Citation: Rui-ying Zhao, Xu-qiang Jiang, Jun-feng Zheng, Xiao-qing Liu, Yan-shuang Xu, Shuang Yang, Er-qiang Chen. Columnar Phase of Side-chain Liquid Crystalline Polymers Based on “Multi-chain Column”[J]. Acta Polymerica Sinica, ;2018, 0(8): 973-986. doi: 10.11777/j.issn1000-3304.2018.18065 shu

Columnar Phase of Side-chain Liquid Crystalline Polymers Based on “Multi-chain Column”

1.
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Center for Soft Mater Science and Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871
2.
Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871
3.
College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037

Corresponding author: Er-qiang Chen, eqchen@pku.edu.cn
Received Date: 23 February 2018
Revised Date: 26 March 2018

Side-chain liquid crystalline polymer (SCLCP) can form columnar liquid crystalline (LC) phases, in addition to the conventional nematic and smectic phase. For the SCLCP containing the discotic mesogenic group attached to the main-chain through a flexible spacer, the columnar phase relies on the assembly of the discotic mesogens. On the other hand, the SCLCP with extended conformation, such as mesogen-jacketed LC polymers and dendronized polymers, can exhibit the columnar phase based on the parallel packing of the cylindrical chains. In this case, " single chain column” is considered to be the building block of the columnar phase in general. Recently, our work on hemiphasmid SCLCP demonstrates that the " multi-chain column” is also important for the columnar phases of SCLCP. Hemiphasmid SCLCP possesses the hemiphasmid side-chain composed of a rod-like mesogen linked with a half-disk end group. It can readily self-organize into columnar phases with a pretty lager lattice parameter (e.g., 5 – 10 nm). It is found that the number of repeating units (Z_rep) packed in a column stratum with a thickness of ~ 0.4 nm is surprisingly large. As an example, for the hexagonal columnar phase with the a parameter of ~ 6 nm, the value of Z_rep is ~ 10. Squeezing a chain segment with 10 repeating units into the 0.4 nm-thick column stratum is physically unreasonable. The " unusual Z_rep” indicates the existence of " multi-chain column” that consists of a bundle of chains (e.g., 4 – 5 chains) laterally associated together. We synthesized a series of hemiphasmid SCLCPs with different chemical structures. Various main-chains have been employed, including polystyrene, poly(methacrylate), polyacetylene, and polynorbornene. The hemiphasmid moieties can invoke different rod-like mesogens, and can be attached to the main-chain directly or via a flexible spacer. For all the samples obtained, we have verified that the " multi-chain column” is applicable. The formation of " multi-chain column” can be understood from the nano-segregation among the main-chain, the rod-like mesogen and the flexible tails. Theoretical analysis indicates that the " multi-chain column” is a structure of thermodynamic equilibrium. The number of chains in the column is dependent on the volume fraction of the rigid component of the SCLCP. We propose that the chains in the column can interlock and intertwine, resulting in the intra-column entanglement. This hypothesis is supported by the study of hemiphasmid side-chain polynorbornene, which illustrates that the intra-column entanglement can endow the polymer with properties of thermoplastic elastomer. Moreover, the polymer can further exhibit excellent multi-shape memory effect at high strain. We anticipate that the further study of the " multi-chain column”, which has been overlooked for years, will deepen our understanding of some fundamental issues of the structure and dynamics of polymers, and will also help to explore the new properties and applications of SCLCPs.
- Side-chain liquid crystalline polymer,
- Hemiphasmid mesogen,
- Multi-chain column,
- Intra-column entanglement,
- Shape memory
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沈阳化工大学材料科学与工程学院沈阳 110142

Columnar Phase of Side-chain Liquid Crystalline Polymers Based on “Multi-chain Column”

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com