Modified acidic ion-exchange resin and method for preparing bisphenol

Abstract

The present invention provides an ion-exchange resin catalyst, as a catalyst for preparing bisphenol from phenol compounds and ketone, which has a higher selectivity to bisphenol and a longer life time, as compared to a conventional ion-exchange resin, and a method for preparing the same. The present invention also provides a method for preparing bisphenol comprising reacting phenol compounds with ketone, wherein the modified acidic ion-exchange resin in which at least one kind of cationic compound selected from the following (a), (b), (c) and (d) ionically binds to an acidic functional group, is used as a catalyst: (a) a quaternary phosphonium ion, (b) a quaternary ammonium ion, (c) a bis(phosphoranylidene) ammonium ion, and (d) an N-substituted nitrogen-containing aromatic cation.

1 . A modified acidic ion-exchange resin wherein at least one kind of cationic compound selected from the following (A), (B), (C) and (D) ionically binds to an acidic functional group of an acidic ion-exchange resin: 
 (A) A cationic compound represented by the formula (1):                          wherein P represents a phosphorus atom; and R 1 , R 2 , R 3  and R 4  independently represent a hydrogen atom, or an alkyl group, an aryl group or an alkoxy group, each of which contains 1 to 20 carbon atoms and does not contain any of a mercapto group and a precursor thereof, provided that at least one of R 1 , R 2 , R 3  and R 4  is a group other than a hydrogen atom;    (B) A cationic compound represented by the formula (2):                          wherein N represents a nitrogen atom; and R 1 , R 2 , R 3  and R 4  independently represent an alkyl group or an aryl group, each of which contains 1 to 20 carbon atoms and does not contain any of a mercapto group, a precursor thereof and an amide bond;    (C) A cationic compound represented by the formula (3):                          wherein P represents a phosphorus atom; and R 1 , R 2 , R 3 , R 4 , R 5  and R 6  independently represent a hydrogen atom, or an alkyl group, an aryl group or an alkoxy group, each of which contains 1 to 20 carbon atoms and does not contain any of a mercapto group, a precursor thereof and an amide bond, provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5  and R 6  is a group other than a hydrogen atom; and    (D) A cationic N-substituted nitrogen-containing aromatic compound which does not contain any of a mercapto group, a precursor thereof and an amide bond.    
     
     
         2 . The modified acidic ion-exchange resin according to  claim 1 , wherein 0.1 to 50 mole % of the total acidic functional groups which are present in the acidic ion-exchange resin tonically bind with the cationic compound.  
     
     
         3 . The modified acidic ion-exchange resin according to  claim 1  or  2 , wherein the acidic ion-exchange resin is one in which a sulfone group is introduced into a styrene polymer and/or a styrene-divinylbenzene copolymer.  
     
     
         4 . A catalyst for preparing bisphenol, comprising the modified acidic ion-exchange resin according to  claim 1  or  2 .  
     
     
         5 . A method for preparing bisphenol comprising reacting phenol compounds with ketone and/or aldehyde, wherein the modified acidic ion-exchange resin according to  claim 1  or  2  is used as a catalyst.  
     
     
         6 . A method for preparing bisphenol comprising reacting phenol compounds with ketone and/or aldehyde, wherein one in which a nitrogen-containing compound containing a mercapto group, further ionically binds to the modified acidic ion-exchange resin according to  claim 1  or  2 , is used as a catalyst.  
     
     
         7 . A method for preparing bisphenol comprising reacting phenol compounds with ketone and/or aldehyde, wherein at least one compound containing a mercapto group is allowed to coexist in reaction raw materials and the modified acidic ion-exchange resin according to  claim 1  or  2  is used as a catalyst.  
     
     
         8 . A method for preparing bisphenol comprising reacting phenol compounds with ketone, wherein the modified acidic ion-exchange resin in which at least one kind of cationic compound selected from the following (A), (B), (C) and (D) tonically binds to an acidic functional group of an acidic ion-exchange resin, is used as a catalyst: 
 (A) A cationic compound represented by the formula (1):                          wherein P represents a phosphorus atom; and R 1 , R 2 , R 3  and R 4  independently represent a hydrogen atom, or an alkyl group, an aryl group or an alkoxy group, each of which contains 1 to 20 carbon atoms and does not contain a mercapto group and/or a precursor thereof, provided that at least one of R 1 , R 2 , R 3  and R 4  is a group other than a hydrogen atom;    (B) A cationic compound represented by the formula (2):                          wherein N represents a nitrogen atom; and R 1 , R 2 , R 3  and R 4  independently represent an alkyl group or an aryl group, each of which contains 1 to 20 carbon atoms and does not contain a mercapto group and/or a precursor thereof;    (C) A cationic compound represented by the formula (3):                          wherein P represents a phosphorus atom; and R 1 , R 2 , R 3 , R 4 , R 5  and R 6  independently represent a hydrogen atom, or an alkyl group, an aryl group or an alkoxy group, each of which contains 1 to 20 carbon atoms and does not contain a mercapto group and/or a precursor thereof, provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5  and R 6  is a group other than a hydrogen atom; and    (D) A cationic N-substituted nitrogen-containing aromatic compound which does not contain a mercapto group and/or a precursor thereof.    
     
     
         9 . The method for preparing bisphenol according to  claim 8 , wherein 0.1 to 50 mole % of the total acidic functional groups which are present in the acidic ion-exchange resin, ionically bind with the cationic compound.  
     
     
         10 . The method for preparing bisphenol according to  claim 8  or  9 , wherein the acidic ion-exchange resin is one which a sulfone group is introduced into a styrene polymer and/or a styrene-divinylbenzene copolymer.  
     
     
         11 . A method for preparing bisphenol comprising reacting phenol compounds with ketone, wherein one which a nitrogen-containing compound containing a mercapto group, further ionically binds to the modified acidic ion-exchange resin according to  claim 8  or  9 , is used as a catalyst.  
     
     
         12 . The method for preparing bisphenol according to  claim 8  or  9 , wherein at least one compound containing a mercapto group is allowed to coexist in reaction raw materials.  
     
     
         13 . The method for preparing bisphenol according to  claim 8  or  9 , wherein the ketone is acetone, and the phenol compounds are phenol.