Polymers and methods of producing thereof

Abstract

Provided herein are methods of producing polymers from furan and optionally diol compounds, using an organocatalyst. A polymer composition comprising a polymer prepared by the method is contemplated. Provided herein are also polymer compositions, such as poly(alkylene-2,5-furandicarboxylate). In some embodiments, polymer compositions have any one of the characteristics discussed herein, or any combinations thereof.

1 . A composition comprising a polymer with a polymer backbone,
 wherein the polymer backbone comprises an optionally substituted furandicarboxylate moiety or an optionally substituted tetrahydrofurandicarboxylate moiety,   wherein the composition is free from metal catalysts or residues thereof;   wherein the composition has an number average molecular weight of at least 10,000 Da; and   wherein a solution of 5 mg/mL of the composition has an absorbance of less than 0.05 at 400 nm.   
     
     
         2 . A composition comprising a polymer with a polymer backbone,
 wherein the polymer backbone comprises an optionally substituted furandicarboxylate moiety or an optionally substituted tetrahydrofurandicarboxylate moiety,   wherein the composition has a metal content that does not come from metal catalysts used to produce the polymer or precursors thereof, and wherein a solution of 5 mg/mL of the composition has an absorbance of less than 0.05 at 400 nm.   
     
     
         3 . The composition of  claim 1 , wherein the metal catalysts are transesterification catalysts. 
     
     
         4 . The composition of  claim 1 ,
 wherein the composition has a total metal content of less than 0.1 wt %.   
     
     
         5 . The composition of  claim 4 , wherein the total metal content includes the content of transition metals, post-transition metals, metalloids, or lanthanoid metals, or any combinations thereof. 
     
     
         6 . The composition of  claim 4 , wherein the total metal content excludes the content of alkali metals, alkaline earth metals, and silicon. 
     
     
         7 . The composition of  claim 1 , wherein the optionally substituted furandicarboxylate moiety is an optionally substituted 2,5-furandicarboxylate moiety, and the optionally substituted tetrahydrofurandicarboxylate moiety is an optionally substituted 2,5-tetrahydrofurandicarboxylate moiety. 
     
     
         8 . The composition of  claim 1 , wherein the optionally substituted furandicarboxylate moiety is: 
       
         
           
           
               
               
           
         
       
     
     
         9 . The composition of  claim 1 , wherein the polymer is poly(alkylene-2,5-furandicarboxylate) or poly(alkylene-2,5-tetrahydrofurandicarboxylate). 
     
     
         10 . The composition of  claim 9 , wherein the polymer is poly(ethylene-2,5-furandicarboxylate) or poly(ethylene-2,5-tetrahydrofurandicarboxylate). 
     
     
         11 . A method, comprising polymerizing a furan or tetrahydrofuran in the presence of an organocatalyst to produce a polymer composition,
 wherein the furan or tetrahydrofuran is a compound of formula (G):   
       
         
           
           
               
               
           
         
         
           wherein:
    is a double bond or a single bond;
 j is 2 when   is a double bond, or j is 6 when   is a single bond j; 
 each R n  is independently H or alkyl; and 
 each R g  is independently alkyl, and 
 
 
         
         wherein 
         a) the furan or tetrahydrofuran is polymerized in the presence of an organocatalyst and an antioxidant; or 
         b) the furan or tetrahydrofuran is polymerized at a temperature of less than 200° C.; 
         or a combination of a) and b); and 
         wherein the polymer composition comprises a polymer with a polymer backbone, wherein the polymer backbone comprises a moiety of formula (Q′): 
       
       
         
           
           
               
               
           
         
         
           wherein  , j is 2, R n  and R g  are as defined above for formula (G); and 
         
         wherein a solution of 5 mg/mL of the composition has an absorbance of less than 0.05 at 400 nm. 
       
     
     
         12 . The method of  claim 11 , wherein the organocatalyst is generated in situ. 
     
     
         13 . The method of  claim 11 , wherein the organocatalyst is a non-transition metal catalyst, a non-post-transition metal catalyst, a non-metalloid catalyst, or a non-lanthanoid catalyst, or any combinations thereof. 
     
     
         14 . The method of  claim 11 , wherein the organocatalyst is an N-heterocyclic carbene. 
     
     
         15 - 21 . (canceled) 
     
     
         22 . A polymer composition produced according to the method of  claim 11 , wherein a solution of 5 mg/mL of the composition has an absorbance of less than 0.05 at 400 nm. 
     
     
         23 . The polymer composition of  claim 1 , wherein the solution is in hexafluoroisopropanol. 
     
     
         24 . The method of  claim 11 , wherein the solution is in hexafluoroisopropanol. 
     
     
         25 . A composition comprising a poly(ethylene-2,5-furandicarboxylate) (PEF) and a N-heterocyclic carbene residue. 
     
     
         26 . The composition of  claim 25 , wherein the composition further comprises an antioxidant residue. 
     
     
         27 . The composition of  claim 25 , wherein the composition has an average molecular weight of at least 10,000 Da. 
     
     
         28 - 30 . (canceled)