Kirila Tatyana, Amirova Alina, Blokhin Alexey, Tenkovtsev Andrey, Filippov Alexander
Institute of Macromolecular Compounds of the Russian Academy of Sciences, Bolshoy Pr. 31, 199004 Saint Petersburg, Russia.
Polymers (Basel). 2021 Jul 29;13(15):2507. doi: 10.3390/polym13152507.
Star-shaped polymers with arms of block and gradient copolymers of 2-ethyl- and 2-isopropyl-2-oxazolines grafted to the upper rim of calix[8]arene were synthesized by the "grafting from" method. The ratio of 2-ethyl- and 2-isopropyl-2-oxazoline units was 1:1. Molar masses and hydrodynamic characteristics were measured using molecular hydrodynamics and optics methods in 2-nitropropane. The arms of the synthesized stars were short and the star-shaped macromolecules were characterized by compact dimensions and heightened intramolecular density. The influence of the arm structure on the conformation of star molecules was not observed. At low temperatures, the aqueous solutions of the studied stars were not molecular dispersed but individual molecules prevailed. One phase transition was detected for all solutions. The phase separation temperatures decreased with a growth of the content of more hydrophobic 2-isopropyl-2-oxazoline units. It was shown that the way of arms grafting to the calix[8]arene core affects the behavior of aqueous solutions of star-shaped poly-2-alkyl-2-oxazoline copolymers. In the case of upper rim functionalization, the shape of calix[8]arene resembles a plate. Accordingly, the core is less shielded from the solvent and the phase separation temperatures are lower than those for star-shaped poly-2-alkyl-2-oxazolines with lower rim functionalization of the calix[8]arene.
通过“接枝自”方法合成了臂为2-乙基-2-恶唑啉和2-异丙基-2-恶唑啉的嵌段共聚物及梯度共聚物的星型聚合物,其接枝到杯[8]芳烃的上缘。2-乙基-2-恶唑啉单元与2-异丙基-2-恶唑啉单元的比例为1:1。在2-硝基丙烷中使用分子流体动力学和光学方法测量了摩尔质量和流体动力学特性。合成的星型聚合物的臂较短,星型大分子具有紧密的尺寸和较高的分子内密度。未观察到臂结构对星型分子构象的影响。在低温下,所研究的星型聚合物的水溶液不是分子分散的,而是以单个分子为主。所有溶液均检测到一个相变。相分离温度随着疏水性更强的2-异丙基-2-恶唑啉单元含量的增加而降低。结果表明,臂接枝到杯[8]芳烃核上的方式影响星型聚-2-烷基-2-恶唑啉共聚物水溶液的行为。在上缘功能化的情况下,杯[8]芳烃的形状类似于平板。因此,核受到溶剂的屏蔽较少,相分离温度低于杯[8]芳烃下缘功能化的星型聚-2-烷基-2-恶唑啉的相分离温度。