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 formula (I), wherein R 1 , R 2 , R 3 , M, X and Ring A are as defined herein.

1 . A method of synthesizing a poly(ethylene carbonate) polymer, comprising a step of reacting ethylene oxide and carbon dioxide in the presence of a metal complex, wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 the poly(ethylene carbonate) polymer is made up of Y, and optionally Z, and wherein the percentage of Y is greater than the percentage of Z, 
 
       
         
           
           
               
               
           
         
         M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium or manganese; 
         X is absent or is a nucleophilic ligand; 
         each instance of R 1 , R 2 , and R 3  is, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl, or R 1  and R 2 , or R 2  and R 3 , are joined to form an optionally substituted aryl or optionally substituted heteroaryl ring; and 
         Ring A forms an optionally substituted 5- to 6-membered ring. 
       
     
     
         2 . The method according to  claim 1 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 R 4A , R 5A , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A  and R 16B  are, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl; and/or, optionally, R 13A  and R 13B , and/or R 14A  and R 14B , and/or R 15A  and R 15B , and/or R 16A  and R 16B  are optionally joined to form an oxo (═O) group, an oxime (═NOR a ) group, an imine (═NN(R a ) 2 ) group, an alkenyl (═C(R b ) 2 ) group, and/or a 3- to 6-membered spirocyclic ring, wherein each instance of R a  and R b  is, independently, hydrogen or optionally substituted aliphatic, wherein optionally two R a  groups or two R b  groups are joined to form a 5- to 6-membered ring. 
 
     
     
         3 . The method according to  claim 2 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
       or any mixture thereof. 
     
     
         4 . The method according to  claim 2 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
       wherein:
 R 7 , R 8 , R 9 , and R 10 , are, independently, selected from hydrogen, halogen, —OR c , —OC(═O)R c , —OC(═O)OR c , —OC(═O)N(R d ) 2 , —OSO 2 R d , —C(═O)OR c , —C(═O)N(R d ) 2 , —CN, —CNO, —NCO, —N 3 , —NO 2 , —N(R d ) 2 , —N(R d )C(═O)OR c , —N(R d )C(═O)R c , —N(R d )SO 2 R d , —SO 2 R d , —SOR d , —SO 2 N(R d ) 2 , optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, wherein each instance of R c  is, independently, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, and each instance of R d  is, independently, hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl; and/or two groups selected from R 7 , R 8 , R 9 , and R 10  adjacent to each other are joined to form an optionally substituted 5- to 6-membered ring. 
 
     
     
         5 . The method according to  claim 4 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
     
     
         6 . The method according to  claim 1 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
       wherein
 each instance of R 17  is, independently, selected from hydrogen, halogen, —OR c , —OC(═O)R c , —OC(═O)OR c , —OC(═O)N(R d ) 2 , —OSO 2 R d , —C(═O)OR c , —C(═O)N(R) 2 , —CN, —CNO, —NCO, —N 3 , —NO 2 , —N(R d ) 2 , —N(R d )C(═O)OR c , —N(R d )C(═O)R c , —N(R d )SO 2 R d , —SO 2 R d , —SOR d , —SO 2 N(R d ) 2 , optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, wherein each instance of R c  is, independently, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, and each instance of R d  is, independently, hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl; and/or two R 17  groups adjacent to each other are joined to form an optionally substituted 5- to 6-membered ring; and 
 d is 0 to 4. 
 
     
     
         7 . The method according to  claim 6 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
     
     
         8 . The method according to  claim 7 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
     
     
         9 . The method according to  claim 4 , wherein R 7  is an optionally substituted C 1-10  aliphatic group. 
     
     
         10 . The method according to  claim 9 , wherein R 7  is an optionally substituted C 1-10  alkyl group. 
     
     
         11 . The method according to  claim 10 , wherein R 7  is selected from methyl, trichloromethyl, trifluoromethyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, iso-butyl, n-pentyl, neopentyl, amyl, trityl, adamantyl, thexyl, benzyl and cumyl. 
     
     
         12 . The method according to  claim 4 , wherein R 9  is an optionally substituted C 1-10  aliphatic group. 
     
     
         13 . The method according to  claim 12 , wherein R 9  is an optionally substituted C 1-10  alkyl group. 
     
     
         14 . The method according to  claim 13 , wherein R 9  is selected from methyl, trichloromethyl, trifluoromethyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, iso-butyl, n-pentyl, neopentyl, amyl, trityl, adamantyl, thexyl, benzyl and cumyl. 
     
     
         15 . The method according to  claim 4 , wherein the A value of R 7  is greater than the A value of R 9 . 
     
     
         16 . The method according to  claim 15 , wherein the A value of R 7  is at least 1.5 times greater than the A value of R 9 . 
     
     
         17 . The method according to  claim 16 , wherein the A value of R 7  is greater than about 2.5 kcal/mol. 
     
     
         18 . The method according to  claim 4 , wherein the A value of R 7  is greater than about 2.5 kcal/mol. 
     
     
         19 . The method according to  claim 18 , wherein the A value of R 9  is between about 0 to about 2.5 kcal/mol. 
     
     
         20 . The method according to  claim 1 , wherein the metal complex is selected from any of the following formulae: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         21 . The method according to  claim 1 , wherein M is cobalt. 
     
     
         22 - 31 . (canceled) 
     
     
         32 . The method according to  claim 1 , wherein the polymer has greater than about 85 percent of Y. 
     
     
         33 . The method according to  claim 32 , wherein the polymer has greater than about 90% of Y. 
     
     
         34 . The method according to  claim 32 , wherein the polymer has greater than about 95% of Y. 
     
     
         35 . The method according to  claim 32 , wherein the polymer has greater than about 99% of Y. 
     
     
         36 . The method according to  claim 32 , wherein the polymer is 100% of Y and 0% of Z. 
     
     
         37 - 53 . (canceled) 
     
     
         54 . A method of synthesizing a poly(ethylene carbonate) polymer, comprising a step of reacting ethylene oxide with carbon dioxide in the presence of a cobalt complex,
 wherein the cobalt complex is any one of the formulae:   
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein X is absent or is a nucleophilic ligand. 
       
     
     
         55 . 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; 
 R 3  is, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl; 
 Ring A forms an optionally substituted cyclohexyl or phenyl ring; 
 R 7  and R 9  are, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl; 
 wherein at least one of R 7  and R 9  is selected from the group consisting of: —[C(CH 3 ) 2 CH 2 CH 2 N(Bu) 3 ] + , —C(CH 3 ) 2 CH 2 C(CH 3 ) 3 , —CH(CH 2 CH 3 )C 6 H 5 , —CH(C 6 H 5 )CH═CH 2 , —C(CH 3 ) 2 CH 2 CH 3 , 1-methyl-cyclohexyl, cyclohexyl and —C(CH 3 ) 2 Ph; 
 wherein R 9  is other than —[C(CH 3 ) 2 CH 2 CH 2 N(Bu) 3 ] +  when R 7  is —[C(CH 3 ) 2 CH 2 CH 2 N(Bu) 3 ] + ; 
 wherein R 9  is other than hydrogen when R 7  is —CH(CH 2 CH 3 )C 6 H 5 ; 
 wherein R 9  is other than —C(CH 3 ) 2 CH 2 C(CH 3 ) 3  when R 7  is —C(CH 3 ) 2 CH 2 C(CH 3 ) 3 ; 
 wherein R 9  is other than —C(CH 3 ) 3  when R 7  is —CH(C 6 H 5 )CH═CH 2 ; 
 wherein R 9  is other than —C(CH 3 ) 3  when R 7  is —C(CH 3 ) 2 CH 2 CH 3 ; 
 wherein R 9  is other than —C(CH 3 ) 2 CH 2 CH 3  when R 7  is —C(CH 3 ) 2 CH 2 CH 3 ; 
 wherein R 9  is other than —C(CH 3 ) 3  when R 7  is 1-methyl-cyclohexyl; 
 wherein R 9  is other than —C(CH 3 ) 2 CH 2 CH 3  when R 7  is 1-methyl-cyclohexyl; 
 wherein R 9  is other than —CH 3  when R 7  is cyclohexyl; and 
 wherein R 9  is other than —C(CH 3 ) 2 Ph when R 7  is —C(CH 3 ) 2 Ph. 
 
     
     
         56 - 61 . (canceled) 
     
     
         62 . 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; 
 R 7  and R 9  are, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl; and 
 R 4A , R 4B , R 5A , R 5B , and R 6A , R 6B  are independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, and/or, R 4A  and R 4B , and/or R 5A  and R SB , and/or and R 6A  and R 6B  are optionally joined to form an oxo (=O) group, an oxime (=NOR a ) group, an imine (=NN(R a ) 2 ) group, an alkenyl (=C(R b ) 2 ) group, and/or a 3- to 6-membered spirocyclic ring, wherein each instance of R a  and R b  is, independently, hydrogen or optionally substituted aliphatic, wherein optionally two R a  groups or two R b  groups are joined to form a 3- to 6-membered ring. 
 
     
     
         63 - 72 . (canceled) 
     
     
         73 . 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; 
 R 1 , R 2 , R 3  are, 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 
 Ring A forms an optionally substituted cyclohexyl or phenyl ring. 
 
     
     
         74 - 98 . (canceled)