Phosphorus-borates with low melting points

Abstract

The present invention relates to phosphorous borates, methods for their preparation and to the use of these salts in primary batteries, secondary batteries, capacitors, supercapacitors and/or galvanic cells. Furthermore, the present invention relates to the use of these salts as hydraulic liquid, conducting salt, catalyst, solvent, electrolyte or starting compound.

1 . Salts of the general formula [I],  
         [PR 1 R 2 R 3 R 4 ] + [B(OR 5 ) n (OR 6 ) m (OR 7 ) o (OR 8 ) p ] −   [I] 
       wherein 
 R 1 , R 1 , R 3 , R 4  denote, in each case independently of one another, a C 1-20  linear, branched or cyclic, saturated or unsaturated aliphatic radical or a C 6-20 -aromatic or heteroaromatic radical,  
 wherein the aliphatic, aromatic or heteroaromatic radicals may comprise one or more ether functional groups and/or may be further substituted, preferably further substituted by at least one radical of the formula —C q F (2q+1−x) H x , wherein 1≦q≦6 and 0≦x≦2q+1,  
 R 5 , R 6 , R 7  and R 8  denote, in each case independently of one another, a C 6-20  aromatic or heteroaromatic radical, that may be further substituted by at least one halogen-radical, preferably a F- or Cl-radical and/or at least one radical of the formula —C q F (2q+1−x) H x , wherein 1≦q≦6 and 0≦x≦2q+1,  
 or a C 1-8 , linear, branched or cyclic, saturated or unsaturated, aliphatic radical, that may be further substituted by at least one halogen-radical, preferably a F- or Cl-radical and/or at least one radical of the formula —N(C q F (2q+1−x) H x ) 2 , —O(C q F (2q+1−x) H x ), —SO 2  (C q F (2q+1−x) H x ) or —C q F (2q+1−x) H x , wherein 1≦q≦6 and 0≦x≦2q+1,  
 or a carboxylic-, dicarboxylic- or hydroxycarboxylic, linear, branched or cyclic, saturated or unsaturated C 1-8 -aliphatic or C 6-20 -aromatic or heteroaromatic radical that may be further substituted by at least one halogen-radical, preferably a F- or Cl-radical and/or at least one radical of the formula —N(C q F (2q+1−x) H x ) 2 , —O(C q F (2q+1−x) H x ), —SO 2  (C q F (2q+1−x) H x ) or —C q F (2q+1−x) H x , wherein 1≦q≦6 and 0≦x≦2q+1,  
 and wherein  
 at least two of the radicals R 1 , R 2 , R 3 , R 4  may be bound to each other by single or double bonds, and/or  
 at least two of the radicals R 5 , R 6 , R 7 , R 8  may be bound to each other by single or double bonds,  
 and 0≦n, m, o, p≦4 and m+n+o+p=4  
 and wherein the following salts are disclaimed:  
 Bis[salicylato(2-)]borate (III)-tetrabutylphosphonium,  
 Tetrakis[1-naphthalenolato(1-)]-borate-tetraphenylphosphonium,  
 Bis[2-hydroxybenzoato(2-)]-borate-tetrabutylphosphonium,  
 Bis[1,2-benzodiolato(2-), O,O′]-borate-tetraphenylphosphonium,  
 Tetrabutoxy(1-)borate-tetraphenylphosphonium,  
 Tetrakis(1,1′biphenyl-4,4′-diolato)-borate-tetraphenylphosphonium,  
 Bis[2,3-naphthalendiolato(2-) O,O′]-borate-tetraphenylphosphonium.  
 
     
     
         2 . Salts according to  claim 1 , characterized in that at least two of the radicals R 1 , R 2 , R 3 , R 4  are identical and/or bound to each other by single or double bonds.  
     
     
         3 . Salts according to  claim 1 , characterized in that at least two of the radicals R 5 , R 6 , R 7 , R 8  are identical and/or bound to each other by single or double bonds.  
     
     
         4 . Salts according to  claim 1 , characterized in that at least one of the radicals, R 5 , R 6 , R 7  and R 8  denotes, in each case independently of one another, a radical selected from the group consisting of phenyl-, naphthyl-, anthracenyl, phenanthrenyl, pyridyl-, pyracyl- or pyrimidyl-radicals, that may be further substituted by at least one halogen radical, preferably a F- or Cl-radical and/or at least one radical of the formula —C q F (2q+1−x) H x , wherein 1≦q≦6 and 0≦x≦2q+1.  
     
     
         5 . Salt according to  claim 1 , wherein at least one of the radicals R 1 , R 2 , R 3 , R 4  denotes phenyl or C 1-20 -alkyl, preferably C 6 H 13 - oder C 14 H 29 -alkyl.  
     
     
         6 . Salt according to  claim 1 , wherein at least two of the radicals R 5 , R 6 , R 7  or R 8  denote a 2,2′-biphenyl-diolato(2′)O,O′-, a 1,2-benzen-diolato(2-) O,O′- or a salicylato(2-)-radical.  
     
     
         7 . Salt according to  claim 1 , wherein [B(OR 5 ) n (OR 6 ) m (OR 7 ) o (OR 8 ) p ] −  denotes bis[2,2′-biphenyl-diolato(2′)O,O′]-borate, bis[1,2-benzen-diolato(2-)O,O′]-borate or bis[salicylato(2-)]-borate.  
     
     
         8 . Method for the preparation of salts, wherein a salt of the general formula [II] 
         [PR 1 R 2 R 3 R 4 ] a   + A a−   [II] 
       and a salt of the general formula [III] 
         K b+ [B(OR 5 ) n (OR 6 ) m (OR 7 ) o (OR 8 ) p ] b   −   [III] 
       wherein 
 A −  denotes an anion, a=1 to 3, preferably a=1, more preferably an anion chosen from Cl, Br or I,  
 K +  denotes a cation, b=1 to 3, preferably b=1, more preferably a cation chosen from H, Li, K, Na, Ag or NR 1   4   + ,  
 and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8  , n, m, o, p, have the meanings according to  claim 1 , are disolved in a suitable solvent and mixed and the resulting salt is isolated and/or purified.  
 
     
     
         9 . Method according to  claim 8 , wherein the resulting salt is purified by separating the byproduct K + A −  by precipitation, ionic exchange chromatography or by evaporation, if K +  denotes hydrogen.  
     
     
         10 . Method according to  claim 8 , wherein the suitable solvent is acetonitrile or THF (tetrahydrofurane) or a mixture of at least two of these solvents.  
     
     
         11 . Method according to  claim 8 , wherein the suitable solvent is an aprotic solvent, preferably acetonitrile or THF (tetrahydrofurane) or a mixture of at least two aprotic solvents, wherein the resulting salt K + A −  is unsoluble.  
     
     
         12 . Method according to  claim 8  wherein the mixing of the salts of formula [II] and [III] is performed at a temperature of 0 to 100° C., preferably 0 to 50° C., more preferably 10 to 40° C.  
     
     
         13 . Method according to  claim 8 , wherein the reaction is carried out in a solvent or solvent mixture that is directly suitable for use in a secondary or primary battery, a capacitor, a supercapacitor or a galvanic cell.  
     
     
         14 . Method according to  claim 13 , wherein the solvent is an organic carbonate, preferably an ethylenecarbonate, propylenecarbonate, butylene-carbonate, dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate, methylpropylcarbonate or a mixture of at least two of these solvents.  
     
     
         15 . Use of at least one of the salts according to  claim 1  alone or in combination with further salts and/or additives in primary batteries, secondary batteries, capacitors, supercapacitors and/or galvanic cells.  
     
     
         16 . Electrolyte, preferably for primary batteries, secondary batteries, capacitors, supercapacitors and/or galvanic cells, comprising at least one compound of the general formula [I] according to  claim 8 .  
     
     
         17 . Electrolyte according to  claim 16 , wherein the salt concentration of the electrolyte is 0.01-3 mol/l, preferably 0.01-2 mol/l, most preferably 0.1-1.5 mol/l.  
     
     
         18 . Primary battery comprising at least one compound of the general formula [I] according to  claim 1 .  
     
     
         19 . Secondary battery comprising at least one compound of the general formula [I] according to  claim 1 .  
     
     
         20 . Capacitor comprising at least one compound of the general formula [I] according to  claim 1 .  
     
     
         21 . Supercapacitor comprising at least one compound of the general formula [I] according to  claim 1 .  
     
     
         22 . Galvanic cell comprising at least one compound of the general formula [I] according to  claim 1 .  
     
     
         23 . Hydraulic liquid comprising at least one compound of the general formula [I] according to  claim 1 .  
     
     
         24 . Use of a salt according to  claim 1  as an ionic liquid or as a conducting salt in an electrolyte of electrochemical devices.  
     
     
         25 . Use of a salt according to  claim 1  as a catalyst, solvent, electrolyte or starting compound for the preparation of organic compounds.