Polymers, substrates, methods for making such, and devices comprising the same

Abstract

The present invention relates generally to substrates for making polymers and methods for making polymers. The present invention also relates generally to polymers and devices comprising the same.

1 . A method of preparing a cross-linked polyazine polymer, comprising:
 reacting an organic substrate with a multiamine to form an organic polymer, wherein the organic substrate comprises a substituted moiety selected from the group consisting of tetrahydronaphthyl, azulenyl, indanyl, indenyl, diphenylether, diphenylamine, pyridyl, pyrimidinyl, imidazolyl, pyrazinyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, isoindolyl, indolizinyl, triazolyl, pyridazinyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, isothiazolyl, benzo[b]thienyl, and benzophenone, and the organic substrate is substituted with at least two aldehydes and/or ketones; and   oxidizing said organic polymer to form said cross-linked polyazine polymer.   
     
     
         2 . The method of  claim 1 , wherein said oxidizing step is carried out by enzymatic oxidative polymerization. 
     
     
         3 . The method of  claim 2 , wherein said enzymatic polymerization is carried out using an oxidase selected from the group consisting of a phenol oxidase, a polyphenol oxidase, a catechol oxidase, a tyrosinase, a laccase, and any combination thereof. 
     
     
         4 . The method of  claim 1 , wherein said oxidizing step is carried out by chemical oxidative polymerization with an oxidizing agent. 
     
     
         5 .- 7 . (canceled) 
     
     
         8 . The method of  claim 1 , wherein said moiety is substituted with said at least two aldehydes and/or ketones. 
     
     
         9 . (canceled) 
     
     
         10 . The method of  claim 1 , wherein said organic substrate comprises at least three aldehydes and/or ketones. 
     
     
         11 . The method of  claim 1 , wherein said multiamine is selected from the group consisting of hydrazine, triaminobenzene, and any combination thereof. 
     
     
         12 . The method of  claim 1 , wherein said cross-linked polyazine polymer is a heteropolymer. 
     
     
         13 . The method of  claim 1 , further comprising reacting said organic polymer with a second organic substrate comprising at least two aldehydes and/or ketones and a multiamine, prior to said oxidizing step. 
     
     
         14 . The method of  claim 1 , further comprising reacting a monocarbonyl compound with said organic polymer and a multiamine to form a capped organic polymer, prior to said oxidizing step. 
     
     
         15 . The method of  claim 14 , wherein said monocarbonyl compound has the structure 
       
         
           
           
               
               
           
         
         wherein 
         R is a conjugated moiety; and 
         R 1  is selected from the group consisting of hydrogen, alkyl, and alkenyl. 
       
     
     
         16 . The method of  claim 1 , wherein said organic substrate has the structure 
       
         
           
           
               
               
           
         
         wherein 
         R is a conjugated moiety selected from the group consisting of tetrahydronaphthyl, azulenyl, indanyl, indenyl, diphenylether, diphenylamine, pyridyl, pyrimidinyl, imidazolyl, pyrazinyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, isoindolyl, indolizinyl, triazolyl, pyridazinyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, isothiazolyl, benzo[b]thienyl, and benzophenone; and 
         R 1  and R 2  each independently selected from the group consisting of hydrogen, alkyl, and alkenyl. 
       
     
     
         17 . The method of  claim 1 , wherein said organic substrate has the structure 
       
         
           
           
               
               
           
         
         wherein 
         R is a conjugated moiety selected from the group consisting of tetrahydronaphthyl, azulenyl, indanyl, indenyl, diphenylether, diphenylamine, pyridyl, pyrimidinyl, imidazolyl, pyrazinyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, isoindolyl, indolizinyl, triazolyl, pyridazinyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, isothiazolyl, benzo[b]thienyl, and benzophenone; and 
         R 1 , R 2 , and R 3  are each independently selected from the group consisting of hydrogen, alkyl, and alkenyl. 
       
     
     
         18 . The method of  claim 1 , wherein said organic substrate comprises a metal. 
     
     
         19 . An electrochemical device comprising: a working electrode; a counter electrode; and said networked polyazine polymer of  claim 1 , wherein said working electrode is in operative communication with said counter electrode, and said cross-linked polyazine polymer is in operative communication with said working electrode or said counter electrode. 
     
     
         20 . The electrochemical device of  claim 19 , wherein said cross-linked polyazine polymer is disposed on a least a portion of the working electrode. 
     
     
         21 . The electrochemical device of  claim 19 , wherein the electrochemical device is a battery, a fuel cell, a capacitor or a device formed of a combination thereof, a supercapacitor, an ultracapacitor, or an electric double-layer capacitor. 
     
     
         22 .- 26 . (canceled) 
     
     
         27 . The method of  claim 1 , wherein said cross-linked polyazine polymer comprises a portion having the structure —C═N—N═C— or —C═N—R—N═C—, wherein R comprises said substituted moiety.