論文

査読有り
2015年6月

Radical Polymerization of Pendant (Meth)acrylates on a Rigid Helical Polyisocyanate Backbone Producing Poly(meth)acrylates with "Ideally" Atactic Main Chain Configuration

MACROMOLECULES
  • Atsushi Narumi
  • ,
  • Hitomi Baba
  • ,
  • Tetsuya Akabane
  • ,
  • Yuta Saito
  • ,
  • Satoshi Ohno
  • ,
  • Daichi Togashi
  • ,
  • Kazushi Enomoto
  • ,
  • Moriya Kikuchi
  • ,
  • Osamu Halm
  • ,
  • Seigou Kawaguchi

48
11
開始ページ
3395
終了ページ
3405
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acs.macromol.5b00771
出版者・発行元
AMER CHEMICAL SOC

This study includes a topic that poly(methyl methacrylate) (PMMA) with an ideally atactic main chain configuration, approximately triad tacticities of mm/mr/rr = 1/2/1, has been produced in solution by the one-dimensionally regulated radical polymerization using rigid helical polyisocyanate as a macromolecular template. Three types of isocyanate monomers with pendant (meth)acryloxy groups, such as 2-(methacryloxy)ethyl isocyanate (MOI), 2-[2-(methacryloxy)ethoxy]ethyl isocyanate (MOI-EO), and 2-(acryloxy)ethyl isocyanate (AOI), were polymerized using a titanium alkoxide complex to produce the corresponding polyisocyanates, MOI-n, MOI-EO-n, and AOI-n, respectively, in which n represents the number-averaged degree of polymerization. From the SAXS measurements of MOI-26 in hexafluoro-2-propanol and MOI-EO-38 in tetrahydrofuran at 25 degrees C, the polyisocyanates were found to be considered as rigid rod molecules. The radical polymerization of the pendant (meth)acryloxy groups was performed, and the polyisocyanate template was removed by alkali hydrolysis followed by methyl esterification, eventually producing the poly[methyl (meth)acrylate]s. The diad, triad, and pentad tacicities of the products were determined by the H-1 and C-13 NMR spectra, and these probabilities followed those calculated based on the Bernoulli statistics. The influences of the polymerization conditions, such as polymerization temperature and monomer concentration, on the tacticity of the final polymers were clarified. The effect of the flexible spacer between the polymerizable group and polyisocynate template was also evaluated. The radical polymerizations in which the polymerizable groups are molecularly regulated on a rod-like helical polyisocyanate backbone produced vinyl polymers with inimitable tacticities even in the solution state.

Web of Science ® 被引用回数 : 8

リンク情報
DOI
https://doi.org/10.1021/acs.macromol.5b00771
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000356201100001&DestApp=WOS_CPL

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