Solid-State Phase Reaction And Characterization Of The Derivatives Of Thiophene

The derivatives of polythiophene usually have desirable electrochemical activity, environmental stability and easy processibility, which provide potential applications in various fields as electronics, optics, biology, etc. The solid state reaction at low-heating temperatures should be developed in the future chemical industry due to its advantages of being absent of solvent, conserving energy, the simple and convenient of equipment and operation, good selectivity , achieving good yield, and producting almost no pollution.The solid state reaction at low-heating temperatures, emerging as a chemical synthesis in accord with the principle and request of Green Synthesis, is increasingly recognized in the syntheses of materials.A serial of novel thiophene-based main chain conjugated compounds with varieties of aromatic rings and heterocycle, such as pyridazine, benzene and 2,1,3-benzothiadiazole,have been synthesized on the base of looking for lots of references and summarized others research work. Then these homopolymers, copolymers and polymerized with 2,1,3-benzoselenadiazole andα-T have been prepared with solid-state phase reaction synthesis method at room temperature . The copolymerization method and the condition of the copolymer of the 1,4-dithiophenyl-benzene and 2,1,3-benzoselenadiazole have been studied. The structure of those polymers have been characterized by FT-IR, UV-vis, SEM, TEM, XRD and Cyclic Voltammogram.(1) A serial of novel thiophene-based main chain conjugated compounds with varieties of aromatic rings and heterocycle, such as pyridazine ,benzene and 2,1,3-benzothiadiazole have been prepared by tetra(triphenylphosphine)palladium (Pd(PPh3)4) catalyzed method. These compounds were characterized by FT-IR, 1H-NMR and elemental analysis.(2) Poly(3,6-dithiophenyl-pyridazine)(P(DThPD)),Poly(1,4-dithiophenyl-benzene)(P(DThPh)) and Poly(4,7-dithiophenyl-2,1,3-benzothiadiazole)(P(DThB)) have been prepared by a novel solid-state phase reaction synthesis method at room temperature and were characterized by FT-IR, Uv-vis, XRD, SEM,TEM, CV. The TEM images showed that P(DThPD) and P(DThPh) had nanostructures. The UV-vis spectra of P(DThPD) showed absorption peaks at about 336 nm , 450 nm and 580 nm(w) , P(DThPh) showed absorption peaks at about 325 nm and 410 nm, P(DThB) showed absorption peaks at about 460 nm , 550 nm and 700 nm, respectively. P(DThPh) and P(DThB) were 488 nm and 599 nm in the photoluminescence spectra , respectively. These polymers prepared by the method had good electrochemical properties.(3) The copolymer I of 3,6-dithiophenyl-pyridazine and 1,4-dithiophenyl-benzene, the copolymer II of 3,6-dithiophenyl-pyridazine and 4,7-dithiophenyl-2,1,3-benzothiadiazole, the copolymer III of 4,7-dithiophenyl-2,1,3-benzothiadiazole and 1,4-dithiophenyl-benzene have been prepared by a novel solid-state phase reaction synthesis method at room temperature and were characterized. The SEM images showed that three polymers have the samdwish structure with nanoparticals cluster. The UV-vis spectra of copolymer I showed absorption peaks at about 334 nm,422 nm(w) and 542 nm(w) , respectively. The UV-vis spectra of copolymer II showed absorption peaks at about 331 nm,435nm(w) and 537nm(w), respectively. The UV-vis spectra of copolymer III showed absorption peaks at about 309 nm,449 nm and 750 nm(w), respectively. These polymers prepared by solid-state reaction synthesis had good electrochemical properties.(4) The copolymer I of 3,6-dithiophenyl-pyridazine and 2,1,3-benzoselenadiazole, the copolymer II of 1,4-dithiophenyl-benzene and 2,1,3-benzoselenadiazole, the copolymer III of 4,7-dithiophenyl-2,1,3-benzothiadiazole and 2,1,3-benzoselenadiazole, the copolymer IV of 3,6-dithiophenyl-pyridazine andα-T, the copolymer V of 1,4-dithiophenyl-benzene andα-T, the copolymer VI of 4,7-dithiophenyl-2,1,3-benzothiadiazole andα-T have been prepared by a novel solid-state reaction synthesis method at room temperature and were characterized. The SEM images showed that copolymers have no especial sructure. The UV-vis showed that the maximal absorbance of copolymers were all Einstein shift, which illuminates that the chain unit of conjugate is increased and the capability of conjugate become better. These copolymers prepared by the method had good electrochemical properties.(5) The copolymerization method and the condition of the copolymer of the 1,4-dithiophenyl-benzene and 2,1,3-benzoselenadiazole have been studied. According to UV-vis test, we found the best copolymerization method and condition .That is, at room temperature, the copolymer was synthesized by solid-state phase reaction with FeCl3 as the polymerization starter for 2 hours(nmonpmer:n FeCl3 is 1:10).