Controlling the Polymer Microstructure in Anionic Polymerization by Compartmentalization,Angewandte Chemie International Edition

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Controlling the Polymer Microstructure in Anionic Polymerization by Compartmentalization
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-01-18 , DOI: 10.1002/anie.201710417
Elisabeth Rieger ₁ , Jan Blankenburg _{2,

3} , Eduard Grune _{2,

3} , Manfred Wagner ₁ , Katharina Landfester ₁ , Frederik R. Wurm ₁

Affiliation

An ideal random anionic copolymerization is forced to produce gradient structures by physical separation of two monomers in emulsion compartments. One monomer (M) is preferably soluble in the droplets, while the other one (D) prefers the continuous phase of a DMSO‐in‐cyclohexane emulsion. The living anionic copolymerization of two activated aziridines is thus confined to the DMSO compartments as polymerization occurs selectively in the droplets. Dilution of the continuous phase adjusts the local concentration of monomer D in the droplets and thus the gradient of the resulting copolymer. The copolymerizations in emulsion are monitored by real‐time ¹H NMR kinetics, proving a change of the reactivity ratios of the two monomers upon dilution of the continuous phase from ideal random to adjustable gradients by simple dilution.

中文翻译：

通过区室控制阴离子聚合中的聚合物微结构

理想的无规阴离子共聚被迫通过乳液隔室中两种单体的物理分离产生梯度结构。一种单体（M）优选可溶于液滴，而另一种（D）则更喜欢DMSO-环己烷乳液的连续相。由于在液滴中选择性地发生聚合，因此两个活化的氮丙啶的活性阴离子共聚被限制在DMSO隔室中。连续相的稀释调节液滴中单体D的局部浓度，从而调节所得共聚物的梯度。通过实时监控乳液中的共聚¹1 H NMR动力学证明了通过连续稀释将连续相稀释后，两种单体的反应率从理想的无规梯度变化到可调梯度的变化。

更新日期：2018-01-18

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