RAFT Polymerization of Styrene and Maleimide in the Presence of Fluoroalcohol: Hydrogen Bonding Effects with Classical Alternating Copolymerization as Reference
RAFT Polymerization of Styrene and Maleimide in the Presence of Fluoroalcohol: Hydrogen Bonding Effects with Classical Alternating Copolymerization as Reference
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氟醇存在下苯乙烯和马来酰亚胺的 RAFT 聚合：以经典交替共聚为参考的氢键效应
DOI：
10.3390/polym9030089
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发表时间：
2017-03
期刊：
影响因子：
5
通讯作者：
Zhu Xiulin
中科院分区：
文献类型：
--
作者：
Yao Fangjun;Liu Qingqing;Zhang Zhengbiao;Zhu Xiulin
氢键对聚合行为的影响一直是人们关注的焦点，但目前还缺乏普遍性和深入的理解。首次探讨了氢键对苯乙烯-马来酰亚胺交替共聚反应的影响。以N-苯基马来酰亚胺（N-PMI）/苯乙烯（St）为模型单体对，在氢键供体溶剂1，1，1，3，3，3-六氟-2-丙醇（HFIP）存在下，N-PMI与HFIP通过氢键相互作用。采用可逆加成-断裂链转移聚合（RAFT）技术，保证了“活性”聚合，从而保证了链组成的均匀性。与在非氢键给体溶剂（甲苯）中的聚合相比，在HFIP中的共聚表现出高速率和轻微偏离交替共聚趋势。N-PMI和St的竞聚率分别为0.078和0.068，而在甲苯中的竞聚率分别为0.026和0.050。这些有趣的结果通过计算机模拟得到了合理的解释，其中揭示了HFIP和N-PMI之间氢键的空间排斥和电子诱导。本工作首次阐明了经典交替型共聚反应中的氢键相互作用，丰富了氢键诱导聚合反应的研究。
The impacts of hydrogen bonding on polymerization behavior has been of interest for a long time; however, universality and in-depth understanding are still lacking. For the first time, the effect of hydrogen bonding on the classical alternating-type copolymerization of styrene and maleimide was explored. N-phenylmaleimide (N-PMI)/styrene was chosen as a model monomer pair in the presence of hydrogen bonding donor solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), which interacted with N-PMI via hydrogen bonding. Reversible addition-fragmentation chain transfer polymerization (RAFT) technique was used to guarantee the “living” polymerization and thus the homogeneity of chain compositions. In comparison with the polymerization in non-hydrogen bonding donor solvent (toluene), the copolymerization in HFIP exhibited a high rate and a slight deviation from alternating copolymerization tendency. The reactivity ratios of N-PMI and St were revealed to be 0.078 and 0.068, respectively, while the reactivity ratios in toluene were 0.026 and 0.050. These interesting results were reasonably explained by using computer simulations, wherein the steric repulsion and electron induction by the hydrogen bonding between HFIP and N-PMI were revealed. This work first elucidated the hydrogen bonding interaction in the classical alternating-type copolymerization, which will enrich the research on hydrogen bonding-induced polymerizations.
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DOI：
10.1002/chin.201011274
发表时间：
2010-03
期刊：
ChemInform
影响因子：
--
作者：
K. Satoh;M. Kamigaito
通讯作者：
K. Satoh;M. Kamigaito
影响因子：
4.6
作者：
C. Zeng;H. Seino;Jie Ren;K. Hatanaka;N. Yoshie
通讯作者：
C. Zeng;H. Seino;Jie Ren;K. Hatanaka;N. Yoshie
影响因子：
56.9
作者：
FUKUI, K
通讯作者：
FUKUI, K
影响因子：
3.8
作者：
Mathammal, R.;Sangeetha, K.;Gadheeja, S.
通讯作者：
Gadheeja, S.
影响因子：
15
作者：
Satoh, Kotaro;Matsuda, Masaru;Kamigaito, Masami
通讯作者：
Kamigaito, Masami