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Molecular Engineering of Nanostructures in Disordered Block Polymers
ACS Macro Letters ( IF 5.1 ) Pub Date : 2020-02-26 , DOI: 10.1021/acsmacrolett.0c00036 Nicholas Hampu 1 , Marc A Hillmyer 2
ACS Macro Letters ( IF 5.1 ) Pub Date : 2020-02-26 , DOI: 10.1021/acsmacrolett.0c00036 Nicholas Hampu 1 , Marc A Hillmyer 2
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A series of symmetric poly(methyl methacrylate-stat-styrene)-block-polylactide (P(MMA-s-S)-b-PLA) diblock terpolymers with nearly constant molar masses yet varying block interaction parameters were synthesized as a model system to probe the extent and utility of composition fluctuations in the disordered state. A combination of differential scanning calorimetry, dynamic mechanical analysis, and small-angle X-ray scattering revealed that a broad range of segregation strengths ranging from what we ascribe to essentially a mean-field disordered to a fluctuating disordered to an ordered system could be readily obtained by tuning the molar fraction of styrene in these diblocks. The P(MMA-s-S)-b-PLA diblocks were annealed above their order–disorder transition temperatures (TODT) and rapidly quenched to low temperatures to trap the disordered state via vitrification, as confirmed by scanning electron microscopy. Small-angle X-ray scattering and N2 sorption analysis post-removal of PLA demonstrated that a transition from a very weakly structured, mean-field-like melt to a bicontinuous fluctuating disordered state occurred with increasing segregation strength. This work demonstrates that the extent of microphase segregation as well as the domain continuity of the disordered block polymer melt can be tuned using both synthetic design and thermal stimuli, guiding the design of disordered block polymers with targeted nanostructures that have potential technological utility.
中文翻译：
无序嵌段聚合物中纳米结构的分子工程
一系列对称的聚（甲基丙烯酸甲酯-stat-苯乙烯）-嵌段-聚丙交酯 (P(MMA- s -S) -b - PLA) 二嵌段三元共聚物，其摩尔质量几乎恒定，但嵌段相互作用参数不同，作为模型系统合成探索无序状态下成分波动的程度和效用。差示扫描量热法、动态力学分析和小角 X 射线散射的组合表明，从我们认为基本上无序的平均场到无序的波动无序到有序系统的范围广泛的分离强度可以很容易地得到。通过调整这些二嵌段中苯乙烯的摩尔分数获得。P(MMA- s -S) -b-PLA二嵌段在其有序-无序转变温度（T ODT）以上退火，并迅速淬火至低温以通过玻璃化捕获无序状态，正如扫描电子显微镜所证实的那样。小角 X 射线散射和 N 2PLA 去除后的吸附分析表明，随着分离强度的增加，从结构非常弱的平均场状熔体转变为双连续波动的无序状态。这项工作表明，可以使用合成设计和热刺激来调节无序嵌段聚合物熔体的微相偏析程度和域连续性，从而指导设计具有潜在技术实用性的目标纳米结构的无序嵌段聚合物。
更新日期：2020-02-27
中文翻译：
无序嵌段聚合物中纳米结构的分子工程
一系列对称的聚（甲基丙烯酸甲酯-stat-苯乙烯）-嵌段-聚丙交酯 (P(MMA- s -S) -b - PLA) 二嵌段三元共聚物，其摩尔质量几乎恒定，但嵌段相互作用参数不同，作为模型系统合成探索无序状态下成分波动的程度和效用。差示扫描量热法、动态力学分析和小角 X 射线散射的组合表明，从我们认为基本上无序的平均场到无序的波动无序到有序系统的范围广泛的分离强度可以很容易地得到。通过调整这些二嵌段中苯乙烯的摩尔分数获得。P(MMA- s -S) -b-PLA二嵌段在其有序-无序转变温度（T ODT）以上退火，并迅速淬火至低温以通过玻璃化捕获无序状态，正如扫描电子显微镜所证实的那样。小角 X 射线散射和 N 2PLA 去除后的吸附分析表明，随着分离强度的增加，从结构非常弱的平均场状熔体转变为双连续波动的无序状态。这项工作表明，可以使用合成设计和热刺激来调节无序嵌段聚合物熔体的微相偏析程度和域连续性，从而指导设计具有潜在技术实用性的目标纳米结构的无序嵌段聚合物。
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