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Living Anionic Polymerization of Isocyanates

  • Chapter
Anionic Polymerization

Abstract

Polyisocyanates are rodlike polymers with dynamic helical conformations likely to be synthesized using anionic polymerization. Although many scientists have tried to obtain polyisocyanates with a controlled molecular weight and a narrow weight distribution, the trimerization precluded controlled polyisocyanate formation. To overcome the lack of a living nature, special anionic polymerizations were invented. The use of effective additives and dual functional initiators stabilized the living chain end to prevent the trimerization. These polymerizations eventually achieved the living nature indicating quantitative yield and predictable molecular weight and narrow molecular weight distribution. The state of art of anionic polymerization of isocyanates and the effective functionalization techniques led to synthesis of well-defined linear, telechelic, chiral, star, rod-coil block, and graft polymers. From the controlled molecular architectures, a comprehensive understanding on helical properties and morphologies for polyisocyanates and their block copolymers has been accomplished.

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Acknowledgments

This work was supported by the “GIST-Caltech Research Collaboration” Project through a grant provided by GIST.

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Authors and Affiliations

  1. School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), 123 Cheomdangwagi-ro, Buk-gu, Gwangju, 500-712, Republic of Korea

    Chang-Geun Chae, Ho-Bin Seo & Jae-Suk Lee

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  1. Chang-Geun Chae
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  3. Jae-Suk Lee
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Correspondence to Jae-Suk Lee .

Editor information

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

1,4-DVB:

1,4-Divinylbenzene

2VP:

2-Vinylpyridine

3MeOPI:

3-Methoxyphenyl isocyanate

AIBN:

2,2′-Azobisisobutyronitrile

C60 :

Fullerene

calcd:

Calculated

CCD effect:

Covalent chiral domino effect

CD:

Circular dichroism

DCCD effect:

Double covalent chiral domino effect

DMF:

N,N-Dimethylformamide

DNA:

Deoxyribonucleic acid

DPM-K:

Diphenylmethyl potassium

GIST effect:

Governing initiation-supporting termination effect

HIC:

n-Hexyl isocyanate

K-Naph:

Potassium naphthalenide

Li-Naph:

Lithium naphthalenide

M helix:

Left-handed helix

MAHI:

Methoxycarbonylaminohexyl isocyanate

M n :

Number-average molecular weight

M-Naph:

Metal naphthalenide

M w/M :

Molecular weight distribution

M w :

Weight-average molecular weight

Na-BA:

Sodium benzanilide

Na-BH:

Sodium benzhydroxide

NaBPh4 :

Sodium tetraphenylborate

Na-DB:

Sodium deoxybenzoin

Na-DPM:

Diphenylmethyl sodium

Na-Naph:

Sodium naphthalenide

obsd:

Observed

P helix:

Right-handed helix

P2VP:

Poly(2-vinylpyridine)

P2VP-b-PHIC:

Poly(2-vinylpyridine)-block-poly(n-hexyl isocyanate)

P2VP-b-PHIC-b-P2VP:

Poly(2-vinylpyridine)-block-poly(n-hexyl isocyanate)-block-poly(2-vinylpyridine)

PAHI:

n-Propyloxycarbonylaminohexyl isocyanate

PEAHI:

n-Pentyloxycarbonylaminohexyl

PEG:

Poly(ethylene glycol)

PFIC:

Poly(furfuryl isocyanate)

PFIC-b-PHIC:

Poly(furfuryl isocyanate)-block-poly(n-hexyl isocyanate)

PHIC:

Poly(n-hexyl isocyanate)

PHIC-b-P2VP-b-PHIC:

Poly(n-hexyl isocyanate)-block-poly(2-vinylpyridine)-block-poly(n-hexyl isocyanate)

PHIC-b-PTMSPMA:

Poly(n-hexyl isocyanate)-block-poly(3-(trimethoxysilyl)propyl methacrylate)

PHIC-b-PVP:

Poly(n-hexyl isocyanate)-block-poly(N-vinylpyrrolidone)

PI:

Polyisoprene

PI-b-PHIC:

Polyisoprene-block-poly(n-hexyl isocyanate)

PPA:

Poly(phenylacetylene)

PPA-g-P3MeOPI:

Poly(phenyl acetylene)-graft-poly(3-methoxyphenyl isocyanate)

PS:

Polystyrene

PS-g-PHIC:

Polystyrene-graft-poly(n-hexyl isocyanate)

PTESPI:

Poly(3-(triethoxysilyl)propyl isocyanate)

PTMSPMA:

Poly(3-(trimethoxysilyl)propyl methacrylate)

PVP:

Poly(N-vinylpyrrolidone)

Rh(nbd)BPh4 :

Rh+(2,5-norbornadiene)[(η 6-C6H5)B-(C6H5)3]

RNA:

Ribonucleic acid

SEC:

Size exclusion chromatography

SEC-MALLS:

Size exclusion chromatography-multiangle laser light scattering

TEMPO-ONa:

Sodium-4-oxy-2,2,6,6-tetramethylpiperidinyloxy

TESPI:

3-(Triethoxysilyl)propyl isocyanate

THF:

Tetrahydrofuran

TMSPMA:

3-(Trimethoxysilyl)propyl methacrylate

VP:

N-Vinylpyrrolidone

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© 2015 Springer Japan

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Chae, CG., Seo, HB., Lee, JS. (2015). Living Anionic Polymerization of Isocyanates. In: Hadjichristidis, N., Hirao, A. (eds) Anionic Polymerization. Springer, Tokyo. https://doi.org/10.1007/978-4-431-54186-8_7

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