Copolymerization 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 . A method of synthesizing a poly(ethylene carbonate) polymer,
 wherein the poly(ethylene carbonate) polymer is made up of Y, and optionally Z, and wherein the poly(ethylene carbonate) polymer has greater than 85% of Y,   
       
         
           
           
               
               
           
         
         the method comprising reacting ethylene oxide and carbon dioxide in the presence of a metal complex, wherein the metal complex is of the formula: 
       
       
         
           
           
               
               
           
         
       
       wherein:
 M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium and 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 . (canceled) 
     
     
         3 . The method according to  claim 1 , wherein the metal complex is a cobalt metal complex. 
     
     
         4 . The method according to  claim 3 , wherein the cobalt metal complex is a Co (III) complex. 
     
     
         5 . (canceled) 
     
     
         6 . 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, and optionally substituted heteroaryl; or, 
         R 13A  and R 13B , or R 14A  and R 14B , or R 15A  and R 15B , or R 16A  and R 16B  are 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, 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. 
       
     
     
         7 . The method according to  claim 6 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
       or any mixture thereof. 
     
     
         8 . The method according to  claim 6 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
         wherein: 
         each instance of R 7 , R 8 , R 9 , and R 10 , 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 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, and optionally substituted heteroaryl,
 wherein each instance of R c  is, independently, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or optionally substituted heteroaryl, and 
 each instance of R d  is, independently, hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or optionally substituted heteroaryl; 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. 
 
       
     
     
         9 . The method according to  claim 8 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
     
     
         10 . 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 d ) 2 , —CN, —CNO, —NCO, —N 3 , —NO 2 , —N(R d ) 2 , —N(R d )C(═O)OR, —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, and optionally substituted heteroaryl,
 wherein each instance of R c  is, independently, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or optionally substituted heteroaryl, and 
 each instance of R d  is, independently, hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or optionally substituted heteroaryl; 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. 
       
     
     
         11 . The method according to  claim 10 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
     
     
         12 . The method according to  claim 11 , wherein the metal complex is of the formula: 
       
         
           
           
               
               
           
         
       
     
     
         13 . The method according to  claim 1 , wherein R 7  is an optionally substituted C 1-10  aliphatic group. 
     
     
         14 . The method according to  claim 13 , wherein R 7  is an optionally substituted C 1-10  alkyl group. 
     
     
         15 . The method according to  claim 14 , 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. 
     
     
         16 . The method according to  claim 1 , wherein R 9  is an optionally substituted C 1-10  aliphatic group. 
     
     
         17 . The method according to  claim 16 , wherein R 9  is an optionally substituted C 1-10  alkyl group. 
     
     
         18 . The method according to  claim 17 , 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. 
     
     
         19 . The method according to  claim 1 , wherein the A value of R 7  is greater than the A value of R 9 . 
     
     
         20 . The method according to  claim 19 , wherein the A value of R 7  is at least 1.5 times greater than the A value of R 9 . 
     
     
         21 - 22 . (canceled) 
     
     
         23 . The method according to  claim 1 , wherein the A value of R 9  is between about 0 to about 2.5 kcal/mol. 
     
     
         24 . The method according to  claim 1 , wherein the metal complex is selected from any of the following formulae: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         25 . (canceled) 
     
     
         26 . The method according to  claim 1 , wherein X is absent or is —OR x , —SR x , —O(C═O)R x , —O(C═O)OR x , —O(C═O)N(R x ) 2 , —N(R x )(C═O)R x , —NC, —CN, halo, —N 3 , or PR x   3 , wherein each R x  is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl. 
     
     
         27 . The method according to  claim 26 , wherein X is —OC(═O)C 6 F 5 , —O(C═O)C 6 H 5 , —OC(═O)CF 3 , —O(C═O)CH 3 , —NC, —CN, —N 3 , —Cl, or —Br. 
     
     
         28 . The method according to  claim 27 , wherein X is —OC(═O)C 6 F 5 . 
     
     
         29 . The method according to  claim 1 , wherein the method comprises reacting ethylene oxide and carbon dioxide in the presence of a metal complex and a co-catalyst. 
     
     
         30 - 31 . (canceled) 
     
     
         32 . The method according to  claim 29 , wherein the co-catalyst is a salt. 
     
     
         33 . The method according to  claim 32 , wherein the salt is an ammonium, phosphonium, or arsonium salt. 
     
     
         34 . The method according to  claim 33 , wherein the ammonium salt is (n Bu) 4 NCl, (n-Bu) 4 NBr, (n-Bu) 4 NN 3 , [PPN]Cl, [PPN]Br, or [PPN]N 3 . 
     
     
         35 - 37 . (canceled) 
     
     
         38 . The method according to  claim 1 , wherein the poly(ethylene carbonate) polymer has greater than about 90% of Y. 
     
     
         39 . The method according to  claim 38 , wherein the poly(ethylene carbonate) polymer has greater than about 95% of Y. 
     
     
         40 . The method according to  claim 39 , wherein the poly(ethylene carbonate) polymer has greater than about 99% of Y. 
     
     
         41 . The method according to  claim 40 , wherein the poly(ethylene carbonate) polymer is 100% of Y and 0% of Z. 
     
     
         42 . The method according to  claim 1 , wherein the poly(ethylene carbonate) polymer is of the formula: 
       
         
           
           
               
               
           
         
         P is an integer of between about 5,000 to about 20,000, inclusive; and 
         each F and G are, independently, suitable terminating groups. 
       
     
     
         43 - 58 . (canceled) 
     
     
         59 . The method of  claim 1 , wherein the metal complex is any one of the formulae: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein X is absent or is a nucleophilic ligand. 
     
     
         60 . A metal complex of the formula: 
       
         
           
           
               
               
           
         
         wherein: 
         M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium and manganese; 
         X is absent or is a nucleophilic ligand; 
         each instance of R 3  is independently selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl; 
         each instance of R 7  and R 9  is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl; and 
         Ring A forms an optionally substituted 5- to 6-membered ring; 
         wherein at least one instance 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 )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. 
       
     
     
         61 - 103 . (canceled) 
     
     
         104 . A metal complex of the formula: 
       
         
           
           
               
               
           
         
         wherein: 
         M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium and manganese; 
         X is absent or is a nucleophilic ligand; 
         each instance of R 7  and R 9  is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl; and 
         each instance of R 4A , R 4B , R 5A , R 5B , R 6A , and R 6B  is independently selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl, or, 
         R 4A  and R 4B , or R 5A  and R 5B , or R 6A  and R 6B  are 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, 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. 
       
     
     
         105 - 114 . (canceled) 
     
     
         115 . A metal complex of the formula: 
       
         
           
           
               
               
           
         
         wherein: 
         M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium and 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, and optionally substituted heteroaryl; and 
         Ring A forms an optionally substituted 5- to 6-membered ring. 
       
     
     
         116 - 140 . (canceled) 
     
     
         141 . The method of  claim 1 , wherein the metal complex is: 
       
         
           
           
               
               
           
         
         wherein: 
         each instance of R 3  is independently selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl; and 
         each instance of R 7  and R 9  is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.