Method for preparing and using supported phosphazenium catalysts

Abstract

Crosslinked organic polymers such as styrene-divinylbenzene copolymers contain pendant phosphazene or phosphazenium groups. These polymers are excellent alkylene oxide polymerization catalysts.

What is claimed is:  
     
         1 . A method for producing a polyether comprising subjecting an alkylene oxide to polymerization conditions in the presence of an initiator compound and a catalytically effective amount of a crosslinked organic polymer having pendant phosphazene or phosphazenium groups wherein said crosslinked organic polymer is substantially insoluble in said alkylene oxide and said polyether.  
     
     
         2 . The method of  claim 1  wherein the crosslinked organic polymer contains pendant phosphazenium groups having from about 1 to about 6 phosphorus atoms.  
     
     
         3 . The method of  claim 2  wherein said alkylene oxide is ethylene oxide, propylene oxide, 1,2-butylene oxide, or a mixture thereof.  
     
     
         4 . The method of  claim 2  wherein the alkylene oxide is ethylene oxide, the initiator compound is a secondary hydroxyl-terminated polyether polyol and the resulting polyether is EO-capped.  
     
     
         5 . The method of  claim 4  wherein the secondary hydroxyl-terminated polyether polyol is a poly(propylene oxide)polyol made using a DMC catalyst.  
     
     
         6 . The method of  claim 3  wherein said crosslinked organic polymer has a structure represented by the general formula  
       Polymer-[NR 1 —P + {[—N═P(A 2 )] x —NR 2 } 3 ] x    
       wherein R and R 1  are independently in each occurrence (a) an unsubstituted or inertly substituted alkyl or aryl group, (b) an unsubstituted or inertly substituted alkylene or arylene group that, together with another R or R 1  group on the same nitrogen atom, forms a ring structure including that nitrogen atom, (c) an unsubstituted or inertly substituted alkylene or arylene group that, together with a R or R 1  group bonded to a different nitrogen atom bonded to a common phosphorus atom, forms a ring structure including an —N—P—N— or —N—P═N— moiety, or (d) hydrogen; each A is independently —[N═P(A 2 )] x —NR 2 ; x is zero or a positive integer; and z is a positive integer.  
     
     
         7 . The method of  claim 6  wherein each R is a C 1-10  alkyl group, or together with another R forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety, and each R 1  is hydrogen, methyl or ethyl, or together with an R group forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety.  
     
     
         8 . The method of  claim 7  wherein each R is methyl or ethyl, and each R 1  is hydrogen, methyl or ethyl.  
     
     
         9 . The method of  claim 3  wherein said crosslinked organic polymer has a structure represented by the general formula  
       Polymer-{NR—[P(A 2 )═N] x —P + (A 2 )—NRR 1 } z    
       wherein R and R 1  are independently in each occurrence (a) an unsubstituted or inertly substituted alkyl or aryl group, (b) an unsubstituted or inertly substituted alkylene or arylene group that, together with another R or R 1  group on the same nitrogen atom, forms a ring structure including that nitrogen atom, (c) an unsubstituted or inertly substituted alkylene or arylene group that, together with a R or R 1  group bonded to a different nitrogen atom bonded to a common phosphorus atom, forms a ring structure including an —N—P—N— or —N—P═N— moiety, or (d) hydrogen; each A is independently —[N═P(A 2 )] x —NR 2 ; x is zero or a positive integer, and z is a positive integer.  
     
     
         10 . The method of  claim 9  wherein each R is a C 1-10  alkyl group, or together with another R forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety, and each R 1  is hydrogen, methyl or ethyl, or together with an R group forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety.  
     
     
         11 . The method of  claim 10  wherein each R is methyl or ethyl, and each R 1  is hydrogen, methyl or ethyl.  
     
     
         12 . The method of  claim 1  wherein the crosslinked organic polymer contains pendant phosphazene groups having from about 2 to about 6 phosphorus atoms.  
     
     
         13 . The method of  claim 12  wherein said alkylene oxide is ethylene oxide, propylene oxide, 1,2-butylene oxide, or a mixture thereof.  
     
     
         14 . The method of  claim 12  wherein the alkylene oxide is ethylene oxide, the initiator compound is a secondary hydroxyl-terminated polyether polyol and the resulting polyether is EO capped.  
     
     
         15 . The method of  claim 14  wherein the secondary hydroxyl-terminated polyether polyol is a poly(propylene oxide)polyol made using a DMC catalyst.  
     
     
         16 . The method of  claim 12  wherein said crosslinked organic polymer has pendant phosphazene groups and a structure represented by the general formula  
       Polymer-[N=P{[—N═P(A 2 )] x —NR 2 } 3 ] z    
       wherein each R is independently (a) an unsubstituted or inertly substituted alkyl or aryl group, (b) an unsubstituted or inertly substituted alkylene or arylene group that, together with another R group on the same nitrogen atom, forms a ring structure including that nitrogen atom, (c) an unsubstituted or inertly substituted alkylene or arylene group that, together with a R group bonded to a different nitrogen atom bonded to a common phosphorus atom, forms a ring structure including an —N—P—N— or —N—P═N— moiety, or (d) hydrogen; each A is independently —[N═P(A 2 )] z —NR 2 ; each x is zero or a positive integer provided that the number of phosphorus atoms in each phosphazene group from 2-6, and z is a positive number.  
     
     
         17 . The method of  claim 16  wherein each R is a C 1-10  alkyl group, or together with another R forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety.  
     
     
         18 . The method of  claim 17  wherein each R is methyl or ethyl.  
     
     
         19 . The method of  claim 12  wherein said crosslinked organic polymer has pendant phosphazene groups and a structure represented by the general formula  
       Polymer-{NR—[P(A 2 )═N] x —P(A 2 )═NR} z    
       wherein each R is independently in each occurrence (a) an unsubstituted or inertly substituted alkyl or aryl group, (b) an unsubstituted or inertly substituted alkylene or arylene group that, together with another R group on the same nitrogen atom, forms a ring structure including that nitrogen atom, (c) an unsubstituted or inertly substituted alkylene or arylene group that, together with a R group bonded to a different nitrogen atom bonded to a common phosphorus atom, forms a ring structure including an —N—P—N— or —N—P═N— moiety, or (d) hydrogen; each A is independently —[N═P(A 2 )] x —NR 2 , each x is independently zero or a positive integer provided that the number of phosphorus atoms in each phosphazene group from 2 to about 6 and z is a positive integer.  
     
     
         20 . The method of  claim 19  wherein each R is a C 1-10  alkyl group, or together with another R forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety.  
     
     
         21 . The method of  claim 20  wherein each R is methyl or ethyl.  
     
     
         22 . A cross-linked organic polymer having pendant phosphazene groups including at least two phosphorus atoms or phosphazenium groups including one or more phosphorus atoms, or a mixture of such phosphazene and phosphazenium groups.  
     
     
         23 . The crosslinked organic polymer of  claim 22  wherein said crosslinked organic polymer has a structure represented by the general formula  
       Polymer-{NR—[P(A 2 )═N] x —P + (A 2 )—NRR 1 } z    
       wherein R and R 1  are independently in each occurrence (a) an unsubstituted or inertly substituted alkyl or aryl group, (b) an unsubstituted or inertly substituted alkylene or arylene group that, together with another R or R 1  group on the same nitrogen atom, forms a ring structure including that nitrogen atom, (c) an unsubstituted or inertly substituted alkylene or arylene group that, together with a R or R 1  group bonded to a different nitrogen atom bonded to a common phosphorus atom, forms a ring structure including an —N—P—N— or —N—P═N— moiety, or (d) hydrogen; each A is independently —[N═P(A 2 )] x —NR 2 , each x is zero or a positive integer; and z is a positive number.  
     
     
         24 . The crosslinked organic polymer of  claim 23  wherein each R is a C 1-10  alkyl group, or together with another R forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety, and each R 1  is hydrogen, methyl or ethyl, or together with an R group forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety.  
     
     
         25 . The crosslinked organic polymer of  claim 24  wherein each R is methyl or ethyl, and each R 1  is hydrogen, methyl or ethyl.  
     
     
         26 . The crosslinked organic polymer of  claim 22  wherein said crosslinked organic polymer has a structure represented by the general formula  
       Polymer-[NR 1 —P + {[—N═P(A 2 )] x —NR 2 } 3 ] z    
       wherein R and R 1  are independently in each occurrence (a) an unsubstituted or inertly substituted alkyl or aryl group, (b) an unsubstituted or inertly substituted alkylene or arylene group that, together with another R or R 1  group on the same nitrogen atom, forms a ring structure including that nitrogen atom, (c) an unsubstituted or inertly substituted alkylene or arylene group that, together with a R or R 1  group bonded to a different nitrogen atom bonded to a common phosphorus atom, forms a ring structure including an —N—P—N— or —N—P═N— moiety, or (d) hydrogen; each A is independently —[N═P(A 2 )] x —NR 2 ; each x is zero or a positive integer; and z is a positive integer.  
     
     
         27 . The crosslinked organic polymer of  claim 26  wherein each R is a C 1-10  alkyl group, or together with another R forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety, and each R 1  is hydrogen, methyl or ethyl, or together with an R group forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety.  
     
     
         28 . The crosslinked organic polymer of  claim 27  wherein each R is methyl or ethyl, and each R 1  is hydrogen, methyl or ethyl.  
     
     
         29 . The crosslinked organic polymer of  claim 22  wherein said crosslinked organic polymer has pendant phosphazene groups and a structure represented by the general formula  
       Polymer-[N═P{[—N═P(A 2 )] x —NR 2 } 3 ] z    
       wherein each R is independently (a) an unsubstituted or inertly substituted alkyl or aryl group, (b) an unsubstituted or inertly substituted alkylene or arylene group that, together with another R group on the same nitrogen atom, forms a ring structure including that nitrogen atom, (c) an unsubstituted or inertly substituted alkylene or arylene group that, together with a R group bonded to a different nitrogen atom bonded to a common phosphorus atom, forms a ring structure including an —N—P—N— or —N—P═N— moiety, or (d) hydrogen; each A is independently —[N═P(A 2 )] z —NR 2 ; each x is zero or a positive integer provided that the number of phosphorus atoms in each phosphazene group from 2-6, and z is a positive number.  
     
     
         30 . The crosslinked organic polymer of  claim 29  wherein each R is a C 1-10  alkyl group, or together with another R forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety.  
     
     
         31 . The crosslinked organic polymer of  claim 30  wherein each R is methyl or ethyl.  
     
     
         32 . The crosslinked organic polymer of  claim 22  wherein said crosslinked organic polymer has pendant phosphazene groups and a structure represented by the general formula  
       Polymer-{NR—[P(A 2 )═N] x —P(A 2 )═NR} z    
       wherein each R is independently in each occurrence (a) an unsubstituted or inertly substituted alkyl or aryl group, (b) an unsubstituted or inertly substituted alkylene or arylene group that, together with another R group on the same nitrogen atom, forms a ring structure including that nitrogen atom, (c) an unsubstituted or inertly substituted alkylene or arylene group that, together with a R group bonded to a different nitrogen atom bonded to a common phosphorus atom, forms a ring structure including an —N—P—N— or —N—P═N— moiety, or (d) hydrogen; each A is independently —[N═P(A 2 )] x —NR 2 , each x is independently zero or a positive integer provided that the number of phosphorus atoms in each phosphazene group from 2 to about 6 and z is a positive integer.  
     
     
         33 . The crosslinked organic polymer of  claim 30  wherein each R is a C 1-10  alkyl group, or together with another R forms a C 2-5  alkylene group that forms part of a ring structure with a nitrogen atom or an —N—P—N— or —N—P═N— moiety.  
     
     
         34 . The crosslinked organic polymer of  claim 31  wherein each R is methyl or ethyl.