Method for producing ester condensed product

Abstract

The present invention is to provide a method for preparing an ester condensate and a catalyst therefor; wherein the method enables synthesis of enormous amounts of ester condensates comprising a specific structure in good yield, by a reaction of carboxylic acid and alcohol in equimolar amounts, while generation of by-products is prevented; wherein the catalyst exhibits good catalytic efficiency as a catalyst for use, the use of the catalyst in small amount is sufficient, and the catalyst is reusable and can be used repeatedly; therefore, the method for preparing an ester condensate of the present invention and the catalyst therefor can be applied to industrial methods which are preferable in view of green chemistry. Esterification reaction is performed by using a catalyst comprising a zirconium(IV) compound and/or a hafnium(IV) compound and an iron compound and a gallium compound. It is preferable that the zirconium(IV) compound is a compound represented by Zr(OH) a (OR 1 ) b , (wherein, R 1 represents an acyl group or an alkyl group, and each of a and b is 0 or any one of integers of 1 to 4 and the relationship of a+b=4 is satisfied), and a zirconium(IV) halide.

1 . A method for preparing an ester condensate, wherein an esterification reaction is carried out using a catalyst containing a zirconium (IV) compound and/or a hafnium(IV) compound and an iron(III) compound and/or a gallium(III) compound.  
   
   
       2 . The method for preparing an ester condensate according to  claim 1 , wherein the zirconium (IV) compound is a compound represented by a general formula (1):  
       Zr(OH) a (OR 1 ) b   (1)  
     (wherein, R 1  represents an acyl group or an alkyl group, and each of a and b is 0 or any one of integers of 1 to 4 and the relationship of a+b=4 is satisfied).  
   
   
       3 . The method for preparing an ester condensate according to  claim 1 , wherein the zirconium (IV) compound is a compound represented by a general formula (3):  
       ZrX 4 Y e   (3)  
     (wherein X represents a halogen atom, Y represents tetrahydrofuran, and e represents 0 or 2).  
   
   
       4 . The method for preparing an ester condensate according to  claim 1 , wherein the hafnium (IV) compound is a compound represented by a general formula (2):  
       Hf(OH) c (OR 2 ) d   (2)  
     (wherein, R 2  represents an acyl group or an alkyl group, and each of c and d is 0 or any one of integers of 1 to 4 and the relationship of c+d=4 is satisfied).  
   
   
       5 . The method for preparing an ester condensate according to  claim 1 , wherein the hafnium (IV) compound is a compound represented by a general formula (4):  
       HfX 4 Y f   (4)  
     (wherein X represents a halogen atom, Y represents tetrahydrofuran, and f represents 0 or 2).  
   
   
       6 . The method for preparing an ester condensate according to any one of  claims 1  to  5 , wherein the iron compound is iron(III) alkoxide, and the gallium compound is gallium(III) alkoxide.  
   
   
       7 . The method for preparing an ester condensate according to any one of  claims 1  to  6 , wherein the abundance of the iron compound is 5 mol % or more in relation to the zirconium (IV) compound and/or the hafnium (IV) compound.  
   
   
       8 . The method for preparing an ester condensate according to any one of  claims 1  to  7 , wherein the esterification reaction is carried out by heating to ref lux with a solvent, and removing azeotropic water from a reaction system.  
   
   
       9 . The method for preparing an ester condensate according to  claim 8 , wherein a nonpolar or a low-polar solvent is used as the solvent.  
   
   
       10 . The method for preparing an ester condensate according to  claim 9 , wherein the nonpolar or the low-polar solvent is one or more of solvents selected from the group of toluene, xylene, mesitylene, or anisole.  
   
   
       11 . The method for preparing an ester condensate according to any one of  claims 1  to  10 , wherein an ionic liquid is added to the reaction system after the esterification reaction is finished, ester is obtained from an organic layer, and then an ionic liquid layer per se is used as a catalytic solution.  
   
   
       12 . The method for preparing an ester condensate according to  claim 11 , wherein the ionic liquid is 1-butyl-3-methyl imidazolium trifluoromethanesulfonimide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate.  
   
   
       13 . The method for preparing an ester condensate according to  claim 11 , wherein the ionic liquid is N-alkylpyridinium trifluoromethane sulfonate imide.  
   
   
       14 . The method for preparing an ester condensate according to any one of  claims 1  to  10 , wherein a hydrochloric acid aqueous solution is added to the reaction system after the esterification reaction is finished, ester is obtained from an organic layer, and then an aqueous layer per se is used as a catalytic solution.  
   
   
       15 . The method for preparing an ester condensate according to any one of  claims 11  to  14 , wherein the low-polar organic solvent such as toluene and heptane is used as the solvent.  
   
   
       16 . The method for preparing an ester condensate according to any one of  claims 1  to  15 , wherein the esterification reaction is a reaction of carboxylic acid and alcohol.  
   
   
       17 . A catalyst for preparing an ester condensate, which is used in the esterification reaction and which contains a zirconium (IV) compound and/or a hafnium (IV) compound, and an iron compound and/or a gallium compound.  
   
   
       18 . The catalyst for preparing an ester condensate according to  claim 17 , wherein the zirconium (IV) compound is a compound represented by a general formula (1):  
       Zr(OH) a (OR 1 ) b   (1)  
     (wherein, R 1  represents an acyl group or an alkyl group, and each of a and b is 0 or any one of integers of 1 to 4 and the relationship of a+b=4 is satisfied).  
   
   
       19 . The catalyst for preparing an ester condensate according to  claim 17 , wherein the zirconium (IV) compound is a compound represented by a general formula (3):  
       ZrX 4 Y e   (3)  
     (wherein X represents a halogen atom, Y represents tetrahydrofuran, and e represents 0 or 2).  
   
   
       20 . The catalyst for preparing an ester condensate according to  claim 17 , wherein the hafnium (IV) compound is a compound represented by a general formula (2):  
       Hf(OH) c (OR 2 ) d   (2)  
     (wherein, R 2  represents an acyl group or an alkyl group, and each of c and d is 0 or any one of integers of 1 to 4 and the relationship of c+d=4 is satisfied).  
   
   
       21 . The catalyst for preparing an ester condensate according to  claim 17 , wherein the hafnium (IV) compound is a compound represented by a general formula (4):  
       ZrX 4 Y f   (4)  
     (wherein X represents a halogen atom, Y represents tetrahydrofuran, and f represents 0 or 2).  
   
   
       22 . The catalyst for preparing an ester condensate according to any one of  claims 17  to  21 , wherein the iron compound is iron(III) alkoxide, and the gallium compound is gallium(III) alkoxide.  
   
   
       23 . The catalyst for preparing an ester condensate according to any one of  claims 17  to  22 , wherein an abundance of the iron compound is 5 mol % or more in relation to the zirconium (IV) compound and/or the hafnium (IV) compound.  
   
   
       24 . The catalyst for preparing an ester condensate according to any one of  claims 17  to  23 , wherein an ionic liquid is added to the reaction system after the esterification reaction is finished, ester is obtained from an organic layer, and then an ionic liquid layer per se is used.  
   
   
       25 . The catalyst for preparing an ester condensate according to  claim 24 , wherein the ionic liquid is 1-butyl-3-methyl imidazolium trifluoromethanesulfonimide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate.  
   
   
       26 . The catalyst for preparing an ester condensate according to  claim 24 , wherein the ionic liquid is N-alkylpyridinium trifluoromethane sulfonate imide.  
   
   
       27 . The catalyst for preparing an ester condensate according to any one of  claims 17  to  23 , wherein a hydrochloric acid aqueous solution is added to the reaction system after the esterification reaction is finished, ester is obtained from an organic layer, and then an aqueous layer per se is used as a catalytic solution.  
   
   
       28 . The catalyst for preparing an ester condensate according to any one of  claims 17  to  27 , wherein the esterification reaction is a reaction of carboxylic acid and alcohol.