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Tricomponent thermoresponsive polymers based on an amine-containing monomer with tuneable hydrophobicity: Effect of composition
European Polymer Journal ( IF 6 ) Pub Date : 2020-05-01 , DOI: 10.1016/j.eurpolymj.2020.109655
Anna P. Constantinou , Tian Lan , Dean R. Carroll , Theoni K. Georgiou

Abstract In the present study, six dual-responsive ABC triblock copolymers were synthesised via group transfer polymerisation (GTP) and investigated through visual inspections in terms of their thermoresponsive behaviour. The copolymers consist of i) penta(ethylene glycol) methyl ether methacrylate (PEGMA), which is hydrophilic and thermoresponsive at high temperatures, ii) n-butyl methacrylate (BuMA) as the hydrophobic counterpart to promote self-assembly, and iii) 2-(diethylamino)ethyl methacrylate (DEAEMA), which is pH-responsive by adjusting its hydrophilicity depending on the pH. The effect of the degree of ionisation of DEAEMA units as well as the ionic strength effect on the self-assembly behaviour of the copolymers was tested via dynamic light scattering (DLS). The dissociation constants (pKa) of the amine units of DEAEMA were determined via potentiometric titrations. The thermoresponse has primarily been investigated in means of cloud points (CPs) at various pH values in deionised water. Detailed phase diagrams were constructed for all the polymer solutions in phosphate buffered saline (PBS), with the interest being focused on the gelation area. It has been clearly proven that gelation is promoted as the content in BuMA and DEAEMA is increased. The polymer that presented the widest gelation area has been further investigated via rheology in terms of its gelation temperature, gelation time and shear-thinning properties.

中文翻译:

基于具有可调疏水性的含胺单体的三组分热敏聚合物:组成的影响

摘要 在本研究中,通过基团转移聚合 (GTP) 合成了六种双响应 ABC 三嵌段共聚物,并通过目视检查它们的热响应行为。该共聚物由 i) 五(乙二醇)甲基醚甲基丙烯酸酯 (PEGMA) 组成,其在高温下具有亲水性和热响应性,ii) 甲基丙烯酸正丁酯 (BuMA) 作为促进自组装的疏水对应物,以及 iii) 2 -(二乙氨基)乙基甲基丙烯酸酯 (DEAEMA),通过根据 pH 值调节其亲水性而具有 pH 响应性。通过动态光散射 (DLS) 测试 DEAEMA 单元电离度的影响以及离子强度对共聚物自组装行为的影响。DEAEMA 胺单元的解离常数 (pKa) 通过电位滴定确定。热响应主要通过去离子水中各种 pH 值下的浊点 (CP) 进行研究。为磷酸盐缓冲盐水 (PBS) 中的所有聚合物溶液构建了详细的相图,重点关注凝胶化区域。已经清楚地证明,随着BuMA和DEAEMA中含量的增加,凝胶化得到促进。已经通过流变学在凝胶温度、凝胶时间和剪切稀化性能方面对呈现最宽凝胶区域的聚合物进行了进一步研究。为磷酸盐缓冲盐水 (PBS) 中的所有聚合物溶液构建了详细的相图,重点关注凝胶化区域。已经清楚地证明,随着BuMA和DEAEMA中含量的增加,凝胶化得到促进。已经通过流变学在凝胶温度、凝胶时间和剪切稀化性能方面对呈现最宽凝胶区域的聚合物进行了进一步研究。为磷酸盐缓冲盐水 (PBS) 中的所有聚合物溶液构建了详细的相图,重点关注凝胶化区域。已经清楚地证明,随着BuMA和DEAEMA中含量的增加,凝胶化得到促进。已经通过流变学在凝胶温度、凝胶时间和剪切稀化性能方面对呈现最宽凝胶区域的聚合物进行了进一步研究。
更新日期:2020-05-01
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