Crosslinkable arylamine compounds and conjugated oligomers or polymers based thereon

Abstract

Crosslinkable arylamine compounds; oligomers and polymers prepared from such crosslinkable arylamine compounds; films and coatings; and multilayer electronic devices comprising such films are disclosed.

1 . An arylamine compound of the formula:  
       Z-(Ar—NX) n —Ar—(NX—Ar) n′ -Z,   (I)  wherein,    Ar independently each occurrence is a group comprising one or more divalent aromatic groups, and optionally two Ar groups separated by a single NX group may be joined together by a second covalent bond or by a bridging group, thereby forming a fused multiple ring system;    X is an inert substituent or a cross-linkable group, with the proviso that in at least one occurrence in said compound, X is a crosslinkable group;    Z independently each occurrence is hydrogen or a leaving group,    n is 1 or 2; and    n′ is 0, 1 or 2.    
   
   
       2 . A compound according to  claim 1  wherein X in at least one occurrence is a moiety containing a double bond, a triple bond, a precursor capable of in situ formation of a double bond, or a heterocyclic, addition polymerizable group.  
   
   
       3 . A compound according to  claim 1  wherein X in at least one occurrence is selected from the group consisting of benzocyclobutanyl groups and substituted C 6-12  arylene groups containing one or more substituents selected, from the group consisting of benzocyclobutane, azide, oxirane, di(hydrocarbyl)amino, cyanate ester, hydroxy, glycidyl ether, C 1-4  alkylacrylate, C 1-4  alkylmethacrylate, ethenyl, ethenyloxy, perfluoroethenyloxy, ethynyl, maleimide, nadimide, tri(C 1-4 )-alkylsiloxy, tri(C 1-4 )alkylsilyl, and halogenated derivatives thereof.  
   
   
       4 . A compound according to  claim 1  wherein X in at least one occurrence is 1-benzo-3,4-cyclobutane or 4-phenyl-1-(benzo-3,4-cyclobutane).  
   
   
       5 . A compound according to  claim 1  wherein Z each occurrence is halo, cyano, triflate, azide, —B(OR 1 ) 2 , or  
     
       
         
         
             
             
         
       
       wherein R 1 , independently in each occurrence, is hydrogen or a C 1-10  alkyl group, and  
       R 2 , independently each occurrence, is a C 2-10  alkylene group.  
     
   
   
       6 . A compound according to  claim 1  wherein Ar each occurrence is phenylene, 9,9-di(C 1-20 alkyl)fluorenyl, or a combination thereof; X is 3,4-benzocyclobutan-1-yl, ethenyl or p-ethenylphenyl; Z is bromine or hydrogen; n is 1 or 2; and n′ is 0 or 1.  
   
   
       7 . A compound according to  claim 6  wherein Ar each occurrence is phenylene; each X group is 3,4-benzocyclobutan-1-yl; Z each occurrence is bromine; n is 1 or 2; and n′ is 0.  
   
   
       8 . A compound according to  claim 7  wherein n is 1.  
   
   
       9 . A compound according to  claim 1  having the formula:  
     
       
         
         
             
             
         
       
       wherein Y is a covalent bond, O, S or NR; where  
       R independently each occurrence is i) hydrogen; ii) halogen; iii) a C 1-20  hydrocarbyl group; iv) a hydrocarbyl group substituted with one or more heteroatom containing groups containing up to 20 atoms not counting hydrogen and wherein the heteroatom is selected from S, N, O, P, B or Si; v) a halogenated derivative of iii) or iv); or vi) a substituted derivative of iii) or iv) wherein the substituent is a crosslinkable X group; and  
       n, n′, X, and Z are as previously defined in  claim 1 .  
     
   
   
       10 . An oligomer or polymer having one or more repeating groups of the formula:  
       Z′-(Ar—NX′) n —Ar—(NX′—Ar) n′ -Z′,   (Ia)  where X′ is X or a divalent crosslinked remnant formed by addition polymerization of a crosslinkable X group;    Z′ is Z, a covalent bond, or a terminal group formed by replacement or reaction of a leaving group;    Ar independently each occurrence is a divalent aromatic group, and optionally two Ar groups separated by a single NX group may be joined together by a second covalent bond or by a bridging group, thereby forming a fused multiple ring system;    X is an inert substituent, with the proviso that in at least one occurrence in said compound, X is a crosslinkable group;    Z independently each occurrence is hydrogen or a leaving group,    n is 1 or 2; and    n′ is 0, 1 or 2.    
   
   
       11 . An oligomer or polymer according to  claim 10  having one or more repeating groups Ia) of the formula:  
     
       
         
         
             
             
         
       
       where X′ is X or a divalent crosslinked remnant formed by addition polymerization of a crosslinkable X group;  
       X is an inert substituent or a group capable of forming crosslinking functionality;  
       Y is O, S or NR′;  
       R independently each occurrence is i) hydrogen; ii) halogen; iii) a C 1-20  hydrocarbyl group; iv) a hydrocarbyl group substituted with one or more heteroatom containing groups containing up to 20 atoms not counting hydrogen and wherein the heteroatom is selected from S, N, O, P, B or Si; v) a halogenated derivative of iii) or iv); or vi) a substituted derivative of iii) or iv) wherein the substituent is a crosslinkable X group;  
       Z′ is Z, a covalent bond or a terminal group formed by replacement or reaction of a leaving group;  
       n is 1 or 2; and  
       n′ is 0, 1 or 2.  
     
   
   
       12 . A crosslinked polymer according to  claim 10  or  11  wherein X′ in at least one occurrence is a divalent crosslinked remnant formed by addition polymerization of a crosslinkable X group.  
   
   
       13 . A crosslinked polymer according to  claim 12 , wherein X′ comprises conjugated unsaturation.  
   
   
       14 . A process for preparing oligomers or polymers according to  claim 10 , which comprises heating a composition comprising a compound according to  claim 1  under reaction conditions sufficient to form an oligomer or polymer.  
   
   
       15 . A film comprising one or more of the oligomers or polymers according to  claim 10  or preparable according to  claim 14 .  
   
   
       16 . An electronic device comprising one or more layers of polymer films, at least one of which comprises a film according to  claim 15.