One-pot synthesis of structure-controlled temperature-responsive polymer gels,Polymer Chemistry

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One-pot synthesis of structure-controlled temperature-responsive polymer gels
Polymer Chemistry ( IF 4.1 ) Pub Date : 2022-06-17 , DOI: 10.1039/d2py00554a
Tomoki Sakai ₁ , Nagisa Ito ₁ , Mitsuo Hara ₁ , Takahiro Seki ₁ , Mineto Uchiyama ₁ , Masami Kamigaito ₁ , Kotaro Satoh ₂ , Taiki Hoshino ₃ , Yukikazu Takeoka ₁

Affiliation

The simultaneous use of metal Lewis acids and photo-radical generators for dithioesters, which are the common dormant species for cationic and radical polymerization, made it possible to convert a cationic species into a radical upon photoirradiation. In this study, we attempted one-pot synthesis of temperature-responsive polymer gels with controlled network structure by using temperature-responsive telechelic polymers prepared by cationic polymerization in the dark followed by the mechanistic transformation into radical cross-linking reaction under photoirradiation. Specifically, the polymerization of 2-(2-ethoxy)ethoxyethyl vinyl ether (EO2) in the presence of a crosslinking agent (divinyl adipate) was performed at 4 °C in toluene using a vinyl ether-type bifunctional RAFT reagent as initiator, a Lewis acid (Et₃Al₂Cl₃) and a photo radical generator (TPO). The conditions for gelation by radical polymerization with photoirradiation were investigated in detail by considering the molecular weight control and overlapping concentration of the telechelic polymers obtained by cationic polymerization. As a result, small-angle X-ray scattering revealed that polymer gels with a relatively uniform network structure can be obtained compared to the cross-linked network of polymer gels obtained by conventional free-radical polymerization.

中文翻译：

一锅法合成结构可控的温度响应性聚合物凝胶

同时使用金属路易斯酸和用于二硫酯的光自由基产生剂是阳离子和自由基聚合的常见休眠物质，使得在光辐照时将阳离子物质转化为自由基成为可能。在这项研究中，我们尝试一锅法合成具有可控网络结构的温度响应型聚合物凝胶，方法是使用在黑暗中阳离子聚合制备的温度响应型遥爪聚合物，然后在光辐照下机理转化为自由基交联反应。具体而言，2-(2-乙氧基)乙氧基乙基乙烯基醚 (EO2) 在交联剂 (己二酸二乙烯酯) 存在下的聚合反应是在 4°C 的甲苯中使用乙烯基醚型双功能 RAFT 试剂作为引发剂进行的。路易斯酸（Et ₃Al ₂ Cl ₃ ) 和光自由基产生剂 (TPO)。通过考虑通过阳离子聚合获得的遥爪聚合物的分子量控制和重叠浓度，详细研究了通过光辐照自由基聚合凝胶化的条件。结果，小角X射线散射表明，与传统的自由基聚合得到的聚合物凝胶交联网络相比，可以得到具有相对均匀网络结构的聚合物凝胶。

更新日期：2022-06-17

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