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How the modification of the hyperbranched terminals affects the solution self-assembly of linear-block-hyperbranched copolymers

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Abstract

In this article, we reported the solution self-assembly of a series of amphiphilic linear-block-hyperbranched copolymers, which are composed of linear polyethylene (PE) blocks and hyperbranched poly(glycidol) (hbPG) blocks with 100% hydroxyl terminals (PE157-b-hbPG26-OH27, E1), partially acetyl terminals (PE157-b-hbPG26-acetyl≈50%, E2) and fully acetyl terminals (PE157-b-hbPG26-acetyl≈100%, E3) respectively. In the selective solvent of PE blocks, the epitaxial growth characteristics of crystalline PE conferred the ability of block copolymer (E1) to generate perfect two-dimensional lamellar structure. Fully hydroxyl acylation will reinforce the repulsion of the lamellar surface and interfere with the epitaxial growth of lamellae, forming an imperfect lamellar structure (E3). For E2, the hydrogen bonds formed between hydroxyl and carbonyl oxygen prevented the unimers from approaching the growth interface of lamellae, forming a disordered lamellar structure. In the selective solvent for hbPG block, the solvent induced the copolymers to self-assemble into spherical (E1 and E2) and wormlike (E3) primary micelles. Furthermore, the spherical and wormlike primary micelles were assembled at higher level into more stable spherical (E1), rod-shaped (E2) and spindle-shaped (E3) aggregates. Mechanisms of terminal acylation on the morphology of self-assembly in block-selective solutions were proposed.

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Acknowledgements

The Bio-ultrastructure Analysis Laboratory of the Key Laboratory of Applied Marine Biotech- nology of the Ministry of Education, Ningbo University provides assistance with testing equipments.

Funding

The project of the Natural Science Foundation of Ningbo (2019A610149).

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  1. Ningbo Key Laboratory of Specialty Polymers, School of Material Science and Chemical Engineering, Ningbo University, Ningbo, 315211, People’s Republic of China

    Yu Hu & Jingshan Mu

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  1. Yu Hu
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Correspondence to Jingshan Mu.

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Hu, Y., Mu, J. How the modification of the hyperbranched terminals affects the solution self-assembly of linear-block-hyperbranched copolymers. J Polym Res 29, 229 (2022). https://doi.org/10.1007/s10965-022-03088-1

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