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Nonpolar Monomers: Styrene and 1,3-Butadiene Derivatives

  • Chapter
Anionic Polymerization

Abstract

This chapter reviews the living anionic polymerization of styrene, 1,3-butadiene, and their functional derivatives mainly achieved since the mid-1980s. Attention is first focused on the living anionic polymerization of functional styrene derivatives. With the finding of anion-stable functionalities and the successful development of two strategies using protective groups to mask the reactive functionalities and electron-withdrawing functional groups to change the reactivities of monomers and their chain-end anions, a large number of styrene derivatives carrying almost all the useful functionalities acquire the ability to undergo the living anionic polymerization. Secondly, the anionic polymerization of several functional 1,3-butadiene derivatives and the stereochemistry of the resulting polymers will be described. Finally, a variety of chain-functionalization reactions using functional 1,1-diphenylethylene derivatives via a 1:1 addition reaction will be introduced.

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Authors and Affiliations

  1. Polymeric and Organic Materials Department, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1, Ohokayama, Meguro-ku, Tokyo, 152-8552, Japan

    Akira Hirao

  2. Institute of Polymer Science and Engineering, National Taiwan University, No.1, Sec.4, Roosevelt Road, Taipei, 10617, Taiwan

    Akira Hirao

  3. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren Ai Road, Suzhou Industrial Park, Suzhou, 215123, China

    Akira Hirao

  4. Department of Materials Science and Technology, Nagaoka University of Technology, 1603-1, Kamitomioka, Nagaoka, Niigata, 940-2188, Japan

    Katsuhiko Takenaka

Authors
  1. Akira Hirao
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  2. Katsuhiko Takenaka
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Correspondence to Katsuhiko Takenaka .

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Editors and Affiliations

  1. King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia

    Nikos Hadjichristidis

  2. Tokyo Institute of Technology, Tokyo, Japan

    Akira Hirao

Abbreviations

Abbreviations

(NCA)s:

α-Amino acid N-carboxyanhydrides

(TMS)2B:

2,3-Bis(trimethylsilyl)-1,3-butadiene

2VP:

2-Vinylpyridine

BF:

Benzofulvene

CHD:

1,3-Cyclohexadiene

DPE:

1,1-Diphenylethylene

DVB:

1,4-Divinylbenzene

EWGs:

Electron-withdrawing groups

HMPT:

N,N,N′,N′,N′′,N′′-hexamethylphosphortriamide

KOBut :

Potassium tert-butoxide

MMA:

Methyl methacrylate

MOP3D:

2-(4-Methoxyphenyl)[3]dendralene

MWD:

Molecular weight distribution

P3D:

2-Phenyl[3]dendralene

PA:

Phosphaalkene

PB:

Poly(1,3-butadiene)

PI:

Polyisoprene

PS:

Polystyrene

PSLi:

Poly(styryl)lithium

RLi:

Organolithium

SABB:

2-(4-Bis(trimethylsilyl)amino)butyl-1,3-butadiene

SAMB:

2-Bis(trimethylsilyl)aminomethyl-1,3-butadiene

SEC:

Size exclusion chromatography

sec-BuLi:

sec-Butyllithium

TBDMS:

tert-Butyldimethylsilyl

TBDMSOS:

4-tert-Butyldimethylsilyloxystyrene

TBSOM-DPE:

1,1-Bis(3-tert-butyldimethylsilyloxymethylphenyl)ethylene

TBSOMP:

3-tert-Butyldimethylsilyloxymethylphenyl

TESB:

2-Triethylsilyl-1,3-butadiene

TGIC:

Temperature gradient interaction chromatography

TIPOSB:

2-Triisopropoxysilyl-1,3-butadiene

TMEDA:

N,N,N′,N′-Tetramethylethylenediamine

TMOSB:

2-Trimethoxysilyl-1,3-butadiene

TMS:

Trimethylsilyl

TMSB:

2-Trimethylsilyl-1,3-butadiene

TMSMB:

2-(Trimethylsilyl)methyl-1,3-butadiene

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Hirao, A., Takenaka, K. (2015). Nonpolar Monomers: Styrene and 1,3-Butadiene Derivatives. In: Hadjichristidis, N., Hirao, A. (eds) Anionic Polymerization. Springer, Tokyo. https://doi.org/10.1007/978-4-431-54186-8_3

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