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Peer-reviewedCC BY-NCPolymer chemistry

Accessing block copolymers with independently modulated tacticities using sequential cationic-anionic polymerization of vinyl ethers and thiiranes.

  • William Ramos1
  • Nicholas M Legaux2
  • Brandon M Hosford1
  • Hanlin M Wang3
  • Elizabeth A Murphy3
  • Alicia C Huggett1
  • Frank A Leibfarth2
  • Jessica R Lamb1
  1. 1Department of Chemistry, University of Minnesota-Twin Cities 207 Pleasant Street SE Minneapolis MN 55455 USA [email protected].
  2. 2Department of Chemistry, University of North Carolina Chapel Hill NC 27599 USA.
  3. 3Materials Research Laboratory and Department of Chemistry & Biochemistry, University of California Santa Barbara CA 93106 USA.
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Abstract

Tacticity can have profound effects on the physical properties of polymers, such as self-assembly of block copolymers (BCPs). Despite its promise, previous reports on changing tacticity of BCPs have primarily focused on changing a single block or comparing fully isotactic to fully atactic copolymers. Herein, we report a platform to easily access fully atactic, fully isotactic, and mixed tacticity poly(vinyl ether)-block-poly(thiirane) BCPs. Isotacticity was independently accessed via stereoselective polymerization of vinyl ethers and by using enantiopure thiirane monomers, respectively. Thermal analyses of these materials were performed and semi-crystallinity was observed in aryl-containing isotactic blocks. For BCPs with alkyl side chains or atactic aryl side chains, fractionation on the basis of composition was performed to accelerate self-assembly studies. These fractionated BCPs were characterized via small-angle X-ray scattering (SAXS), where we observed hexagonally-packed cylinder or lamellar morphologies for some fractions. The development of this framework of selective tacticity modulation opens up facile access to diverse BCPs with varying thermal, solution-state, and bulk properties.

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Cite

BibTeXRIS
BibTeX
@article{ramos2026accessing,
  title = {{Accessing block copolymers with independently modulated tacticities using sequential cationic-anionic polymerization of vinyl ethers and thiiranes.}},
  author = {William Ramos and Nicholas M Legaux and Brandon M Hosford and Hanlin M Wang and Elizabeth A Murphy and Alicia C Huggett and Frank A Leibfarth and Jessica R Lamb},
  journal = {Polymer chemistry},
  year = {2026},
  month = oct,
  doi = {10.1039/d6py00788k},
  url = {https://europepmc.org/article/MED/42903849},
  note = {CC BY-NC},
}
RIS
TY  - JOUR
TI  - Accessing block copolymers with independently modulated tacticities using sequential cationic-anionic polymerization of vinyl ethers and thiiranes.
AU  - William Ramos
AU  - Nicholas M Legaux
AU  - Brandon M Hosford
AU  - Hanlin M Wang
AU  - Elizabeth A Murphy
AU  - Alicia C Huggett
AU  - Frank A Leibfarth
AU  - Jessica R Lamb
PY  - 2026
DA  - 2026/10/19
JO  - Polymer chemistry
DO  - 10.1039/d6py00788k
UR  - https://europepmc.org/article/MED/42903849
AB  - Tacticity can have profound effects on the physical properties of polymers, such as self-assembly of block copolymers (BCPs). Despite its promise, previous reports on changing tacticity of BCPs have primarily focused on changing a single block or comparing fully isotactic to fully atactic copolymers. Herein, we report a platform to easily access fully atactic, fully isotactic, and mixed tacticity poly(vinyl ether)-block-poly(thiirane) BCPs. Isotacticity was independently accessed via stereoselective polymerization of vinyl ethers and by using enantiopure thiirane monomers, respectively. Thermal analyses of these materials were performed and semi-crystallinity was observed in aryl-containing isotactic blocks. For BCPs with alkyl side chains or atactic aryl side chains, fractionation on the basis of composition was performed to accelerate self-assembly studies. These fractionated BCPs were characterized via small-angle X-ray scattering (SAXS), where we observed hexagonally-packed cylinder or lamellar morphologies for some fractions. The development of this framework of selective tacticity modulation opens up facile access to diverse BCPs with varying thermal, solution-state, and bulk properties.
SN  - 1759-9954
SN  - 1759-9962
ER  -