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Overcoming Kinetic Trapping for Morphology Evolution during Polymerization-Induced Self-Assembly.

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|June 22, 2019
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Summary

Researchers developed a new method to control polymer self-assembly morphology. By adding small amounts of solvophilic monomers during polymerization-induced self-assembly (PISA), they achieved diverse structures beyond simple spheres.

Keywords:
RAFT copolymerizationmorphology evolutionpolymerization-induced self-assemblysolvophilic co-monomers

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Polymerization-induced self-assembly (PISA) is a key method for creating complex polymer structures.
  • PISA often results in kinetically trapped spherical morphologies due to long stabilizing chains.
  • Controlling morphology evolution in PISA remains a significant challenge in polymer science.

Purpose of the Study:

  • To develop a general strategy for promoting morphology evolution in PISA.
  • To overcome the limitation of kinetically trapped spheres in PISA.
  • To expand the range of accessible morphologies through controlled copolymerization.

Main Methods:

  • Incorporation of solvophilic monomers, such as 3-(triethoxysilyl)propyl methacrylate (TESPMA), into block copolymer spheres during PISA.
  • Utilizing poly(N,N-dimethylaminoethyl methacrylate)-b-poly(benzyl methacrylate) (PDMA-b-PBzMA) as the model system.
  • Investigating the effect of copolymerization with various solvophilic monomers (DMA, DEA, HPMA) on morphology.

Main Results:

  • Copolymerization of PDMA-b-PBzMA spheres with 7% TESPMA induced significant morphology evolution.
  • Observed transformations included spheres evolving into worms, octopi-like, jellyfish-like structures, vesicles, and large compound vesicles.
  • This morphology evolution was confirmed with other solvophilic monomers, demonstrating a non-specific effect.

Conclusions:

  • Copolymerization with small amounts of solvophilic monomers is an effective strategy to promote morphology evolution in PISA.
  • This approach offers a convenient route to access a wide range of complex polymer architectures.
  • The findings contribute to the rational design of formulations for advanced PISA applications.