Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: <italic style="font-style: italic">In Situ</italic> Kinetics Evidences Tapered Block Copolymer Formation

Ann-Kathrin Danner; Daniel Leibig; Lea-Marie Vogt; Holger Frey

doi:10.1007/s10118-019-2296-y

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Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation

ARTICLE | Updated：2021-02-18

- Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation
- Chinese Journal of Polymer Science Vol. 37, Issue 9, Pages: 912-918(2019)
- Affiliations：
  
  a.Institute of Organic Chemistry, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, 55128 Mainz, Germany
  b.Graduate School Materials Science in Mainz, Staudinger Weg 9, 55128 Mainz, Germany
- Author bio：
  
  hfrey@uni-mainz.de
- Funds：
- DOI：10.1007/s10118-019-2296-y
  CLC：
- Received：12 April 2019，
  
  Revised：2019-5-16，
  
  Accepted：16 May 2019，
  
  Online First：04 July 2019，
  
  Published：2019-09
- Accepted：
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Citation: Danner, A. K.; Leibig, D.; Vogt, L. M.; Frey, H. Monomer-activated copolymerization of ethylene oxide and epichlorohydrin: In situ kinetics evidences tapered block copolymer formation. Chinese J. Polym. Sci. 2019, 37, 912–918

Ann-Kathrin Danner, Daniel Leibig, Lea-Marie Vogt, et al. Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation[J]. Chinese Journal of Polymer Science, 2019, 37(9): 912-918. DOI: 10.1007/s10118-019-2296-y.
Citation: Danner, A. K.; Leibig, D.; Vogt, L. M.; Frey, H. Monomer-activated copolymerization of ethylene oxide and epichlorohydrin: In situ kinetics evidences tapered block copolymer formation. Chinese J. Polym. Sci. 2019, 37, 912–918 DOI： 10.1007/s10118-019-2296-y.

Ann-Kathrin Danner, Daniel Leibig, Lea-Marie Vogt, et al. Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation[J]. Chinese Journal of Polymer Science, 2019, 37(9): 912-918. DOI: 10.1007/s10118-019-2296-y. DOI：

摘要

Abstract

The monomer-activated anionic ring-opening copolymerization (AROP) of ethylene oxide (EO) and epichlorohydrin (ECH) using tetraoctylammonium bromide as an initiator and triisobutylaluminum (

-Bu

Al) as an activator was studied. The properties of the copolymers as well as the microstructure have been analyzed in detail

via

in situ

NMR kinetics study. The statistical copolymers exhibited molecular weights ranging from 2350 g·mol

–1

to 38000 g·mol

–1

(measured by SEC

PEG-standards) and moderate dispersities of 1.27–1.44. The thermal property tests revealed both a glass transition and melting for all copolymers

supporting a block-like nature. Applying

in situ

NMR kinetic measurements

the reactivity ratios of EO and ECH were determined to be strongly disparate

i.e

= 9.2 and

ECH

= 0.10. This shows that the simple one-pot statistical anionic copolymerization of EO and ECH

via

the monomer-activated AROP resulted in the formation of strongly tapered

block-like structures. Furthermore

post-polymerization functionalization of the reactive chloromethyl groups by nucleophilic displacement was investigated for the copolymers. Copolymerization of EO and ECH offers a broad platform for further functionalization and therefore the possibility to prepare a variety of multifunctional PEGs.

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references

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Monomer-activated Copolymerization of Ethylene Oxide and Epichlorohydrin: In Situ Kinetics Evidences Tapered Block Copolymer Formation

DOI：10.1007/s10118-019-2296-y

摘要

Abstract

关键词

Keywords

references