Influence of the Primary Structure of Syndiotactic Poly(Methyl Methacrylate) on the Inclusion Complex Formation with [60]Fullerene: Robustness of the Helix against Primary Structural Errors
Influence of the Primary Structure of Syndiotactic Poly(Methyl Methacrylate) on the Inclusion Complex Formation with [60]Fullerene: Robustness of the Helix against Primary Structural Errors
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间规聚甲基丙烯酸甲酯的一级结构对[60]富勒烯包合物形成的影响：螺旋对一级结构误差的鲁棒性
DOI：
10.1021/acs.macromol.0c02046
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发表时间：
2020
期刊：
影响因子：
5.5
通讯作者：
T. Kawauchi
中科院分区：
文献类型：
--
作者：
Kouta Kajihara;Ituki Tousya;T. Ueno;T. Kawauchi
已知间同立构聚（甲基丙烯酸甲酯）（st-PMMA）与富勒烯在甲苯中形成包合物。我们详细研究了苯乙烯-聚甲基丙烯酸甲酯的一级结构，如分子量和立构规整性，对与C60形成包合物的影响。当C60浓度为10和2 mg/mL时，在甲苯中，当聚合物中的nr含量为89%、nMn大于7.8 × 103时，C60与st-PMMA形成包合物，并伴有凝胶化现象，而当聚合物中的nMn为4.6 × 103时，没有观察到凝胶化现象。st-PMMA凝胶化率和C60包封率随分子量的增加而增加，当Mn大于2.9 × 104时，其值趋于稳定。客体C60分子对st-PMMA螺旋结构的形成也有很大的影响。为了定量地获得不含富勒烯的凝胶，必须使用Mn为5.8 × 105的st-PMMA，而在C60存在下，Mn为2.9 × 104的st-PMMA就足够了。用具有足够高分子量（Mn> 3.0 × 105）的st-PMMA和不同的trr含量考察了立构规整性对包合物形成的影响。即使st-PMMA含量从97%降低到89%，C60的包封率也没有降低。由于具有89%的无规含量的st-PMMA的主链在每个螺旋圈中包含大约一个缺陷（m-二联体），因此得出结论，当缺陷处于该水平时，聚合物链的螺旋结构得以维持。
Syndiotactic poly(methyl methacrylate) (st-PMMA) is known to form an inclusion complex with fullerenes in toluene. We investigated in detail the influence of the primary structure of st-PMMA, such as the molecular weight and stereoregularity, on the inclusion complex formation with C60. The formation of an inclusion complex with C60was accompanied by gelation that occurred in toluene by using st-PMMAs with anrrcontent of 89% and anMnof over 7.8 × 103in the polymer, with C60concentrations of 10 and 2 mg/mL, while no gelation was observed when using st-PMMA with anMnof 4.6 × 103. The st-PMMA gelation ratio and the C60encapsulation ratio increased with the increasing molecular weight and became constant at anMnof over 2.9 × 104. The guest C60molecule also had a large influence on the formation of the helical structure of st-PMMA. To obtain a gel quantitatively without fullerene, it was necessary to use st-PMMA with a highMnof 5.8 × 105, whereas in the presence of C60, st-PMMA with anMnof 2.9 × 104was sufficient. The influence of stereoregularity on the inclusion complex formation was also investigated using st-PMMA with a sufficiently high molecular weight (Mn> 3.0 × 105) and differentrrcontents. Even when therrcontent of st-PMMA decreased from 97 to 89%, the C60encapsulation ratio did not decrease. Since the main chain of st-PMMA with anrrcontent of 89% incorporates approximately one defect (m-diad) per helical turn, it was concluded that the helical structure of the polymer chains is maintained when the defects are at this level.
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影响因子：
16.6
作者：
Kawauchi, Takehiro;Kumaki, Jiro;Yashima, Eiji
通讯作者：
Yashima, Eiji
影响因子：
5.5
作者：
M. Kawauchi;T. Kawauchi;T. Takeichi
通讯作者：
M. Kawauchi;T. Kawauchi;T. Takeichi
影响因子：
16.6
作者：
Kumaki, Jiro;Kawauchi, Takehiro;Yashima, Eiji
通讯作者：
Yashima, Eiji
影响因子：
64.8
作者：
WATSON, JD;CRICK, FHC
通讯作者：
CRICK, FHC
影响因子：
15
作者：
Kawauchi, Takehiro;Kitaura, Atsushi;Yashima, Eiji
通讯作者：
Yashima, Eiji