Method of preparing derivatives of polyarylene vinylene and method of preparing an electronic device including same

Abstract

A technique is described for the preparation of polymers according to a process in which the starting compound of formula (I) is polymerized in the presence of a base in an organic solvent. No end chain controlling agents are required during the polymerisation to obtain soluble precursor polymers. The precursor polymer such obtained comprises structural units of the formula (II). In a next step, the precursor polymer (II) is subjected to a conversion reaction towards a soluble or insoluble conjugated polymer by thermal treatment. The arylene or heteroarylene polymer comprises structural units of the formula III. In this process the dithiocarbamate group acts as a leaving group and permits the formation of a precursor polymer of structural formula (II), which has an average molecular weight from 5000 to 1000000 Dalton and is soluble in common organic solvents. The precursor polymer with structural units of formula (II) is thermally converted to the conjugated polymer with structural formula (III).

1 . A conjugated polymer with the general formula: 
       
         
           
           
               
               
           
         
         wherein Ar is an aromatic divalent group or an heteroaromatic divalent group; 
         wherein each R 3  and R 4  is independently selected from the group consisting of hydrogen, a C 1 -C 20  alkyl group, a cyclic C 3 -C 20  alkyl group, an aryl group, an alkylaryl group, an arylalkyl group and a heterocyclic group; and 
         wherein n is an integer from 5 to 2000 and which are formed with the method according to an embodiment. 
       
     
     
         2 . The conjugated polymer of  claim 1 , wherein Ar comprises from 4 to 20 carbon atoms. 
     
     
         3 . The conjugated polymer of  claim 1 , wherein Ar is substituted with a substituent selected from the group consisting of C 1 -C 20  alkyl, C 3 -C 20  alkoxy, C 1 -C 20  alkylsulfate, poly(ethylene oxide), poly(ethylene glycol), phenyl, and benzyl 
     
     
         4 . The conjugated polymer of  claim 1 , wherein Ar comprises up to four ring heteroatoms selected from the group consisting of oxygen, sulphur, and nitrogen. 
     
     
         5 . The conjugated polymer of  claim 1 , wherein Ar is selected from the group consisting of 2,6-naphthalenediyl, 1,4-naphthalenediyl, 1,4-anthracenediyl, 2,6-anthracenediyl, 9,10-anthracenediyl, 2,4-thienylene, 2,3-thienylene, 2,5-furanediyl, 2,5-pyrrolediyl, 1,3,4-oxadiazole-2,5-diyl, 1,3,4-thiadiazole-2,5-diyl, 2,5-benzo[c]thienylene, thieno[3,2-b]thiophene-2,5-diyl, pyrrolo[3,2-b]pyrrole-2,5-diyl, pyrene-2,7-diyl, 4,5,9,10-tetrahydropyrene-2,7-diyl, 4,4′-bi-phenylene, phenantrene-2,7-diyl, 9,10-dihydrophenantrene-2,7-diyl, dibenzofurane-2,7-diyl, and dibenzothiophene-2,7-diyl. 
     
     
         6 . The conjugated polymer of  claim 1 , wherein Ar is 1,4-phenylene. 
     
     
         7 . The conjugated polymer of  claim 1 , wherein Ar is 2,5-thienylene. 
     
     
         8 . The conjugated polymer of  claim 1 , having a formula: 
       
         
           
           
               
               
           
         
         wherein the conjugated polymer has a peak at a wavelength higher than 520 nm in the absorption spectrum. 
       
     
     
         9 . The conjugated polymer of  claim 1 , wherein the conjugated polymer has a peak at a wavelength of 570 nm in the absorption spectrum. 
     
     
         10 . The conjugated polymer of  claim 1 , having an average molecular weight of from 5000 daltons to 1000000 daltons. 
     
     
         11 . The conjugated polymer of  claim 1 , having an average molecular weight of from 5000 daltons to 500000 daltons. 
     
     
         12 . The conjugated polymer of  claim 1 , wherein a polydispersity of the conjugated polymer is from 1.5 to 5.5. 
     
     
         13 . The conjugated polymer of  claim 1 , wherein a polydispersity of the conjugated polymer is from 2 to 3. 
     
     
         14 . The conjugated polymer of  claim 1 , wherein the conjugated polymer is a linear polymer. 
     
     
         15 . The conjugated polymer of  claim 1 , wherein the conjugated polymer is fully converted. 
     
     
         16 . The conjugated polymer of  claim 1 , comprising at least two different monomers having a general formula: 
       
         
           
           
               
               
           
         
       
     
     
         17 . The conjugated polymer of  claim 1 , comprising no chain end controlling additive. 
     
     
         18 . A device selected from the group consisting of a solar cell, a light-emitting diode and an integrated circuit, an organic transistor, a chemical sensor, and a biological sensor, wherein the device comprises a layer of a conjugated polymer of  claim 1 . 
     
     
         19 . The device of  claim 18 , wherein Ar is selected from the group consisting of 1,4-phenylene and 2,5-thienylene, and wherein R 3  and R 4  are hydrogen. 
     
     
         20 . The device of  claim 18 , wherein the device is a solar cell, and wherein an active layer of the device comprises the conjugated polymer. 
     
     
         21 . The device of  claim 18 , wherein the device is an organic bulk heterojunction solar cell, and wherein an active layer of the device comprises a blend of an n-type material and the conjugated polymer. 
     
     
         22 . The device of  claim 21 , wherein the n-type material is a C 60  derivative. 
     
     
         23 . The device of  claim 18 , further comprising an electrode atop the layer of conjugated polymer. 
     
     
         24 . The device of  claim 18 , wherein the layer of conjugated polymer is an annealed layer wherein stresses in the polymer chains are reduced.