Well-defined polymer microspheres formed by living dispersion polymerization: precisely functionalized crosslinked polymer microspheres from monomers possessing cumulated double bonds

作者：Yamauchi Akira; Shirai Aya; Kawabe Kazunari; Iwamoto Tadashi; Wakiya Takeshi; Nishiyama Hiroki; Inagi Shinsuke; Tomita Ikuyoshi^*

来源：NPG Asia Materials, 2016, 8(9): e307.

DOI：10.1038/am.2016.123

The precise method for synthesizing well-defined polymer microspheres via pi-allylnickel-catalyzed living coordination polymerization of allene derivatives under dispersion polymerization conditions is described. The p-allylnickel-catalyzed living coordination polymerization of allene derivatives such as phenoxyallene was carried out in protic solvents such as methanol in the presence of stabilizers such as polyvinylpyrrolidone to produce polymer microspheres with a narrowly dispersed diameter distribution (D-w/D-n) at a high yield. For example, polymer microspheres with a number-average diameter (D-n) of 1.10 mu m and Dw/Dn of 1.01 were obtained at a yield of 97%; these microspheres are composed of a polymer with a controlled molecular weight (M-n= 11 700) and narrow molecular weight distribution (M-w/M-n= 1.06). The size of the resulting polymer microspheres proved to be affected by polymerization conditions such as the initial monomer concentrations, monomer structures, polymerization media and stabilizers. Unlike conventional dispersion polymerization systems, the use of a bifunctional monomer, 1,4-diallenoxybenzene, for this living dispersion polymerization successfully produced well-defined crosslinked living polymer microspheres that exhibited high solvent tolerance. The postpolymerization of functional allene monomers in the living dispersion polymerization was also successful, resulting in functionalized polymer microspheres that could be applied in solid-phase organic synthesis and solid-supported transition metal catalysis.

• 出版日期2016-9