Polymers of ethylene oxide and carbon dioxide

Abstract

The present disclosure is directed, in part, to methods of synthesizing a poly(ethylene carbonate) polymer from the reaction of ethylene oxide (EO) and carbon dioxide (CO 2 ) in the presence of a metal complex. The present disclosure also provides novel metal complexes. In one aspect, the metal complex is of the formula (I), wherein R 1 , R 2 , R 3 , M, X and Ring A are as defined herein.

1 - 140 . (canceled) 
     
     
         141 . A metal complex of the formula: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium or manganese; 
 X is absent or is a nucleophilic ligand; 
 ring A forms an optionally substituted 5- to 6-membered ring; 
 each R 3  is, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl; 
 R 7  and R 9  are, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl; and 
 
         characterized in that R 9  has a molecular volume at least two times greater than the molecular volume of R 7 . 
       
     
     
         142 . The metal complex of  claim 141 , wherein the molecular volume of R 9  is at least 3 times larger than the molecular volume of R 7 . 
     
     
         143 . The metal complex of  claim 141 , wherein an A-value of R 9  is at least two times larger than an A-value for R 7 . 
     
     
         144 . The metal complex of  claim 141 , wherein the A-value of R 9  is greater than about 2.5 kcal/mol. 
     
     
         145 . The metal complex of  claim 141 , wherein the A-value of R 9  is greater than about 3 kcal/mol. 
     
     
         146 . The metal complex of  claim 141 , wherein the A-value of R 9  is greater than about 4 kcal/mol. 
     
     
         147 . The metal complex of  claim 141 , wherein each R 3  is hydrogen. 
     
     
         148 . The metal complex of  claim 141 , wherein the complex is of the formula: 
       
         
           
           
               
               
           
         
       
     
     
         149 . The metal complex of  claim 141 , wherein M is cobalt or chromium. 
     
     
         150 . The metal complex of  claim 141 , wherein M is cobalt (III). 
     
     
         151 . A method of synthesizing a poly(ethylene carbonate) polymer, the method comprising reacting ethylene oxide and carbon dioxide in the presence of a metal complex of the formula: 
       
         
           
           
               
               
           
         
         wherein:
 M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium or manganese; 
 X is absent or is a nucleophilic ligand; 
 ring A forms an optionally substituted 5- to 6-membered ring; 
 each R 3  is, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl; 
 R 7  and R 9  are, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl; and 
 
         characterized in that R 9  has a molecular volume at least two times greater than the molecular volume of R 7 . 
       
     
     
         152 . The method of  claim 151 , wherein the molecular volume of R 9  is at least 3 times larger than the molecular volume of R 7 . 
     
     
         153 . The method of  claim 151 , wherein an A-value of R 9  is at least two times larger than an A-value for R 7 . 
     
     
         154 . The method of  claim 151 , wherein the A-value of R 9  is greater than about 2.5 kcal/mol. 
     
     
         155 . The method of  claim 151 , wherein the A-value of R 9  is greater than about 3 kcal/mol. 
     
     
         156 . The method of  claim 151 , wherein the A-value of R 9  is greater than about 4 kcal/mol. 
     
     
         157 . The method of  claim 151 , wherein each R 3  is hydrogen. 
     
     
         158 . The method of  claim 151 , wherein the complex is of the formula: 
       
         
           
           
               
               
           
         
       
     
     
         159 . The method of  claim 151 , wherein M is cobalt or chromium. 
     
     
         160 . The method of  claim 151 , wherein M is cobalt (III).