Method for preparing polyols

Abstract

The present invention relates to a method for preparing a polycarbonate ether polyol, by reacting an epoxide and carbon dioxide in the presence of a catalyst of formula (I), a double metal cyanide (DMC) catalyst and a starter compound. The catalyst of formula (I) is as follows:

1 - 21 . (canceled) 
     
     
         22 . A polycarbonate ether polyol wherein the polycarbonate ether polyol has n ether linkages and m carbonate linkages, wherein n and m are integers, and wherein m/(n+m) is 0.20, 0.25, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, or within any range prepared from these specific values;
 wherein the polycarbonate ether polyol has a molecular weight in the range of from 500 to 10,000 Da, from 700 to 5,000 Da, or from 800 to 2,000 Da.   
     
     
         23 . A polycarbonate ether polyol as claimed in  claim 22 , wherein the polycarbonate ether polyol has a molecular weight in the range of from 500 to 800 Da. 
     
     
         24 . A polycarbonate ether polyol as claimed in  claim 22 , wherein m/(n+m) is from 0.20 to 0.80, from 0.25 to 0.75, from 0.65 to 0.90, or from 0.75 to 0.90. 
     
     
         25 . A polycarbonate ether polyol as claimed in  claim 22 , wherein m/(n+m) is from 0.20 to 0.90. 
     
     
         26 . A polycarbonate ether polyol according to  claim 22 , having the following formula (IV): 
       
         
           
           
               
               
           
         
       
       wherein:
 (a) R e1  and R e2  are each independently selected from H, halogen, hydroxyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heteroalkyl, and optionally substituted heteroalkenyl, or wherein R e1  and R e2  are each independently selected from hydrogen, methyl, ethyl, and phenyl; or 
 (b) each R e1  and R e2  together form a saturated, partially unsaturated or unsaturated ring containing carbon and hydrogen atoms, and optionally one or more heteroatoms (such as O, N or S); 
 wherein each Z′ is independently selected from —O—, —NR′—, —S—, —C(O)O—, —P(O)(OR′)O—, —PR′(O)(O—) 2 , —PR′(O)O—, and combinations thereof, wherein R′ is selected from H, optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl, and heterocycloalkyl; 
 wherein Z is selected from optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted cycloalkylene, optionally substituted cycloalkenylene, optionally substituted heterocycloalkylene, optionally substituted heterocycloalkenylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof; 
 wherein m and n are integers; and 
 wherein a is an integer of at least 2 
 
     
     
         27 . A polycarbonate ether polyol according to  claim 26 , wherein a is between 2 and 8 or between 2 and 6, or wherein a is 3. 
     
     
         28 . A polycarbonate ether polyol according to  claim 22 , wherein the polycarbonate ether polyol is a random copolymer, a statistical copolymer, an alternating copolymer or a periodic copolymer. 
     
     
         29 . A polyurethane or other higher polymer prepared from a polycarbonate ether polyol as defined in  claim 22 . 
     
     
         30 . A polyurethane as claimed in  claim 29 , wherein the polyurethane is prepared by reacting the polycarbonate ether polyol with a composition comprising a di- or polyisocyanate. 
     
     
         31 . A polycarbonate ether polyol according to  claim 22 , having a polydispersity index (PDI) of from 1 to less than 2, from 1 to less than 1.75, from 1 to less than 1.5, or from 1 to less than 1.3. 
     
     
         32 . A polycarbonate ether polyol according to  claim 22 , wherein m/(n+m) is from 0.60 to 0.95; from 0.70 to 0.95; from 0.80 to 0.95; from 0.90 to 0.95; from 0.80 to 0.90; or from 0.85 to 0.90. 
     
     
         33 . A polymerisation system for the copolymerisation of carbon dioxide and an epoxide, comprising:
 (a) 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), Al(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X) 2 , and Ti(IV)-(X) 2 ; 
 R 1  and R 2  are each 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, an acetylide group, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted haloalkyl, an optionally substituted heteroalkyl, an optionally substituted aryl, an optionally substituted heteroaryl, an optionally substituted alkoxy, an optionally substituted aryloxy, an optionally substituted alkylthio, an optionally substituted arylthio, an optionally substituted alicyclic, and an optionally substituted heteroalicyclic group; 
 each R 3  is independently selected from optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted arylene, optionally substituted heteroarylene, and optionally substituted cycloalkylene, wherein each alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene is optionally interrupted by at least one aryl, heteroaryl, alicyclic, or heteroalicyclic group; 
 each R 5  is independently selected from H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkylheteroaryl, and optionally substituted 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 6  are each independently selected from N, NR 4 , O, and S, wherein when E 3 , E 4 , E 5  or E 6  is N,   is  , and wherein when E 3 , E 4 , E 5  or E 6  is NR 4 , O or S,   is    
 each R 4  is independently selected from H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkylheteroaryl, optionally substituted -alkyl-C(O)OR 19 , optionally substituted -alkyl-C≡N, and optionally substituted alkylaryl; 
 each 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, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, and optionally substituted heteroaryl; 
 each R x  is independently hydrogen, optionally substituted aliphatic, optionally substituted haloaliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted alkylaryl, or optionally substituted heteroaryl; 
 G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base; 
 
         (b) A double metal cyanide (DMC) catalyst; 
         (c) A starter compound having the following structure:
   Z-(R Z ) a    (III)
 
 
         wherein:
 Z is selected from optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted cycloalkylene, optionally substituted cycloalkenylene, optionally substituted heterocycloalkylene, optionally substituted heterocycloalkenylene, optionally substituted arylene, and optionally substituted heteroarylene; or Z is a combination of any of these groups; 
 a is an integer which is at least 2; 
 each R Z  is independently —OH, —NHR′, —SH, —C(O)OH, PR′(O)(OH) 2 , —P(O)(OR′)(OH), or —PR′(O)OH; and 
 each R′ is independently selected from H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted cycloalkyl, and optionally substituted heterocycloalkyl. 
 
       
     
     
         34 . A polycarbonate ether polyol prepared by a method comprising reacting carbon dioxide and an epoxide in the presence of a double metal cyanide (DMC) catalyst, a catalyst of formula (I), and a starter compound, 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), Al(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X) 2 , and Ti(IV)-(X) 2 ; 
 R 1  and R 2  are each 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, an acetylide group, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted haloalkyl, an optionally substituted heteroalkyl, an optionally substituted aryl, an optionally substituted heteroaryl, an optionally substituted alkoxy, an optionally substituted aryloxy, an optionally substituted alkylthio, an optionally substituted arylthio, an optionally substituted alicyclic, and an optionally substituted heteroalicyclic group; 
 each R 3  is independently selected from optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted arylene, optionally substituted heteroarylene, and optionally substituted cycloalkylene, wherein each alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene is optionally interrupted by at least one aryl, heteroaryl, alicyclic, or heteroalicyclic group; 
 each R 5  is independently selected from H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkylheteroaryl, and optionally substituted 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 6  are each independently selected from N, NR 4 , O, and S, wherein when E 3 , E 4 , E 5  or E 6  is N,   is  , and wherein when E 3 , E 4 , E 5  or E 6  is NR 4 , O or S,   is    
 each R 4  is independently selected from H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkylheteroaryl, optionally substituted -alkyl-C(O)OR 19 , optionally substituted -alkyl-C≡N, and optionally substituted alkylaryl; 
 each 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, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, and optionally substituted heteroaryl; 
 each R x  is independently hydrogen, optionally substituted aliphatic, optionally substituted haloaliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted alkylaryl, or optionally substituted heteroaryl; 
 G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base; and 
 the starter compound is a compound having the following structure:
   Z-(R Z ) a    (III)
 
 
 
         wherein Z is selected from optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted cycloalkylene, optionally substituted cycloalkenylene, optionally substituted heterocycloalkylene, optionally substituted heterocycloalkenylene, optionally substituted arylene, and optionally substituted heteroarylene, or Z is a combination of any of these groups;
 a is an integer which is at least 2; 
 each R Z  is independently —OH, —NHR′, —SH, —C(O)OH, PR′(O)(OH) 2 , —P(O)(OR′)(OH), or —PR′(O)OH; and 
 each R′ is independently selected from H, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted cycloalkyl, and optionally substituted heterocycloalkyl. 
 
       
     
     
         35 . A polycarbonate ether polyol as claimed in  claim 23 , wherein m/(n+m) is from 0.20 to 0.80, from 0.25 to 0.75, from 0.65 to 0.90, or from 0.75 to 0.90. 
     
     
         36 . A polycarbonate ether polyol as claimed in  claim 23 , wherein m/(n+m) is from 0.20 to 0.90. 
     
     
         37 . A polycarbonate ether polyol according to  claim 23 , having the following formula (IV): 
       
         
           
           
               
               
           
         
         wherein:
 (a) R e1  and R e2  are each independently selected from H, halogen, hydroxyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heteroalkyl, and optionally substituted heteroalkenyl, preferably wherein R e1  and R e2  are independently selected from hydrogen, methyl, ethyl or phenyl; or 
 (b) each R e1  and each R e2  together form a saturated, partially unsaturated or unsaturated ring containing carbon and hydrogen atoms, and optionally one or more heteroatoms (such as O, N or S); 
 each Z′ is independently selected from —O—, —NR′—, —S—, —C(O)O—, —P(O)(OR′)O—, —PR′(O)(O—) 2 , —PR′(O)O—, or a combination thereof, wherein R′ is selected from H, optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or heterocycloalkyl; 
 Z is selected from optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted cycloalkylene, optionally substituted cycloalkenylene, optionally substituted heterocycloalkylene, optionally substituted heterocycloalkenylene, optionally substituted arylene, optionally substituted heteroarylene, or a combination thereof; 
 wherein m and n are integers; and 
 wherein a is an integer of at least 2.