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SCIENCE CHINA Chemistry, Volume 62, Issue 2: 226-237(2019) https://doi.org/10.1007/s11426-018-9360-3

Phase diagrams, mechanisms and unique characteristics of alternating-structured polymer self-assembly via simulations

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  • ReceivedJul 19, 2018
  • AcceptedSep 6, 2018
  • PublishedNov 26, 2018

Abstract

Alternating-structured polymers (ASPs), like alternating copolymers, regular multiblock copolymers and polycondensates, are very important polymer structures with broad applications in photoelectric materials. However, their self-assembly behaviors, especially the self-assembly of alternating copolymers, have not been clearly studied up to now. Meanwhile, the unique characteristics therein have not been systematically disclosed yet by both experiments and theories. Herein, we have performed a systematic simulation study on the self-assembly of ASPs with two coil alternating segments in solution through dissipative particle dynamics (DPD) simulations. Several morphological phase diagrams were constructed as functions of different impact parameters. Diverse self-assemblies were observed, including spherical micelles, micelle networks, worm-like micelles, disk-like micelles, multimicelle aggregates, bicontinuous micelles, vesicles, nanotubes and channelized micelles. Furthermore, a morphological evolutionary roadmap for all these self-assemblies was constructed, along with which the detailed molecular packing models and self-assembly mechanisms for each aggregate were disclosed. The ASPs were found to adopt a folded-chain mechanism in the self-assemblies. Finally, the unique characteristics for the self-assembly of alternating copolymers were revealed especially, including (1) ultra-fine and uniform feature sizes of the aggregates; (2) independence of self-assembled structures from molecular weight and molecular weight distribution; (3) ultra-small unimolecular aggregates. We believe the current work is beneficial for understanding the self-assembly of alternating structured polymers in solution and can serve as a guide for the further experiments.


Funded by

the National Natural Science Foundation of China(21404070,21474062,51773115,21774077,91527304)

the Program for Basic Research of Shanghai Science and Technology Commission(17JC1403400)

and Centre for High-Performance Computing

Shanghai Jiao Tong University.


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21893073010, 21404070, 21474062, 51773115, 21774077, 91527304), the Program for Basic Research of Shanghai Science and Technology Commission (17JC1403400), and Centre for High-Performance Computing, Shanghai Jiao Tong University.


Interest statement

The authors declare that they have no conflict of interest.


Supplement

The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


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  • Figure 1

    The models of ASPs. The solvophilic bead A and solvophobic bead B are denoted in red and cyan, respectively (color online).

  • Figure 2

    (a) A morphological phase diagram as a function of the degree of polymerization (n) and volume fraction of solvophilic A (fA); (b) the corresponding phase structures. The solvophilic A and solvophobic B are denoted in red and cyan, respectively (color online).

  • Figure 3

    Morphological phase diagrams and the characteristic snapshots for (AxBy)6 as a function of fA and various impact factors including: (a) the polymer concentration (φ) at aAS=26, aBS=100, aAB=80; (b) the solvent-selectivity of A (aAS) at φ=0.06, aBS=100, aAB=80; (c) the solvent-selectivity of B (aBS) at φ=0.06, aAS=26, aAB=80; (d) the incompatibility between A and B (aAB) at φ=0.06, aAS=26, aBS=100 (color online).

  • Figure 4

    The all-in-one self-assembly roadmap of alternating-structured polymers. The solvophilic A and solvophobic B are denoted in red and cyan, respectively. It should be noted that this roadmap only shows the self-assembly process starting from ASPs, and it does not contain the information for the phase transition from one aggregate to another (color online).

  • Figure 5

    Morphological snapshots and molecule packing models of solid micelles. (a) Spherical micelle; (b) worm-like micelle; (c) disk-like micelle; (d) micelle network; (e) MMA. The linkers are the molecules segments linking different small micelles. The solvophilic A and solvophobic B are denoted in red and cyan, respectively (color online).

  • Figure 6

    Cartoon schematics illustrated for the formation of solid micelles including: (a) spherical micelles; (b) micelle networks, (c) MMAs, worm-like micelles and disk-like micelles. Red and cyan lines are the solvophilic and solvophobic units of the polymers, respectively. The black dash lines represent there would be more linked chains or micelles (color online).

  • Figure 7

    The structures and formation mechanism of bicontinuous micelles. (a) Various kinds of bicontinuous micelles; (b, c) the detailed structures of bicontinuous micelles obtained in box sizes 403 (b) and 603 (c) with fA=0.06, aAS=30, aBS=100, aAB=80; (d) the typical formation mechanism of the bicontinuous micelle. Red lines are the solvophilic units of the polymers, while the cyan rods denote the solvophobic cores (color online).

  • Figure 8

    Molecular packing models and the formation processes of vesicles and nanotubes from alternating copolymers. (a) Molecular packing model of vesicles; (b) molecular packing model of nanotubes; (c) sequential sliced snapshots illustrated for the formation of vesicles; (d) sequential sliced snapshots and cartoons illustrated for the formation of nanotubes. The solvophilic A and solvophobic B are denoted in red and cyan, respectively (color online).

  • Figure 9

    Channelized micelles and the typical self-assembly mechanisms. (a) Various kinds of channelized micelles; (b, c) the self-assembly mechanisms of channelized micelles. To enhance the contrast, the channel surface was labelled in red, while the outer solvophilic shells of the channelized micelles were in light-red (color online).

  • Figure 10

    The effect of polymer polydispersity on the self-assembly process. (a) Morphological phase diagram formed as a function of the volume fraction of A and PDI; (b) characteristic snapshots of the phase diagram; (c) the effect of PDI on the feature sizes of aggregates; (d) the effect of PDI on the molecular packing model in the aggregates (color online).

  • Figure 11

    Molecular packing behaviors of (A8B8)n alternating copolymer chains (shown by the bold chains) in the bilayers of vesicles. (a) Polymers with various n inside the vesicles with the same PDI=2.49; (b) polymers with n=40 inside the vesicles with various PDIs. Solvophilic and solvophobic segments are denoted in red and cyan, respectively (color online).

  • Figure 12

    Sequential scheme for the formation of the unimolecular aggregates from alternating copolymers. (a) Formation of a unimolecular spherical micelle from an (A12B4)25 polymer; (b) formation of a unimolecular worm-like micelle from an (A10B5)100 polymer; (c) formation of a unimolecular vesicle from an (A8B8)200 polymer. Red and cyan coiled lines are the solvophilic and solvophobic segments of polymers, respectively (color online).

  • Table 1   Interaction parameters () used in this article

    aij

    Solvent (S)

    Solvophilic A

    Solvophobic B

    S

    25

     

    A

    15–30

    25

     

    B

    40–120

    40–120

    25

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