Lactide and glycolide(co)polymerization catalytic system

Abstract

A catalytic lactide and glycolide copolymerization system comprising a trifluoromethane sulfonate as a catalyst and copolymerization additive and a copolymerization process.

1 . A catalytic system comprising  
       (a) a trifluoromethanesulfonate of the formula  
       
         
           
           
               
               
           
         
       
       in which 
 R 1  is selected from the group consisting of hydrogen, deuterium atom,  
 -E 14 (R 14 )(R′ 14 )(R″ 14 );  
 E 14  is an element of group 14;  
 R 14 , R′ 14  and R″ 14  are, independently selected from the group consisting of hydrogen, deuterium atom, substituted or non-substituted; alkyl, cycloalkyl and aryl, and in which said substituent or substituents are selected from the group consisting of halo, alkyl, cycloalkyl and aryl,  
 as catalyst, and  
 (b) a (co)polymerization additive of the formula  
   R 2 -E-R 3   (2)  
 in which  
 E is an element of group 16;  
 R 2  is hydrogen or deuterium atom;  
 R 3  is selected from the group consisting of hydrogen, deuterium atom, and  
 -E′ 14  (T 14 )(T′ 14 )(T″ 14 );  
 E′ 14  is an element of group 14;  
 T 14 , T′ 14  and T″ 14  are, independently, hydrogen; deuterium atom; substituted or non-substituted members; alkyl, cycloalkyl and aryl, and in which said substituent or substituents are selected from the group consisting of: halo, hydroxy, alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl, aryloxy, carboxy, alkoxycarbonyl, cycloalkoxycarbonyl and aryloxycarbonyl for lactide and glycolide (co)polymerization.  
 
     
     
         2 . The catalytic system of  claim 1 , wherein the quantity of (co)polymerization additive with respect to the catalyst is between 0.05 and 5 molar equivalents between 0.5 and 2 molar equivalents.  
     
     
         3 . The catalytic system of  claim 1 , wherein the compound of formula (1) is such that R 1  is either hydrogen or -E 14 (R 14 )(R′ 14 )(R″ 14 ).  
     
     
         4 . The catalytic system of  claim 3 , wherein R 1  hydrogen.  
     
     
         5 . The catalytic system of  claim 3 , wherein the compound of formula (1) is such that R 1  is -E 14 (R 14 )(R′ 14 )(R′ 14 ) and E 14  carbon or silicon.  
     
     
         6 . The catalytic system of  claim 5 , wherein E 14  is a carbon atom and R 14 , R′ 14  and R″ 14  represent are, independently, hydrogen or alkyl.  
     
     
         7 . The catalytic system of  claim 1  wherein the compound of formula (2) is such that 
 E is oxygen or sulfur;    R 2  is hydrogen;    R 3  is hydrogen or E′ 14 (T 14 )(T′ 14 )(T″ 14 );    E′ 14  is carbon or silicon;    T 14 , T′ 14  and T″ 14  represent are, independently, selected from the group consisting of hydrogen substituted or non-substituted members selected from the group consisting of alkyl, cycloalkyl and aryl, in which said substituent or substituents are selected from the group consisting of: halo, alkyl, cycloalkyl, phenyl, naphthyl, carboxy and alkoxycarbonyl.    
     
     
         8 . The catalytic system of  claim 7 , wherein 
 E is oxygen;    R 2  is hydrogen;    R 3  is hydrogen or -E′ 14 (T 14 )(T′ 14 )(T″ 14 ) in which    E 14  a is a carbon and T 14 , T′ 14  and T″ 14  are, independently, hydrogen or alkyl.    
     
     
         9 . The catalytic system of  claim 1  wherein the compound of formula (2) is water or an aliphatic alcohol.  
     
     
         10 . The catalytic system of  claim 1  wherein the compound of formula (2) is isopropanol or pentan-1-ol.  
     
     
         11 . A lactide and glycolide (co)polymerization process comprising bringing together the monomer or monomers considered, a catalytic system of  claim 1 , and optionally a polymerization solvent.  
     
     
         12 . The process according to  claim 11 , wherein the temperature is between −20° C. and approximately 150° C.  
     
     
         13 . The process of  claim 12 , wherein the process is carried out in solution at a temperature between 0° C. and 30° C.  
     
     
         14 . The process of  claim 11 , wherein that the reaction time is between a few minutes and 48 hours, and preferably between 30 minutes and 20 hours.  
     
     
         15 . (canceled)  
     
     
         16 . The process of  claim 1  wherein the reaction time is between 30 minutes and 20 hours.  
     
     
         17 . The catalytic system of  claim 2  wherein the amount is between 0.5 and 2 molar equivalents.