Block Copolymer Sequence Inversion through Photoiniferter Polymerization

Easterling, Charles P.; Xia, Yening; Zhao, Junpeng; Fanucci, Gail E.; Sumerlin, Brent S.

doi:10.1021/acsmacrolett.9b00716

Block Copolymer Sequence Inversion through Photoiniferter Polymerization

Journal Article · Tue Oct 15 00:00:00 EDT 2019 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.9b00716· OSTI ID:1773290

^[1]; Xia, Yening ^[2]; ^[3]; Fanucci, Gail E. ^[3]; ^[3]

Univ. of Florida, Gainesville, FL (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Integrated Nanotechnologies (CINT)
Univ. of Florida, Gainesville, FL (United States); South China Univ. of Technology (SCUT), Guangzhou (China)
South China Univ. of Technology (SCUT), Guangzhou (China)

Block copolymers prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization are often restricted to a specific comonomer blocking sequence that is dictated by intermediate radical stability and relative radical leaving group abilities. Techniques that provide alternative pathways for reinitiation of thiocarbonylthio-terminated polymers could allow access to block copolymer sequences currently unobtainable through the RAFT process. In this paper, we report a method for preparing “inverted” block copolymers, whereby the traditional order of monomer addition has been reversed through the use of photoiniferter-mediated radical polymerization. Specifically, thiocarbonylthio photolysis of xanthate- and dithiocarbamate-functional macromolecular chain transfer agents (macro-CTAs) led to the direct formation of leaving group macroradicals otherwise unaffordable by an addition–fragmentation mechanism. We believe this method could provide a route to synthesize multiblock copolymers of synthetically challenging comonomer sequences.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC04-94AL85000; NA0003525

OSTI ID:: 1773290

Report Number(s):: SAND--2021-3514J; 695023

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 11 Vol. 8; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Block Copolymer Sequence Inversion through Photoiniferter Polymerization

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