Atom transfer radical polymerization of an epoxide-containing monomer, 4-vinylphenyloxirane, employing low concentration of catalyst: synthesis of linear and star-shaped macromolecules

作者：McLeod David C; Tsarevsky Nicolay V^*

来源：Polymer International, 2014, 63(5): 868-875.

DOI：10.1002/pi.4711

• controlled radical polymerization
• ATRP
• functional polymers
• epoxides

4-Vinylphenyloxirane (4VPO) was homopolymerized under initiators for continuous activator regeneration atom transfer radical polymerization (ATRP) conditions using diethyl 2-bromo-2-methylmalonate, ethyl 2-bromoisobutyrate, as well as tri-, tetra- and hexafunctional 2-bromisobutyrates as the initiators to yield well-defined linear and star-shaped epoxide-containing homopolymers. In addition, the chain extension of Br-capped polystyrene with 4VPO afforded well-defined block copolymers. All polymerizations employed 2,2 '-azobisisobutyronitrile as the reducing agent and the Cu-I and Cu-II bromide complexes of tris(2-pyridylmethyl)amine as mediators at total concentration of Cu not exceeding ca. 46 ppm (by weight) or ca. 198 ppm (molar). Excellent polymerization control was observed even when the Cu concentration was decreased to ca. 12 ppm (by weight) or ca. 48 ppm (molar). The successful, well-controlled, low-catalyst-concentration ATRP of 4VPO in the absence of any external reducing agent is also demonstrated. In such systems, the epoxide groups present in the monomer and the polymer derived from it serve as internal reducing agents.

• 出版日期2014-5