Tunable Supramolecular Hexagonal Columnar Structures of Hydrogen-Bonded Copolymers Containing Two Different Sized Dendritic Side Chains
Tunable Supramolecular Hexagonal Columnar Structures of Hydrogen-Bonded Copolymers Containing Two Different Sized Dendritic Side Chains
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含有两种不同尺寸树枝状侧链的氢键共聚物的可调节超分子六方柱状结构
DOI：
10.1021/acsmacrolett.7b00145
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发表时间：
2017
影响因子：
5.8
通讯作者：
Li Christopher Y.
中科院分区：
文献类型：
--
作者：
Cai Yongchen;Zheng Meiqing;Zhu Yalan;Chen Xiao-Fang;Li Christopher Y.
具有可调对称性和尺寸的聚合物结构对于诸如光刻、过滤膜和分离的应用是期望的。本文报道了通过构建含聚乙烯的氢键共聚物，自组装得到晶格尺寸在5 ~ 7 nm范围内可调的超分子六方柱（ΦH）结构（4-乙烯基吡啶）（P4 VP）和两种树枝状分子添加剂，1-[4′-（3″，4 ″，5 ″-十三烷氧基苯甲酰氧基）亚苯氧基羰基]-3-[（4″-羟基苯基）氧羰基]苯（12 CBP）和4-羟基苯基（3，4，5-十三烷氧基）苯甲酸酯（12 CTB）。尽管12 CBP和12 CTB的分子尺寸存在明显差异，但所得三元超分子共聚物P4 VP（12 CBP）x（12 CTB）y在x ≥ 0.1和dy ≥ 0.2时具有均匀的Φ H相。每个柱都是用P4 VP作为主链构建的，其与混合侧链相连。柱径介于相应的P4 VP（12 CBP）x+ y和P4 VP（12 CTB）x+ y之间，并且可以通过改变xandy容易地调节。超分子共聚物中Φ H的增强归因于混合侧链的熵效应和P4 VP主链与两个分子（12 CBP和12 CTB）的氢键相互作用的焓效应。
Polymer structures with tunable symmetry and sizes are desired for applications such as lithography, filtration membranes, and separation. Here we report the self-assembled supramolecular hexagonal columnar (ΦH) structures with tunable lattice size varying from 5 to 7 nm by constructing hydrogen-bonded copolymers bearing poly(4-vinylpyridine) (P4VP) and two dendritic molecular additives, 1-[4′-(3″,4″,5″-tridecyloxybenzoyloxy)phenyleneoxycarbonyl]-3-[(4″-hydroxyphenyl)oxycarbonyl]benzene (12CBP) and 4-hydroxyphenyl (3,4,5-tridecyloxy)benzoate (12CTB). Despite the distinct molecular size difference between 12CBP and 12CTB, the resulting ternary supramolecular copolymers, P4VP(12CBP)x(12CTB)y, possess a homogeneous ΦHphase atx≥ 0.1 andy≥ 0.2. Each column is constructed with P4VP as the backbone tethered with mixed side chains. The column diameter is between the size of the corresponding P4VP(12CBP)x+yand P4VP(12CTB)x+yand could be easily tuned by varyingxandy. The enhancement of ΦHin supramolecular copolymers is attributed to the entropy effect of the mixed side chain and enthalpy effect from hydrogen bonding interaction of the P4VP backbone and two molecules (12CBP and 12CTB).