Dianhydrides, polyimides derived from biscatecol, methods of making, and methods of use

Abstract

The present disclosure provides for a multi-anhydride, a polyimide, a method of making a dianhydride, a method making a multi-anhydride, a method of making a polyimide, and the like.

We claim: 
     
         1 . A method of making a multi-anhydride, comprising: 
       
         
           
           
               
               
           
         
       
       wherein Ar 4  is selected from the following structures: 
       
         
           
           
               
               
           
         
       
       wherein each R 1  and R 2  are independently selected from the group consisting of: H, a linear or branched, substituted or unsubstituted, alkyl group, wherein when the bond is directed to the middle of a ring, this indicates that 1 to 4 of the R groups are optionally attached to the ring and each R group is independently selected from other R groups attached to a ring. 
     
     
         2 . The method of  claim 1 , where the method includes: 
       
         
           
           
               
               
           
         
       
     
     
         3 . The method of  claim 2 , wherein the first step comprises dissolving the reactants under alkaline pH using a solvent selected from the group consisting of dichloromethane, chloroform, tetrahydrofuran, dimethylformamide and dimethylacetamide. 
     
     
         4 . The method of  claim 3 , wherein the solvent is dichloromethane. 
     
     
         5 . The method of  claim 2 , wherein step two comprises reacting in the presence of a catalyst selected from the group consisting of zinc cyanide, palladium(II) chloride, palladium(II) acetate, and tris(dibenzylideneacetone)dipalladium(0). 
     
     
         6 . The method of  claim 2 , wherein the second step comprises reacting in the presence of a ligand selected from the group consisting of triphenylphosphine (PPh 3 ), dibenzylideneacetone, 1,2-Bis(diphenylphosphino)ethane (dppe) 1,3-Bis(diphenylphosphino)propane (dppp), and 1,1′-Bis(diphenylphosphino)ferrocene (dppf). 
     
     
         7 . The method of  claim 2 , wherein the third step comprises refluxing in a mixture of ethanol and water, wherein the ratio ethanol to water is within the range of about 10:1 to about 1:10 (v/v). 
     
     
         8 . The method of  claim 2 , wherein the fourth step comprises refluxing for about 1 hour to about 48 hours within a temperature range of about 100° C. to 140° C. 
     
     
         9 . A multi-anhydride comprising: 
       
         
           
           
               
               
           
         
       
       wherein Ar 4  is selected from the following structures: 
       
         
           
           
               
               
           
         
       
       wherein each R 1  and R 2  are independently selected from the group consisting of H and a linear or branched, substituted or unsubstituted, alkyl group, wherein when the bond is directed to the middle of a ring, this indicates that 1 to 4 of the R groups are optionally attached to the ring and each R group is independently selected from other R groups attached to a ring. 
     
     
         10 . A method of making a polyimide, comprising: 
       
         
           
           
               
               
           
         
       
       wherein Ar 4  is selected from the following structures: 
       
         
           
           
               
               
           
         
       
       wherein each R 1  and R 2  are independently selected from the group consisting of H and a linear or branched, substituted or unsubstituted, alkyl group, wherein when the bond is directed to the middle of a ring, this indicates that 1 to 4 of the R groups are optionally attached to the ring and each R group is independently selected from other R groups attached to a ring; wherein R 6  is H, a substituted or unsubstituted aromatic group or a linear or branched, substituted or unsubstituted, alkyl group; wherein R 7  and R 8  are each independently H, a substituted or unsubstituted aromatic group, or a linear or branched, substituted or unsubstituted, alkyl group, a hydroxyl group, a sulfonic group, or a thiol group. 
     
     
         11 . The method of  claim 10 , comprising reacting the anhydride and the diamine in a solvent selected from the group consisting of N-Methyl-2-pyrrolidone (NMP), m-Cresol, Dimethyl Sulfoxide (DMSO), and Dimethylacetamide (DMAc). 
     
     
         12 . The method of  claim 10 , wherein the diamine is 2,3,5,6-Tetramethyl-p-phenylenediamine. 
     
     
         13 . A composition comprising,
 a polyimide having the following structure:   
       
         
           
           
               
               
           
         
       
       wherein Ar 4  is selected from the following structures: 
       
         
           
           
               
               
           
         
       
       wherein each R 1  and R 2  are independently selected from the group consisting of H and a linear or branched, substituted or unsubstituted, alkyl group, wherein when the bond is directed to the middle of a ring, this indicates that 1 to 4 of the R groups are optionally attached to the ring and each R group is independently selected from other R groups attached to a ring; wherein R 6  is H, a substituted or unsubstituted aromatic group, or a linear or branched, substituted or unsubstituted, alkyl group; wherein R 7  and R 8  are each independently H, a substituted or unsubstituted aromatic group or a linear or branched, substituted or unsubstituted, alkyl group, a hydroxyl group, a sulfonic group, or a thiol group. 
     
     
         14 . The composition of  claim 13 , wherein the composition is in the form of a membrane. 
     
     
         15 . The composition of  claim 13 , wherein the composition is a solid characterized by intrinsic microporosity. 
     
     
         16 . The composition of  claim 13 , wherein the polyimide is in the form of a membrane configured for gas or liquid separation.