US2012042777A1PendingUtilityA1

Gas separation using membranes comprising polybenzoxazoles prepared by thermal rearrangement

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Assignee: LEE YOUNG MOOPriority: Mar 12, 2008Filed: Oct 28, 2011Published: Feb 23, 2012
Est. expiryMar 12, 2028(~1.7 yrs left)· nominal 20-yr term from priority
C08G 61/12C08J 5/22C08G 69/48C08G 61/00B01D 2325/22C08G 73/22C08L 79/04C01B 3/503B01D 71/62B01D 2325/24B01D 69/02C01B 2203/0405C01B 2203/0475C01B 2203/048B01D 53/228
54
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Claims

Abstract

A method of separating components of a gas mixture, the method comprising: passing the gas mixture through a benzoxazole-based polymer membrane at a temperature of from about 30° C. to about 400° C., wherein the benzoxazole-based polymer membrane is represented by the formula: as is defined herein.

Claims

exact text as granted — not AI-modified
1 . A method of separating H 2  and CO 2  from a gas mixture, the method comprising:
 passing the gas mixture comprising H 2  and CO 2  through a benzoxazole-based polymer membrane at a temperature of from about 30° C. to about 400° C., wherein the benzoxazole-based polymer membrane is represented by the formula:   
       
         
           
           
               
               
           
         
         wherein Ar is a bivalent C 5 -C 24  arylene group or a bivalent C 5 -C 24  heterocyclic ring, which is substituted or unsubstituted with at least one substituent selected from the group consisting of C 1 -C 10  alkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkyl and C 1 -C 10  haloalkoxy, or two or more of which are fused together to form a condensation ring, or covalently bonded to each other via a functional group selected from the group consisting of O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p  (in which 1≦p≦10), (CF 2 ) q  (in which 1≦q≦10), C(CH 3 ) 2 , C(CF 3 ) 2  and C(═O)NH; 
         Q is a single bond, O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p  (in which 1≦p≦10), (CF 2 ) q  (in which 1≦q≦10), C(CH 3 ) 2 , C(CF 3 ) 2 , C(═O)NH, C(CH 3 )(CF 3 ), C 1 -C 6  alkyl-substituted phenyl or C 1 -C 6  haloalkyl-substituted phenyl in which Q is linked to opposite both phenyl rings in the position of m-m, m-p, p-m or p-p; and 
         n is an integer of 20 to 400. 
       
     
     
         2 . The method of  claim 1 , wherein Ar is selected from the following compounds: 
       
         
           
           
               
               
           
         
         wherein X is O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p  (in which 1≦p≦10), (CF 2 ) q  (in which 1≦q≦10), C(CH 3 ) 2 , C(CF 3 ) 2 , or C(═O)NH; Y is O, S or C(═O); and Z 1 , Z 2  and Z 3  are identical or different and are O, N or S. 
       
     
     
         3 . The method of  claim 1 , wherein Ar is selected from the following compounds: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         4 . The method of  claim 1 , wherein Q is a single bond, C(CH 3 ) 2 , C(CF 3 ) 2 , C(═O)NH, C(CH 3 )(CF 3 ), 
       
         
           
           
               
               
           
         
       
     
     
         5 . The method of  claim 1 , wherein Ar is 
       
         
           
           
               
               
           
         
       
       and Q is C(CF 3 ) 2 . 
     
     
         6 . A method of separating a pair of gasses from a gas mixture comprising the pair of gases, the method comprising:
 passing the gas mixture through a benzoxazole-based polymer membrane at a temperature of from about 30° C. to about 400° C., wherein the benzoxazole-based polymer membrane is represented by the formula:   
       
         
           
           
               
               
           
         
         wherein Ar is a bivalent C 5 -C 24  arylene group or a bivalent C 5 -C 24  heterocyclic ring, which is substituted or unsubstituted with at least one substituent selected from the group consisting of C 1 -C 10  alkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkyl and C 1 -C 10  haloalkoxy, or two or more of which are fused together to form a condensation ring, or covalently bonded to each other via a functional group selected from the group consisting of O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p  (in which 1≦p≦10), (CF 2 ) q  (in which 1≦q≦10), C(CH 3 ) 2 , C(CF 3 ) 2  and C(═O)NH; 
         Q is a single bond, O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p  (in which 1≦p≦10), (CF 2 ) q  (in which 1≦q≦10), C(CH 3 ) 2 , C(CF 3 ) 2 , C(═O)NH, C(CH 3 )(CF 3 ), C 1 -C 6  alkyl-substituted phenyl or C 1 -C 6  haloalkyl-substituted phenyl in which Q is linked to opposite both phenyl rings in the position of m-m, m-p, p-m or p-p; and
 n is an integer of 20 to 400, wherein the gas pair is selected from the group consisting of H 2 /CH 4 , H 2 /CO 2 , H 2 /N 2 , He/N 2 , O 2 /N 2 , CO 2 /N 2 , and CO 2 /CH 4 . 
 
       
     
     
         7 . The method of  claim 6 , wherein Ar is selected from the following compounds: 
       
         
           
           
               
               
           
         
         wherein X is O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p  (in which 1≦p≦10), (CF 2 ) q  (in which 1≦q≦10), C(CH 3 ) 2 , C(CF 3 ) 2 , or C(═O)NH; Y is O, S or C(═O); and Z 1 , Z 2  and Z 3  are identical or different and are O, N or S. 
       
     
     
         8 . The method of  claim 6 , wherein Ar is selected from the following compounds: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         9 . The method of  claim 6 , wherein Q is a single bond, C(CH 3 ) 2 , C(CF 3 ) 2 , C(═O)NH, C(CH 3 )(CF 3 ), 
       
         
           
           
               
               
           
         
       
     
     
         10 . The method of  claim 6 , wherein Ar is 
       
         
           
           
               
               
           
         
       
       and Q is C(CF 3 ) 2 . 
     
     
         11 . A gas separation membrane comprising polybenzoxazole (TR-β-PBO) represented by the formula: 
       
         
           
           
               
               
           
         
         wherein Ar is a bivalent C 5 -C 24  arylene group or a bivalent C 5 -C 24  heterocyclic ring, which is substituted or unsubstituted with at least one substituent selected from the group consisting of C 1 -C 10  alkyl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkyl and C 1 -C 10  haloalkoxy, or two or more of which are fused together to form a condensation ring, or covalently bonded to each other via a functional group selected from the group consisting of O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p  (in which 1≦p≦10), (CF 2 ) q  (in which 1≦q≦10), C(CH 3 ) 2 , C(CF 3 ) 2  and C(═O)NH; 
         Q is a single bond, O, S, C(═O), CH(OH), S(═O) 2 , Si(CH 3 ) 2 , (CH 2 ) p  (in which 1≦p≦10), (CF 2 ) q  (in which 1≦q≦10), C(CH 3 ) 2 , C(CF 3 ) 2 , C(═O)NH, C(CH 3 )(CF 3 ), C 1 -C 6  alkyl-substituted phenyl or C 1 -C 6  haloalkyl-substituted phenyl in which Q is linked to opposite both phenyl rings in the position of m-m, m-p, p-m or p-p; and 
         n is an integer of 20 to 400, wherein the polybenzoxazole has a weight average molecular weight of from more than about 50,000 Da to about 300,000 Da. 
       
     
     
         12 . The gas separation membrane of  claim 11 , wherein the polybenzoxazole has a weight average molecular weight of from more than about 50,000 Da to about 200,000 Da. 
     
     
         13 . The method of  claim 1  wherein the gas mixture is passed through the benzoxazole-based polymer membrane at a temperature of from about 200° C. to about 350° C. 
     
     
         14 . The method of  claim 6  wherein the gas mixture is passed through the benzoxazole-based polymer membrane at a temperature of from about 200° C. to about 350° C. 
     
     
         15 . The method of  claim 1 , wherein Ar is 
       
         
           
           
               
               
           
         
       
       and Q is C(CF 3 ) 2 . 
     
     
         16 . The method of  claim 1 , wherein Ar is 
       
         
           
           
               
               
           
         
       
       and Q is C(CF 3 ) 2 . 
     
     
         17 . The method of  claim 6 , wherein Ar is 
       
         
           
           
               
               
           
         
       
       and Q is C(CF 3 ) 2 . 
     
     
         18 . The method of  claim 6 , wherein Ar is 
       
         
           
           
               
               
           
         
       
       and Q is C(CF 3 ) 2 . 
     
     
         19 . The gas separation membrane of  claim 11 , wherein Ar is 
       
         
           
           
               
               
           
         
       
       and Q is C(CF 3 ) 2 . 
     
     
         20 . The gas separation membrane of  claim 11 , wherein Ar is 
       
         
           
           
               
               
           
         
       
       and Q is C(CF 3 ) 2 . 
     
     
         21 . The gas separation membrane of  claim 11 , wherein Ar is 
       
         
           
           
               
               
           
         
       
       and Q is C(CF 3 ) 2 .

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