula —(CHR 5 —CHR 6 —O) c —R 9 —(O—CHR 7 —CHR 8 ) d —,
 in which 
 a is an integer from 1 to 5, 
 b is an integer from 0 to 2, 
 c and d are mutually independently an integer from 1 to 5, 
 
 R 5 , R 6 , R 7  and R 8  are mutually independently H or methyl, 
 R 9  is a moiety of the formula —CH 2 —CH═CH—CH 2 —, a moiety of the formula —CH 2 —C≡C—CH 2 —, a 1,2-phenylene moiety, a 1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the formula (II) 
 
       
         
           
           
               
               
           
         
         a moiety of the formula (III) 
       
       
         
           
           
               
               
           
         
         a moiety of the formula (IV) 
       
       
         
           
           
               
               
           
         
         or a moiety of the formula —C(O)—R 12 —C(═O)—, 
         where 
         R 10  and R 11  are respectively mutually independently H or C 1 - or C 2 -alkyl, 
         R 12  is a straight-chain or branched C 2 - to C 6 -alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, or a 1,4-phenylene moiety, and 
         n is an integer from 0 to 100. 
       
     
     
         3 . The phosphoric ester preparations according to  claim 1  in which the oligomer mixture
 a) comprises at least three poly(alkylene phosphates) of the formula (I) 
 in which 
 R 1 , R 2 , R 3  and R 4  are respectively mutually independently a straight-chain or branched C 1 - to C 4 -alkyl moiety or an n-butoxyethyl moiety, 
 A is a straight-chain C 4 - to C 6 -alkylene moiety, or 
 A is a moiety of the formula —CH 2 —CH═CH—CH 2 —, a moiety of the formula —CH 2 —C≡C—CH 2 —, a moiety of the formula —CHR 5 —CHR 6 —(O—CHR 7 —CHR 8 ) a —, a moiety of the formula —CHR 5 —CHR 6 —S(O) b —CHR 7 —CHR 8 — or a moiety of the formula —(CHR 5 —CHR 6 —O) c —R 9 —(O—CHR 7 —CHR 8 ) d —,
 in which 
 a is an integer from 1 to 5, 
 b is an integer from 0 to 2, 
 c and d are mutually independently an integer from 1 to 5, 
 R 5 , R 6 , R 7  and R 8  are mutually independently H or methyl, 
 
 R 9  is a moiety of the formula —CH 2 —CH═CH—CH 2 —, a moiety of the formula —CH 2 —C≡C—CH 2 —, a 1,2-phenylene moiety, a 1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the formula (II) 
 
       
         
           
           
               
               
           
         
         a moiety of the formula (III) 
       
       
         
           
           
               
               
           
         
         a moiety of the formula (IV) 
       
       
         
           
           
               
               
           
         
         or a moiety of the formula —C(═O)—R 12 —C(═O)—,
 where 
 R 10  and R 11  are respectively mutually independently H or C 1 - or C 2 -alkyl, 
 R 12  is a straight-chain or branched C 2 - to C 6 -alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, or a 1,4-phenylene moiety, and 
 n is an integer from 0 to 100. 
 
       
     
     
         4 . The phosphoric ester preparations according to  claim 1  in which the oligomer mixture a) comprises at least three poly(alkylene phosphates) of the formula (I)
 in which 
 R 1 , R 2 , R 3  and R 4  are identical and are ethyl, n-propyl, isopropyl, n-butyl, isobutyl or n-butoxyethyl, 
 A is a straight-chain C 4 - to C 6 -alkylene moiety, or 
 A is a moiety of the formulae 
 
       
         
           
           
               
               
           
         
         A is a moiety —CHR 5 —CHR 6 —(O—CHR 7 —CHR 8 ) a —, in which a is an integer from 1 to 2 and R 5 , R 6 , R 7  and R 8  are identical and are H, or is a moiety —(CHR 5 —CHR 6 —O) c —R 9 —(O—CHR 7 —CHR 8 ) d —, in which c and d are mutually independently an integer from 1 to 2, R 5 , R 6 , R 7  and R 8  are identical and are H, R 9  is a moiety of the formula (II), where R 10  and R 11  are identical and are methyl,
 and 
 n is an integer from 0 to 20. 
 
       
     
     
         5 . The phosphoric ester preparations according to  claim 1  in which the phosphoric esters b) correspond to the formula (VIII) 
       
         
           
           
               
               
           
         
         in which 
         R 13 , R 14 , R 15  and R 16  are respectively mutually independently straight-chain or branched C 4 - to C 12 -alkyl, C 4 - to C 12 -alkoxyalkyl, C 3 - to C 12 -chloroalkyl, C 3 - to C 12 -dichloroalkyl or optionally mono- or poly-C 1 - to C 4 -alkyl-substituted C 6 - to C 10 -aryl, 
         X is a C 4 - to C 8 -alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, a 1,4-phenylene moiety or a moiety of the formula (II), 
       
       
         
           
           
               
               
           
         
         in which R 10  and R 11  are defined as in  claim 1 , 
         and 
         m is 0 or 1. 
       
     
     
         6 . The phosphoric ester preparations according to  claim 1  in which the phosphoric esters b) are selected from the group of triphenyl phosphate, diphenyl cresyl phosphate, tricresyl phosphate, isopropylated or butylated aryl phosphates, bisphenol A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), hydroquinone bis(diphenyl phosphate), neopentyl glycol bis(d(phenyl phosphate), triisobutyl phosphate, tributoxyethyl phosphate, tris(chloroisopropyl)phosphate and tris(dichloropropyl)phosphate. 
     
     
         7 . The phosphoric ester preparation according to  claim 1  in which the materials are liquids with dynamic viscosity from 20 to 5000 mPas at 23° C. 
     
     
         8 . The phosphoric ester preparation according to  claim 1  in which comprises from 30 to 70% by weight, preferably from 40 to 60% by weight, of the oligomer mixture a) and from 30 to 70% by weight, preferably from 40 to 60% by weight, of at least one phosphoric ester b), based on the entire preparation. 
     
     
         9 . The phosphoric ester preparation according to  claim 1  in which comprises one or more auxiliaries selected from the group of the solvents, antioxidants, stabilizers and colorants. 
     
     
         10 . A process for the production of the phosphoric ester preparation according to  claim 1  in which in oligomer mixture a) according to  claim 1  and at least one phosphoric ester b) according to  claim 1  are mixed with one another optionally in the presence of one or more auxiliaries. 
     
     
         11 . The use of the phosphoric ester preparation according to  claim 1  as flame retardant. 
     
     
         12 . The use according to  claim 11  in which the phosphoric ester preparation is used as flame retardant for polyurethanes. 
     
     
         13 . The use according to  claim 12  in which the polyurethanes are foams, preferably flexible polyurethane foams based on polyether polyols or on polyester polyols. 
     
     
         14 . A flame retardant preparation comprising at least one phosphoric ester preparation according to  claim 1 , one or more flame retardants different from the phosphoric ester preparation and optionally one or more auxiliaries. 
     
     
         15 . A polyurethane comprising a phosphoric ester preparation according to at least one of  claim 1 . 
     
     
         16 . A polyurethane foam, preferably a flexible polyurethane foams based on polyether polyols or on polyester polyols, comprising a phosphoric ester preparation according to  claim 1 . 
     
     
         17 . A process for the production of a polyurethane according to  claim 15  in which organic polyisocyanates are reacted, in the presence of a phosphoric ester composition according to at least one of  claim 1  and in the presence of conventional blowing agents, stabilizers, activators and/or other conventional auxiliaries and additives, at a temperature from 20 to 80° C., with compounds having at least 2 hydrogen atoms reactive towards isocyanates. 
     
     
         18 . The process according to  claim 17  in which the quantity used of the phosphoric ester preparation is from 0.5 to 30 parts by weight, preferably from 3 to 25 parts by weight, based on 100 parts by weight of polyol component. 
     
     
         19 . The use of the polyurethanes according to  claim 15  in furniture cushioning, textile inlays, mattresses, vehicle seats, armrests, components, seat cladding and dashboard cladding, cable sheathing, gaskets, coatings, lacquers, adhesives, adhesion promoters and fibres. 
     
     
         20 . A hydraulic fluid comprising a phosphoric ester preparation according to  claim 1 . 
     
     
         21 . A process for reducing the hygroscopicity of poly(alkylene phosphates i) in which the poly(alkylene phosphate) is combined with from 40 to 230% by weight, based on the mass of the poly(alkylene phosphate), at least one phosphoric ester with solubility of less than 3.0 g/l in water at 25° C., and the mixture is homogenized. 
     
     
         22 . The process according to  claim 21  in which the poly(alkylene phosphates) are an oligomer mixture a) according to  claim 1 .