Synthesis And Topochemical Solid-state Polymerization Of Diacetylene Derivatives Containing Nitrobenzene

Nonlinear optical materials have been taking an important part in the information technology and also have good prospects for the development and application value. Polydiacetylene(PDA) derivative is a third-order organic polymeric nonlinear optical material, which has attracted increasing attention becacuse it has the advantages of larger three order nonlinear coefficient, chemical and thermal stability, fast response time, easy processing. PDA was obtained by topological solid-state polymerization of diacetylene derivative monomer. The topological solid-state polymerization occurs that requires a certain conditional. In this paper para-position and meta-position nitrobenzene were introduced to adjust the structure of diacetylene derivative monomer or diacetylene (DA) derivative polymer brushes were prepared by atom transfer radical polymerization to make it meet the solid-state polymerization conditions. Research work is as follows:1. Twelve diacetylene derivatives monomers containing nitrobenzene were synthesized (Figure1), in which six compounds(Nd2、NL3、NL5、Nm2、NY3、NY5) have not been reported. Monomers characterized by MS,1H NMR,13C NMR, IR, UV and Fluorescence spectra.2. The solid-state polymerization of monomers were investigated in cast film under UV irradiation (250nm). Polymerization processes were characterized by UV, IR and the resulting polymer molecular weight was measured by GPC.3. The solid-state polymerization of diacetylene derivativites under heating was investigated. The results showed that irregular solid-state polymerization occurred instead of regular polymerization.4. The crystal of NY3monomer can partially turn into purple at room temperature. The purple solid was obtained by dissolving it in an organic solvent such as chloroform, tetrahydrofuran and its properties were in progress.5. Four monomers which were not reported before were grafted to the substrate by ATRP to form polymer brushes which was characterized by Contact angle, UV and AFM methods (Figure2).6. The polymerization of the four polymer brushes were investigated by UV irradiation and was characterized by contact angle, UV absorption and fluorescence emission spectra. The results indicated that irregular polymerization of the four kind of polymer brush occurred under UV irradiation conditions.