New Multi-core-containing Phosphine Of Cu (i) Atom Transfer Radical Polymerization Catalyst Synthesis And Applied Research

It is 40 years since Szwarc and Levy first reported on living anionic polymerization in 1956, and living polymerizations are important for the industrial production of commodity polymers. Atom transfer radical polymerization (ATRP), which reported on by K.Matyjaszewsi in 1995, has become the best simply method for the synthesis of polymer materials via living polymerization. ATRP include radical polymerization and living/control polymerization, which can synthesis various polymers by one step, such as star polymers, comb polymers and graft polymers. Although chemists obtain excellent achievement in ATRP, the investigation of polynuclear Cu(Ⅰ) catalyst used to ATRP reaction is rare, and the studies of catalysts for ATRP are still limited in mononuclear complexes. For ATRP Cu(Ⅰ) catalyst, their structure, photochemical and thermochemical properties as well as catalytic activity have not been studied systemly. Monodentate phosphorus-based ligands were used to form most transition metals complexes including ruthenium, iron, rhenium, nickel and so on. However, it is still in problem for Cu(Ⅰ) phosphorus complex to be used to as ATRP catalyst. Here we report first the application of the polynuclear Cu(Ⅰ) phosphorus complexes on ATRP reaction.In our studies, we found two kinds of new catalysts containing bidentate phosphorus-based ligand can catalyze the polymerization of styrene. Three Cu(Ⅰ) complexes have been synthesized and their structures determined by crystal X-ray analysis. The main results include four parts as shown below.(1) Three complexes have been synthesized by the mixture of Bis(diphenylphosphino)methane(dppm) and CuBr and their structures determined by crystal X-ray analysis.(2) The absorption and emission spectra of the complexes were characterized.(3) The polymerization of styrene was investigated in sealed glass tubes by various molar ration of dppm and CuBr in a 110℃ oil bath. The results of ATRP catalytic reaction will be presented in the text.(4) The polymerization of styrene was investigated in sealed glass tubes by various molar ration of dcpm and CuBr in a 110℃ oil bath. The results of ATRP catalytic reaction will be presented in the text.