新型偶氮引发剂AIBME引发的衣康酸二甲酯反向原子转移自由基聚合反应
Reverse atom transfer radical polymerization of dimethyl itaconate initiated by a new azo initiator: AIBME.
作者信息
Zhang Xin, Ji HaiJun, Yang Hui, Yu Jie, Wang Jiaqi, Zhang Liqun, Zhou Xinxin, Wang Runguo
机构信息
Beijing Advanced Innovation Center for Soft Matter Science and Engineering, State Key Laboratory of Organic-Inorganic Composites & Beijing Laboratory of Biomedical Materials, Beijing University of Chemical Technology Beijing 100029 P. R. China
出版信息
RSC Adv. 2022 May 4;12(21):13347-13351. doi: 10.1039/d1ra08878e. eCollection 2022 Apr 28.
Reverse atom transfer radical polymerization (RATRP) was used to synthesize poly(dimethyl itaconate) (PDMI) using an AIBME/CuBr/dNbpy system. The number average molecular weight ( ) of PDMI was as high as = 15 000 g mol, the monomer conversion rate reached up to 70%, and the dispersity remained low ( = 1.06-1.38). The first-order kinetics of PDMI are discussed in detail. The AIBME initiator had a higher initiation efficiency than the AIBN initiator. As the ratio of initiator (AIBME) to catalyst (CuBr) decreased, the and of PDMI decreased. At 60 °C and 80 °C, the of PDMI was much higher than the theoretical number average ( ), and the of PDMI broadened with the conversion rate. At 100 °C, the of PDMI remained low, and the of PDMI was closer to the . As the ratio of monomer (DMI) to initiator (AIBME) increased, the of PDMI changed little over time. These phenomena could be explained by the influence of the initiator and catalyst on polymerization kinetics.
采用反向原子转移自由基聚合（RATRP）法，以AIBME/CuBr/dNbpy体系合成了聚衣康酸二甲酯（PDMI）。PDMI的数均分子量（ ）高达 = 15000 g/mol，单体转化率高达70%，且分散度保持较低（ = 1.06 - 1.38）。详细讨论了PDMI的一级动力学。AIBME引发剂的引发效率高于AIBN引发剂。随着引发剂（AIBME）与催化剂（CuBr）的比例降低，PDMI的 和 降低。在60℃和80℃时，PDMI的 远高于理论数均分子量（ ），且PDMI的 随转化率增大而变宽。在100℃时，PDMI的 保持较低，且PDMI的 更接近 。随着单体（DMI）与引发剂（AIBME）比例的增加，PDMI的 随时间变化不大。这些现象可以通过引发剂和催化剂对聚合动力学的影响来解释。
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