Synthesis And Functional Studys Of Thiophene-Substituted Heterocyclic Compounds

Thiophene is a compound containing a flat structure of five membered ring, and the delocalized π bond between lone pair electrons on the sulfur atom of thiophene ring and double bond make it a conjugated molecular, so thiophene posseses properties of excellent electron transport and optics, which are playing an important role in the designing of functional materials. Phenothiazine and carbazole are photosensitizers to 4,4’-dimethyl phenyl iodonium six fluoride phosphate (ION) in photopolymerization. In this thesis, we designed and synthesized novel thiophene-substituted phenothiazine and carbazole compounds (ThArs), in order to not only endow them with good optical properties, and enhance the photosensitive effect to ION.Six thiophene-substituted phenothiazine ThPTZs and five thiophene-substituted carbazole ThCzs were synthesized via Suzuki coupling reaction using phenothiazines bromide and carbazoles bromide with 3-thiophene boronic acid. And they have been characterized via IR, ’H NMR, 13C NMR and MS.The thiophene-substituted heterocyclic compounds containing silicone moiety (ThPCzS and Th2PCzS) were synthesized via hydrosilylation between 1,1,1,3,5,5,5-heptamethyltrisiloxanes(HMTS) and ThACz. Samely, the ThCz-DSiO, Th2Cz-DSiO, ThCz-SiO and Th2Cz-SiO were prepared by the hydrosilylation of D4H and HHMS with ThACz or Th2ACz as main reactants. Using the same method, the four epoxy-organosiloxanes Ep-ThCz-DSiO, Ep-Th2Cz-DSiO, Ep-ThCz-SiO and Ep-Th2Cz-SiO were synthesized by the hydrosilylation of ThCz-DSiO, Th2Cz-DSiO, ThCz-SiO, Th2Cz-SiO and 1,2-epoxy-4-vinylcyclohexane(VCHO) using Lamoreaux’catalyst. And these compounds have been characterized by FT-IR spectrum,1H NMR spectrum and 13C NMR spectrum.The UV-vis spectra, FL Spectra and CV curves of ThArs were studied. The UV-vis results showed that ThPTZs absorbed strongly between 400nm and 500nm. And the charge transfer reaction between ThArs and ION is feasible based on the thermodynamics.The photosensitive effect of ThArs to ION were studied, the results demonstrated that ThArs have a strong photosensitive effect to ION under 405nm and 455nm LED, ThPTZs/ION system can efficiently initiat the photopolymerization of TPGDA and E51, and the order of photoinitiation is ThFEPTZ> Th2EPTZ> ThFEPTZ, at the same time, ThCzs and organosiloxanes modified by ThACzs also have a strong photosensitive effect to ION under halogen lamp.The surface wettability of cured material because of epoxy-organosiloxanes modified by ThACzs also have been studied by the determination of static contact angle, the result indicated that the static contact angle rised obviously as the augment of the content of epoxy-organosiloxanes modified by ThACzs, so epoxy-organosiloxanes modified by ThACzs not only can efficiently photoinitiate the polymerization of TPGDA and E51, but also enhance the hydrophobicity of cured materials.