Fabrication of a multi-charge generable poly(phenyl isocyanide)-block-poly(3-hexylthiophene) rod–rod conjugated copolymer
Fabrication of a multi-charge generable poly(phenyl isocyanide)-block-poly(3-hexylthiophene) rod–rod conjugated copolymer
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DOI：
10.1039/c4py01624f
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发表时间：
2015-03
影响因子：
4.6
通讯作者：
Wei Li;Ya-Guang He;Sheng-yu Shi;Na Liu;Yuanyuan Zhu;Yunsheng Ding;Jun Yin;Zongquan Wu
中科院分区：
文献类型：
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作者：
Wei Li;Ya-Guang He;Sheng-yu Shi;Na Liu;Yuanyuan Zhu;Yunsheng Ding;Jun Yin;Zongquan Wu
报道了一种从同一种棒状共轭聚乙烯出发，通过简单的季铵化反应和紫外光照射，（4-异氰基-苯甲酸5-（2-二甲氨基-乙氧基）-2-硝基-苄基酯）-b-聚（3-己基噻吩）（PPI（-DMAENBA）-b-P3 HT）二嵌段共聚物，以Ni（dppp）Cl_2为催化剂，在单分散体系中，通过4-异氰基苯甲酸叔丁酯（PI）和3-己基噻吩（3 HT）的连续活性共聚合制备了4-异氰基苯甲酸叔丁酯（PI）和3-己基噻吩（3 HT）。罐法，随后进行化学改性。通过季铵化反应和紫外光照射合成了季铵化PPI（-DMAENBA）-b-P3 HT（PPI（-QDMAENBA）-b-P3 HT）和聚（4-异氰酸基苯甲酸）-b-聚（3-己基噻吩）（PPI（-AA）-b-P3 HT）共聚物。将带正电荷的PPI（-QDMAENBA）-b-P3 HT和带负电荷的PPI（-AA）-b-P3 HT共聚物直接分散于水中，可得到具有阳离子和阴离子表面性质的两种不同的聚合物胶束超分子结构。有趣的是，发现具有40%季铵化度的所得PPI（-QDMAENBA/DMAENBA）-b-P3 HT嵌段共聚物表现出独特的光发射，其颜色根据所使用的THF和水的溶剂比例从发光黄色转变为粉红色。这两种类型的相反电荷的胶束之间的精确的化学计量的电荷平衡，实现了一个几乎中性和有序的薄膜，这突出了潜在的共轭共聚物到组装的嵌段共聚物胶束（BCM），以产生多功能的有序薄膜和相关的应用。
A facile construction of diverse polymeric nanostructures was reported by simple quaternization reaction and UV irradiation starting from the same rod–rod conjugated poly(4-isocyano-benzoic acid 5-(2-dimethylamino-ethoxy)-2-nitro-benzyl ester)-b-poly(3-hexylthiophene) (PPI(-DMAENBA)-b-P3HT) diblock copolymers, which were prepared by sequential living copolymerization of 4-isocyano-benzoic acid tert-butyl ester (PI) and 3-hexylthiophene (3HT) using Ni(dppp)Cl2 as a catalyst in a one-pot process with a subsequent chemical modification. The facile quaternization reaction and UV irradiation upon PPI(-DMAENBA)-b-P3HT could afford quaternized PPI(-DMAENBA)-b-P3HT (PPI(-QDMAENBA)-b-P3HT) and poly(4-isocyano-benzoic acid)-b-poly(3-hexylthiophene) (PPI(-AA)-b-P3HT) copolymers. Two different polymeric micellar supramolecular structures with cationic and anionic surface properties could be obtained by direct dispersion of positively charged PPI(-QDMAENBA)-b-P3HT and negatively charged PPI(-AA)-b-P3HT copolymers into water. Interestingly, the resultant PPI(-QDMAENBA/DMAENBA)-b-P3HT block copolymers with a 40% degree of quaternization were found to exhibit unique light emissions with the color transformed from luminous yellow to pink depending on the solvent ratio of THF and water used. An almost neutral and ordered thin film was achieved on the exact stoichiometric charge balance between these two types of oppositely charged micelles, which highlights the potential to incorporate conjugated copolymers into the assembled block copolymer micelles (BCMs) to yield multifunctional ordered films and relevant applications.