Citation: Chen Jiang, Xing Wu, Na Zhang, Fang Chen, Ru-ke Bai. Synthesis and Two-dimentional Self-assembly of Amphiphilic and Conjugated Polymers Based on Poly(phenylenebutadiynylene)s[J]. Acta Polymerica Sinica, ;2018, 0(11): 1442-1450. doi: 10.11777/j.issn1000-3304.2018.18100 shu

Synthesis and Two-dimentional Self-assembly of Amphiphilic and Conjugated Polymers Based on Poly(phenylenebutadiynylene)s

  • Corresponding author: Ru-ke Bai, bairk@ustc.edu.cn
  • Received Date: 4 April 2018
    Revised Date: 22 April 2018
    Available Online: 6 September 2018

  • Amphiphilic and conjugated polymers based on poly(phenylenebutadiynylene)s (A-PPB) were designed and synthesized, which were consisted of a hydrophobic rigid conjugated main chain and hydrophilic flexible side chains with carboxylic anions. Structure and degree of polymerization (DP) of the polymers were examined by proton nuclear magnetic resonance (1H-NMR), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. The two dimensional self-assembly of the amphiphilic conjugated polymers was investigated in different solvents and their mixtures. The morphology of the aggregates was characterized by transmission electron microscopy (TEM). The results showed that A-PPB in water self-assembled into two-dimentional supramolecular nanosheets (2D-SNS) with size ranged from hundred nanometers to several microns. The thickness of 2D-SNS was measured to be about 5 nm by atomic force microscopy (AFM), indicating a stack of 3 layers. The results of high-resolution TEM (HRTEM), selected-area electron diffraction (SAED) and X-ray diffraction (XRD) demonstrated that 2D-SNS was formed by the parallel arrangement of A-PPB, and the distance between the adjacent two A-PPB chains was consistent with the typical π-π stacking distance. On the other hand, A-PPB in methanol formed irregular aggregates because of its high solubility. However, when toluene was added into the methanolsolution of A-PPB, multilayered aggregates were obtained. Moreover, self-assembly of the non-amphiphilic precursor PPB was also examined in a mixed solvent of chloroform and methanol, and the TEM images showed that PPB formed multi-layered aggregates. This result indicated that the amphiphilicity and the electrostatic repulsion of the polymer chains played an important role in the formation of the layered sheets. In addition, DP of A-PPB is also important for 2D self-assembly of the polymers. When DP was 8, amphiphilic oligo(phenylenebutadiynylene)s formed disordered aggregates. In conclusion, this work provides significant information for 2D self-assembly of linear amphiphilic and conjugated polymers.
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