Citation: Zhang Shuo, Cai Chun-hua, Huang Qi-jing, Lin Jia-ping, Xu Zhan-wen. Effect of Intermolecular Interactions on Self-assembled Structures of Polypeptide-based Copolymer/Polystyrene Derivatives Blends[J]. Acta Polymerica Sinica, ;2018, (1): 109-118. doi: 10.11777/j.issn1000-3304.2018.17223 shu

Effect of Intermolecular Interactions on Self-assembled Structures of Polypeptide-based Copolymer/Polystyrene Derivatives Blends

School of Materials Science and Engineering, East China University of Science and Technology, Shanghai Key Laboratory of Advanced Polymeric Materials, Shanghai 200237

Corresponding author: Cai Chun-hua, caichunhua@ecust.edu.cn Lin Jia-ping, jlin@ecust.edu.cn
Received Date: 10 August 2017
Revised Date: 8 September 2017

Herein, poly(γ-benzyl-L-glutamate)-b-poly(ethylene glycol) (PBLG-b-PEG) polypeptide-based rod-coil block copolymer, polystyrene homopolymer (PS), and PS derivatives, such as poly(4-acetoxystyrene) (PAS) homopolymer, poly(vinylphenol) (PVPh) homopolymer, and poly(styrene-co-4-acetoxystyrene) (P(S-co-AS)) copolymer with various AS molar contents, were synthesized. The molecular structures (molecular weight, polydispersity index and composition) of the polymers were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (¹H-NMR) and gel permeation chromatography (GPC). Self-assembly behaviors of the polymer blends composed of PBLG-b-PEG copolymer and PS derivatives (including PS homopolymer) were explored. The self-assembled aggregates were prepared by a dialysis method with water used as selective solvent. The morphologies and structures of the formed aggregates were investigated by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The influence of intermolecular interaction between polymers (e.g., π-π interaction between PBLG and PS, PAS and PVPh, dipole-dipole interaction between PBLG and PAS, and hydrogen-bonding interaction between PBLG and PVPh) on self-assembly behaviors of the polymer blends was investigated. With the strength of intermolecular interaction increasing in the order of PBLG/PS < PBLG/PAS < PBLG/PVPh, a morphological transition was observed. With relatively weak intermolecular interaction, strip-pattern-spheres were formed in the PBLG-b-PEG/PS blends. For PBLG-b-PEG/PAS blends, as the dipole-dipole interaction was stronger than π-π interaction, the strips disappeared and cavity was observed. As the intermolecular interaction was further enhanced by hydrogen bonding, vesicles were self-assembled in PBLG-b-PEG/PVPh blends. Additionally, the surface morphology of the spherical aggregates was tuned by AS molar content and temperature for PBLG-b-PEG/P(S-co-AS) blends. With increasing AS molar content, the dipole-dipole interaction between PBLG and P(S-co-AS) increased, leading to less regular strip patterns on aggregates surfaces compared with PBLG-b-PEG/PS polymer blends. As temperature increases, the strip patterns became more regular due to the weaker interaction between PBLG and PSAS segments.
- Self-assembly,
- Blends,
- Intermolecular interaction,
- Polypeptides,
- Morphological transition
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