The Preparation Of Electropolymers Based On Polyacrylate-grafted Thienyl Groups And Their Properties Characterization

Since the discovery of polyacetylene doped by I2 with high conductivity, the research and application of conducting polymers rapidly attracted researchers’great attention. Until now, a great number of conducting polymers such as polythiophene, polypyrrole, polyaniline and polyphenylene etc. have been known. Electrochemistry is the most important way to prepare conducting polymers in all of ways. In order to lower the onset oxidation potential of electroactive monomers to obtain conducting films with good properties, boron trifluoride diethyl etherate (BFEE) is introduced into electrochemical system as solvent and electrolyte. But, as we are known, the structure of polyconjugation in conducting polymers restrict free rotation and moving of congducting chains, leading to the stiff and fragile and inmeltable and insoluble character, ultimately to limit theirs appilication. In recent years, the novel polymeric unit such as acrylate-modified conducting polymers appear to gradually improve their properties, finally to obtain the free-standing crosslinked films. First, acrylate-modified elecreoactive monomer was prepared by organic synthsis; second, the free radical polymerization of diffrent acrylates and above-prepared polymeric electroactive monomer can obtain precursors copolymers; third, their electrochemistry polymerization in BFEE can gain crosslinked net electropolymers films so as to improve their merchanial and thermal property. This paper mainly designed and prepared acrylate-modified thiophene monomer, and its homopolymerization and copolymerizations with methyl methacrylate (MMA), butyl acrylate (BA) and arylic acid (AA), respectively, were progressed to get four precursors polymers, followed by their electrochemical polymerization to improve the optical and merchanical and thermal property.1、A novel acrylate-modified thiophene (TE-AA) was synthesized and its free radical homopolymerization led to two diffrent molecular mass precursors polymers (TE-PAA) and their secondery electrochemical polymerization in 50%(vol) BFEE+ DCM obtained crosslinked net electropolymers polyacrylate-modified polythiophene (PTE-PAA). The precuesors and electropolymers were charactered by CV、UV-vis、 FT-IR、TGA、TEM and 1H NMR. From the anodic polarization curves, we can see that with increasing of relative molecular mass, the electrochemical behavior and thermal stability as well as their conjugated chain increased while electrochemical stability of polymers decreased. Additionally, fluorescence spectra showed that these obtained crosslinked polymers were still good blue-light emitters.2、The precursor thienyl-group-bearing acrylic polymer TE-PAA-co-PMMA, obtained with above-prepared TE-AA and methyl methacrylate (MMA) through free radical copolymerization, was prepared chemically to free-standing, processible conducting conjugated PTE-PAA-co-PMMA in 50%(vol) BFEE+DCM. The precuesors and electropolymers were charactered by CV、UV-vis、FT-IR、TGA、 TEM and 1H NMR. The onset oxidation potential of precursor was 1.07 V; CVs showed that the resultant electropolymer had good redox reversibility, accompanied with obvious color change from dark blue (oxidized state) to transmissive yellow-green (reduced state). Moreover, CVs and TGA presented that the electropolymer had excellent electrochemical activity and stability and thermal stability.3、The precursor thienyl-group-bearing acrylic polymer TE-PAA-co-PBA, obtained with above-prepared TE-AA and butyl acrylate (BA) through free radical copolymerization, was prepared chemically to free-standing, processible conducting conjugated PTE-PAA-co-PBA in 50%(vol) BFEE+DCM. The precuesors and electropolymers were charactered by CV、UV-vis、FT-IR、TGA、TEM and 1H NMR. Spectroelectrochemistry showed that the resultant electropolymer had good electrochromic property, and it can be applied to electrochromic device. Moreover, its conductivity was 6.67×10-4S cm-1.4、The precursor thienyl-group-bearing acrylic polymer TE-PAA-co-PAA, obtained with above-prepared TE-AA and acrylic acid (AA) through free radical copolymerization, was prepared chemically to free-standing, processible conducting conjugated PTE-PAA-co-PAA in 50%(vol) BFEE+DCM. The precuesors and electropolymers were charactered by CV、UV-vis、FT-IR、TGA、TEM and 1H NMR. The results showed that the onset oxidation potential of precursor was 1.06 V; CVs and TGA curves of resultant electropolymer presented good electrochemical and thermal stability; during the process of redox, there was obvious color change from dark blue in oxidized state to yellow-green in reduced state.