Efficient synthesis of narrowly dispersed brush copolymers and study of their assemblies: the importance of side chain arrangement

Journal of the American Chemical Society
Yan XiaRobert H Grubbs

Abstract

Efficient, one-pot preparation of synthetically challenging, high molecular weight (MW), narrowly dispersed brush block copolymers and random copolymers in high conversions was achieved by ring-opening metathesis (co)polymerization (ROMP) of various macromonomers (MMs) using the highly active, fast-initiating ruthenium olefin metathesis catalyst (H(2)IMes)(pyr)(2)(Cl)(2)RuCHPh. A series of random and block copolymers were prepared from a pair of MMs containing polylactide (PLA) and poly(n-butyl acrylate) (PnBA) side chains at similar MWs. Their self-assembly in the melt state was studied by small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM). In brush random copolymers containing approximately equal volume fractions of PLA and PnBA, the side chains segregate into lamellae with domain spacing of 14 nm as measured by SAXS, which was in good agreement with the lamellar thickness measured by AFM. The domain spacings and order-disorder transition temperatures of brush random copolymers were insensitive to the backbone length. In contrast, brush block copolymers containing approximately equal volume fractions of these MMs self-assembled into highly ordered lamellae with domain spacing over 100 nm. Their assemblies s...Continue Reading

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Citations

Apr 6, 2013·Chemical Reviews·Andreas Walther, Axel H E Müller
Oct 26, 2011·Journal of the American Chemical Society·Yan XiaRobert H Grubbs
Aug 9, 2012·Journal of the American Chemical Society·Yongping ZhaGregory N Tew
Aug 16, 2012·Journal of the American Chemical Society·Garret M MiyakeRobert H Grubbs
Mar 8, 2013·Journal of the American Chemical Society·Patrick J M StalsSergei S Sheiko
Oct 8, 2013·Journal of the American Chemical Society·Victoria A PiunovaRobert H Grubbs
Feb 2, 2013·ACS Nano·Weiyin GuThomas P Russell
Aug 24, 2010·Chemical Communications : Chem Comm·Judith HieroldDavid W Lupton
Mar 15, 2011·Chemical Communications : Chem Comm·Jiong ZouChong Cheng
Aug 23, 2012·Proceedings of the National Academy of Sciences of the United States of America·Benjamin R SveinbjörnssonRobert H Grubbs
Aug 4, 2012·Science·Paul A RuparIan Manners
Jan 16, 2014·Journal of the American Chemical Society·Maria T ProettoNathan C Gianneschi
Oct 16, 2014·Chemical Communications : Chem Comm·Linfeng XiongKun Huang
Mar 7, 2014·Nature Communications·Zachary M HudsonIan Manners
Nov 7, 2015·ACS Nano·Samuel J DalsinMark W Matsen
Oct 4, 2016·Macromolecules·Gary M LeutyMichael Rubinstein
Sep 2, 2016·Journal of the American Chemical Society·Ken KawamotoJeremiah A Johnson
Nov 4, 2016·Scientific Reports·Sungmin ParkDu Yeol Ryu
Feb 22, 2017·Journal of the American Chemical Society·Tzu-Pin LinRobert H Grubbs
Nov 6, 2014·Journal of the American Chemical Society·Robert J MacfarlaneRobert H Grubbs
May 2, 2018·Chemical Society Reviews·O M OgbaR H Grubbs
May 3, 2018·Macromolecular Rapid Communications·Andrea SteinhausMarkus Müllner
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Feb 18, 2015·Chemical Society Reviews·Rafael VerduzcoGila E Stein
May 28, 2014·Nature Communications·Lin JiaMitchell A Winnik
Feb 28, 2018·Angewandte Chemie·Théophile PelrasMarkus Muellner
May 19, 2011·Angewandte Chemie·Yan XiaRobert H Grubbs
Sep 15, 2012·Angewandte Chemie·Garret M MiyakeRobert H Grubbs
Oct 29, 2018·Advanced Healthcare Materials·Daniel C LeeSuzie H Pun
Sep 2, 2017·Science Advances·Jarosław PaturejMichael Rubinstein
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