Polydioxaborines

Abstract

Novel polydioxaborines are prepared by polymerizing novel monomers that contain a dioxaborine group. Polydioxaborines are readily soluble, excellent film formers, and have semiconducting properties useful in various applications.

1 . A dioxaborine monomer comprising: 
 at least one polymerizable group that can be polymerized by a chain polymerization technique selected from the group consisting of radical polymerization, cationic polymerization, and transition metal catalysis; and    a dioxaborine group of the formula (I),                          wherein R 1 , R 2 , R 3 , L 1  and L 2  are each independently selected from the group consisting of hydrogen, linking atom, electron withdrawing group, and electron donating group; and    wherein the polymerizable group is selected from the group consisting of acrylate, methacrylate, acrylamide, alkene, alkyne, styrene, cyclic N-phenyliminocarbonate, cyclic acid anhydride, sultam, lactam, lactone, and epoxy.    
     
     
         2 . The dioxaborine monomer of  claim 1 , wherein the alkene is a carbocyclic alkene.  
     
     
         3 . The dioxaborine monomer of  claim 2 , wherein the carbocyclic alkene is formed by R 1  and R 2  or by R 2  and R 3 .  
     
     
         4 . The dioxaborine monomer of  claim 2 , wherein the carbocyclic alkene is selected from the group consisting of norbornadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl.  
     
     
         5 . The dioxaborine monomer of  claim 1 , wherein L 1  and L 2  are each independently selected from the group consisting of hydrogen, linking atom, halogen, C 1 -C 6  alkyl, C 1 -C 6  alkoxy, C 1 -C 6  thioalkyl, nitrile, and a bridging ligand formed by L 1  and L 2  together; 
 wherein R 1  and R 3  are each independently selected from the group consisting of hydrogen, linking atom, carboxylate, carboxylic acid, aldehyde, amide, epoxy, acid chloride, anhydride, nitrile, sulfonate, sulfonic acid, phosphonate, nitrate, nitro, C 1 -C 18  alkoxy, C 1 -C 18  alkyl, C 1 -C 18  fluoroalkyl, hydroxyl, C 12 -C 20  diarylamino, C 2 -C 10  dialkylamino, C 1 -C 6  alkylhalide, C 1 -C 6  nitroalkyl, C 1 -C 6  alkanoic acid, C 1 -C 6  alkylamide, C 6 -C 10  aryl, C 7 -C 20  alkylaryl, and C 7 -C 20  alkylaryloxy; and    wherein R 2  is selected from the group consisting of hydrogen, linking atom, carboxylate, carboxylic acid, aldehyde, amide, epoxy, acid chloride, anhydride, nitrile, sulfonate, sulfonic acid, phosphonate, nitrate, nitro, C 1 -C 18  alkoxy, C 1 -C 18  alkyl, C 1 -C 18  fluoroalkyl, C 12 -C 20  diarylamino, C 1 -C 6  alkylhalide, C 1 -C 6  nitroalkyl, C 1 -C 6  alkanoic acid, C 1 -C 6  alkylamide, C 7 -C 20  alkylaryl, and C 7 -C 20  alkylaryloxy.    
     
     
         6 . The dioxaborine monomer of  claim 1 , wherein L 1  and L 2  are each independently a halogen selected from the group consisting of fluoro, chloro, and bromo; R 1  is a linking atom, R 2  is hydrogen, and R 3  is selected from the group consisting of hydrogen, C 1 -C 18  alkyl, C 1 -C 18  alkoxy, C 6 -C 10  aryl, C 6 -C 10  aryloxy, C 7 -C 20  alkylaryl, and C 7 -C 20  alkylaryloxy.  
     
     
         7 . The dioxaborine monomer of  claim 1 , wherein the linking atom is selected from the group consisting of carbon atom, nitrogen atom, oxygen atom, and sulfur atom.  
     
     
         8 . The dioxaborine monomer of  claim 1 , wherein the polymerizable group is acrylate or methacrylate, L 1  and L 2  are each independently a halogen selected from the group consisting of fluoro, chloro, and bromo; R 1  is a 4-phenoxy group having an oxygen atom that is adjacent to the carbonyl of the acrylate or methacrylate, R 2  is hydrogen, and R 3  is selected from the group consisting of C 6 -C 10  aryl, C 6 -C 10  aryloxy, C 7 -C 20  alkylaryl, and C 7 -C 20  alkylaryloxy.  
     
     
         9 . The dioxaborine monomer of  claim 1  comprising: 
 a first reactive group and a second reactive group, wherein the first reactive group and the second reactive group are each independently selected from the group consisting of epoxy, ester, phenol, acid chloride, carbamoyl chloride, sulfonyl chloride, hydrazide, acid anhydride, isothiocyanate, and isocyanate.    
     
     
         10 . The dioxaborine monomer of  claim 9 , wherein R 1  is the first reactive group and R 3  is the second reactive group.  
     
     
         11 . The dioxaborine monomer of  claim 9 , wherein R 1  and R 3  each independently represent a linking atom.  
     
     
         12 . A dioxaborine monomer comprising: 
 a first reactive group and a second reactive group, wherein the first reactive group and the second reactive group are each independently selected from the group consisting of epoxy, ester, phenol, acid chloride, carbamoyl chloride, sulfonyl chloride, hydrazide, acid anhydride, isothiocyanate, and isocyanate; and    a dioxaborine group of the formula (I),                          wherein R 1 , R 2 , R 3 , L 1  and L 2  are each independently selected from the group consisting of hydrogen, linking atom, electron withdrawing group, electron donating group, the first functional group, and the second functional group.    
     
     
         13 . The dioxaborine monomer of  claim 12 , wherein R 1  is the first reactive group and R 3  is the second reactive group.  
     
     
         14 . The dioxaborine monomer of  claim 12 , wherein R 1  and R 3  each independently represent a linking atom.