Method for preparing polyether carbonates

Abstract

The present invention relates to a method for preparing a high molecular weight polyether carbonate, by reacting an epoxide and carbon dioxide in the presence of a catalyst of formula (1), and a double metal cyanide (DMC) catalyst. The catalyst of formula (I) has the following structure:

What is claimed is: 
     
         1 . A high molecular weight polyether carbonate having the formula (IV)— 
       
         
           
           
               
               
           
         
       
       
         , wherein X is independently selected from OC(O)R x , OSO 2 R x , OSOR X , OSO(R X ) 2 , S(O)R x,  OR x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl, wherein each X may be the same or different and wherein X may form a bridge between M 1  and M 2 ; R x  is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl, n and m are integers, and R e1  and R e2  depend on the nature of the epoxide used to prepare the polyether carbonate. 
       
     
     
         2 . A high molecular weight polyether carbonate according to  claim 1 , prepared by the method of reacting carbon dioxide and an epoxide in the presence of a double metal cyanide (DMC) catalyst and a catalyst of formula (I), wherein the catalyst of formula (I) has the following structure: 
       
         
           
           
               
               
           
         
       
       
         wherein M 1  and M 2  are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III)-X, Mn(III)-X, Ni(III)-X, Fe(III)-X, Ca(II), Ge(II), AI(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X) 2  or Ti(IV)-(X) 2 ; 
         R 1  and R 2  are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group; R 3  is independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene, may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic; R 5  is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl; 
         E 1  is C, E 2  is O, S or NH or E 1  is N and E 2  is O; 
         E 3 , E 4 , E 5  and E e  are selected from N, NR 4 , O and S, wherein when E 3 , E 4 , E 5  or E 6  are N,   is  , and wherein when E 3 , E 4 , E 5  or E 6  are NR 4 , O or S,  is  ; 
         R 4  is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl, -alkylC(O)OR 19  or -alkylC☰N or alkylaryl; 
         X is independently selected from OC(O)R x , OSO 2 R x , OSOR X , OSO(R x ) 2 , S(O)R x , OR x , phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl, wherein each X may be the same or different and wherein X may form a bridge between M 1  and M 2 ; 
         R x  is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl; and 
         G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base. 
       
     
     
         3 . The high molecular weight polyether carbonate of  claim 1 , wherein n and m are integers of 1 or more. 
     
     
         4 . The high molecular weight polyether carbonate of  claim 1 , wherein m/(n+m) is from greater than zero to less than 1. 
     
     
         5 . The high molecular weight polyether carbonate of  claim 1 , wherein m/(n+m) is greater than about 0.50 to about 0.95. 
     
     
         6 . The high molecular weight polyether carbonate of  claim 1 , wherein the sum of all m and n groups is from 4 to 200. 
     
     
         7 . The high molecular weight polyether carbonate of  claim 1 , wherein m + n ≥ 10, or m+ n ≥ 20, or m + n ≥ 100, or m + n ≥ 200, or m + n ≥ 500, or m + n ≥ 1,000. 
     
     
         8 . The high molecular weight polyether carbonate of  claim 1 , wherein m/(n+m) is from about 0.15 to about 0.85. 
     
     
         9 . The high molecular weight polyether carbonate of  claim 1 , wherein m/(n+m) is from about 0.20 to about 0.80. 
     
     
         10 . The high molecular weight polyether carbonate of  claim 1 , wherein m/(n+m) is from about 0.25 to about 0.75. 
     
     
         11 . The high molecular weight polyether carbonate of  claim 1 , wherein the high molecular weight polyether carbonate has a molecular weight of at least about 25,000 Daltons. 
     
     
         12 . The high molecular weight polyether carbonate of  claim 1 , wherein the high molecular weight polyether carbonate has a molecular weight of at least about 50,000 Daltons. 
     
     
         13 . The high molecular weight polyether carbonate of  claim 1 , wherein the high molecular weight polyether carbonate has a molecular weight of at least about 100,000 Daltons. 
     
     
         14 . The high molecular weight polyether carbonate of  claim 1 , wherein R e1  and R e2  are independently selected from H, halogen, hydroxyl, or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, heteroalkyl or heteroalkenyl, or adjacent R e1  and R e2  groups may be taken together to form a saturated, partially unsaturated or unsaturated ring containing carbon and hydrogen atoms, and optionally one or more heteroatoms (e.g. O, N or S). 
     
     
         15 . The high molecular weight polyether carbonate of  claim 1 , wherein R e1  and R e2  are independently selected from H or optionally substituted alkyl, or adjacent R e1  and R e2  groups may be taken together to form a five or six membered alkyl ring. 
     
     
         16 . The high molecular weight polyether carbonate of  claim 1 , wherein each occurrence of R e1  and/or R e2   is  the same. 
     
     
         17 . The high molecular weight polyether carbonate of  claim 1 , wherein each occurrence of R e1  and/or R e2  is not the same. 
     
     
         18 . The high molecular weight polyether carbonate of  claim 1 , wherein the PDI of the polymer is greater than about 1, preferably greater than about 2, more preferably greater than about 3. 
     
     
         19 . The high molecular weight polyether carbonate of  claim 1 , wherein the polymer is a random copolymer, a statistical copolymer, an alternating copolymer, or a periodic copolymer. 
     
     
         20 . The high molecular weight polyether carbonate of  claim 1 , wherein the polymer is a random copolymer or a statistical copolymer.