Facile Synthesis And Properties Of Stereoregular Helical Poly(Phenyl Isocyanide)s And Its Block Copolymers

Due to the properties such as simply prepared,economical and efficient,Ni(II)complexes have been one of the most widely used catalysts and can initiate several monomers polymerized in "living/controlled" manners.In this paper,we designed and synthesized a series of Ni(II)complexes for the homopolymerization and block copolymerization of isocyanides and 3-hexyl thiophene.We successfully constructed a variety of polyisocyanides and "rigid-rigid" block conjugated copolymers,obtained a lot of polymer materials with excellent properties.In the first part,we designed and synthesized a new type of π-allylnickel complexes for the helix-sense-selective polymerization of achiral isocyanides.The polymerization led to the formation of optically active helical polyisocyanides induced by the chiral Ni(Ⅱ)complexes.Based on this,the influencing factors,reaction controllabilities and end group activities of the polymerization were checked.The most suitable condition for the polymerization was checked and the living manner of the polymerization was proved.The high activity of the Ni(II)complexes allowed us to perform a one-pot block polymerization and we successfully obtained well-defined polythiophene-b-polyisocyanide block copolymer.Characterizations of the obtained copolymer and its optical and self-assembly properties were investigated at last.In the second part,we designed and synthesized a kind of carbazole functionalized isocyanides.The soluble carbazole functionalized conjugated polyisocyanides were obtained and their properties were checked.Some disadvantages in the previous works were overcome and the solubilities and the photoelectric properties of the polymers were greatly improved.After that,we also successfully obtained the well-defined polythiophene-b-polyisocyanides block copolymers by one-pot block polymerization and the characterizations shown that the materials could be used as potential photoelectric materials.