Process for the preparation of dopo-derived compounds and compositions thereof

Abstract

This invention relates to a process for producing compounds derived from 9,10-Dihydro-9-Oxa-10-Phosphaphenantrene-10-oxide (DOPO). In particular, the invention relates to producing DOPO-derived compounds by reacting DOPO with diol compounds in the presence of a catalyst. This invention also relates to DOPO derived composition containing a high melting point diastereomer. The DOPO derived compounds may be useful as flame-retardants.

1 . A process for preparing the compound of Formula I: 
       
         
           
           
               
               
           
         
       
       wherein each R 1 , R 2 , R 3  and R 4  are independently hydrogen, C 1 -C 15  alkyl, C 6 -C 12  aryl, C 7 -C 15  aralkyl or C 7 -C 15  alkaryl; or R 1  and R 2  or R 3  and R 4  taken together can form a saturated or unsaturated cyclic ring, wherein said saturated or unsaturated cyclic ring may be optional substituted by a C 1 -C 6  alkyl; each m is independently 1, 2, 3 or 4; and n is 2 to about 18; comprising reacting a compound of Formula A: 
       
         
           
           
               
               
           
         
       
       wherein R 3 , R 4  and m are defined above; 
       with a diol compound of Formula B in the presence of a catalyst, optionally a solvent, and optionally an entrainer;
   HO—(CH 2 ) n —OH  Formula B
 
 
       wherein n is defined above. 
     
     
         2 . The process of  claim 1 , wherein n is 2 to 6 and R 1 , R 2 , R 3  and R 4  are hydrogen. 
     
     
         3 . A process for preparing the compound of Formula II: 
       
         
           
           
               
               
           
         
       
       comprising reacting a compound of Formula C: 
       
         
           
           
               
               
           
         
       
       with ethylene glycol in the presence of a catalyst, optionally a solvent and optionally an entrainer. 
     
     
         4 . The process of  claim 1 , wherein both the solvent and the entrainer are present. 
     
     
         5 . The process of  claim 1 , wherein said catalyst is an alky halide, alkali halides, alkaline earth metal halides, transition metals and their halides or acid catalysts. 
     
     
         6 . The process of  claim 1 , wherein the temperature of the reaction ranges from about 100° C. to about 250° C. 
     
     
         7 . The process of  claim 1 , wherein the a product of the reaction is water and wherein the water and the diol compound of Formula B or ethylene glycol are continuously recycled back to reactor. 
     
     
         8 . The process of  claim 1 , wherein the catalyst is an acid catalyst. 
     
     
         9 . The compound of Formula I: 
       
         
           
           
               
               
           
         
       
       wherein each R 1 , R 2 , R 3  and R 4  are independently hydrogen, C 1 -C 15  alkyl, C 6 -C 12  aryl, C 7 -C 15  aralkyl or C 7 -C 15  alkaryl; or R 1  and R 2  or R 3  and R 4  taken together can form a saturated or unsaturated cyclic ring, wherein said saturated or unsaturated cyclic ring may be optional substituted by a C 1 -C 6  alkyl; each m is independently 1, 2, 3 or 4; and n is 2 to about 18: produced by the process of  claim 1 . 
     
     
         10 . The compound of Formula II: 
       
         
           
           
               
               
           
         
       
       produced by the process of  claim 3 . 
     
     
         11 . A method for producing a higher melting point composition comprising the compound of Formula II: 
       
         
           
           
               
               
           
         
       
       comprising contacting a composition containing lower amounts of high melting point isomers of Formula II, with alcohols, water, or mixtures thereof in the presence of an acid catalyst, thereby producing a composition containing larger amounts of higher melting point isomers of Formula II. 
     
     
         12 . The composition of  claim 11 , wherein said acid catalyst is sulfuric acid, aryl sulfonic acid, alkyl sulfonic acid, aralkyl sulfonic acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, perchloric acid, trifluoromethane sulfonic acid, fluorosulfonic acid, nitric acid, phosphoric acid, phosphonic acids, phosphinic acids aluminum chloride, diethyl aluminum chloride, triethylaluminum/hydrogen chloride, ferric chloride, zinc chloride, antimony trichloride, stannic chloride, boron trifluoride, acidic zeolites, acidic clays, polymeric sulfonic acids, or mixtures thereof.