A Reactive Platform Approach for the Rapid Synthesis and Discovery of High χ/Low N Block Polymers

Matthew C D Carter, James Jennings, Frank W. Speetjens, David M. Lynn, Mahesh K. Mahanthappa

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

We report a reactive polymer platform for the rapid discovery of strongly segregated diblock polymers that microphase separate into well-defined morphologies with sub-5 nm features. Our strategy employs reactive poly(styrene-block-2-vinyl-4,4-dimethylazlactone) (SV) polymers with low degrees of polymerization (N), in which the V blocks undergo selective and quantitative reactions with functional primary amines, to identify new poly(acrylamides) that are highly immiscible with poly(styrene) and induce block polymer self-assembly. Using a combination of optical birefringence and small-angle X-ray scattering (SAXS), we characterize a library of 17 block polymers produced by amine functionalization of four parent SV diblocks synthesized by sequential RAFT polymerizations. We demonstrate that V block functionalization with hydroxy- and methoxy-functional amines yields diblocks that order into lamellar mesophases with half-pitches as small as 3.8 nm. Thus, this azlactone-based reactive molecular platform enables combinatorial generation of polymer libraries with diverse side chain structures that may be rapidly screened to identify new high χ/low N systems for self-assembly at ever decreasing length scales.

Original languageEnglish (US)
Pages (from-to)6268-6276
Number of pages9
JournalMacromolecules
Volume49
Issue number17
DOIs
StatePublished - Sep 13 2016

Bibliographical note

Funding Information:
This work was supported by the U.S. National Science Foundation Nanoscale Science and Engineering Center at UW-Madison (DMR-0832760) and made use of NSFsupported facilities (DMR-0832760, DMR-1121288 and CHE-1048642)

Publisher Copyright:
© 2016 American Chemical Society.

Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.

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