Well-Defined Multi-Amino-Functional and Stimuli-Responsive Poly(propylene oxide) by Crown Ether Assisted Anionic Ring-Opening Polymerization,Macromolecules

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Well-Defined Multi-Amino-Functional and Stimuli-Responsive Poly(propylene oxide) by Crown Ether Assisted Anionic Ring-Opening Polymerization
Macromolecules ( IF 5.1 ) Pub Date : 2017-11-09 00:00:00 , DOI: 10.1021/acs.macromol.7b01324
Jan Blankenburg _{1,

2} , Manfred Wagner ₃ , Holger Frey ₁

Affiliation

Multi-amino-functional poly(propylene oxide) (PPO) copolymers were synthesized by the anionic ring-opening copolymerization (AROP) of N,N-diethyl glycidyl amine (DEGA) and propylene oxide (PO). A solvent free synthesis route using potassium counterions and crown ether for the AROP enabled controlled (co)polymerization with full conversion. The strategy provided access to PPO-b-PDEGA block copolymers, statistical PPO-co-PDEGA copolymers, and, for the first time, PDEGA homopolymer. Molecular weights in the range of 1400 to 4200 g/mol (M_n) and dispersities (M_w/M_n) below 1.1 were obtained. Both the kinetics and resulting microstructure of the statistical copolymerization were investigated by in situ¹H NMR spectroscopy, revealing reactivity ratios of r_PO = 1.7 and r_DEGA = 0.9. The polyethers exhibit thermoresponsive behavior in aqueous solution, showing cloud points in the range 14–57 °C under neutral conditions. Because of the amine groups, the copolymer structures are strongly affected by the pH of the solution, and therefore the cloud points are highly pH-dependent. By changing the pH of the polymer solution, the cloud points can be tuned between 5 and 100 °C, as studied by turbidity measurements. The copolymers offer new potential for PPO-based structures for surface modification, biomedical purposes and pharmaceutical application.

中文翻译：

冠醚辅助阴离子开环聚合反应，定义完善的多氨基官能团和对刺激敏感的聚环氧丙烷

通过N，N-二乙基缩水甘油胺（DEGA）和环氧丙烷（PO）的阴离子开环共聚（AROP）合成了多氨基官能的聚环氧丙烷（PPO）共聚物。使用钾抗衡离子和冠醚进行AROP的无溶剂合成路线可实现受控（共）聚合和完全转化。该策略提供了对PPO- b- PDEGA嵌段共聚物，统计PPO-共-PDEGA共聚物以及PDEGA均聚物的访问。分子量范围为1400至4200 g / mol（M _n）和分散度（M _w / M _n获得低于1.1的值。通过原位¹ H NMR光谱研究了统计共聚反应的动力学和微观结构，揭示了r _PO = 1.7和r _DEGA的反应率= 0.9。聚醚在水溶液中表现出热响应性，在中性条件下的浊点范围为14–57°C。由于有胺基，溶液的pH值会强烈影响共聚物的结构，因此浊点与pH值高度相关。通过浊度测量研究，通过改变聚合物溶液的pH值，可以在5至100°C之间调节浊点。该共聚物为基于PPO的结构进行表面改性，生物医学目的和制药应用提供了新的潜力。

更新日期：2017-11-09

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