Abstract

The reverse atom transfer radical polymerization (RATRP) technique using FeCl 3/iminodiacetic acid (IMA) complex as a catalyst was applied to the living radical polymerization of acrylonitrile (AN). A hexa-substituted ethane thermal initiator, diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS), was firstly used as the initiator in this iron-based RATRP system. The polymerization in N, N-dimethylformamide not only shows the best control of molecular weight and its distribution but also provides rather rapid reaction rate with the ratio of [AN]:[DCDPS]:[FeCl 3]:[IMA] at 500:1:2:4. The rate of polymerization increases with increasing the polymerization temperature and the apparent activation energy was calculated to be 49.9 kJ mol −1. The polymers obtained were end-functionalized by chlorine atom, and they were used as macroinitiators to proceed the chain extension polymerization in the presence of FeCl 2/IMA catalyst system via a conventional ATRP process. The resultant polyacrylonitrile fibers were obtained with the fineness at 1.16 dtex and the tenacity at 6.01cN dtex −1.

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