Citation: Ann-Kathrin Danner, Daniel Leibig, Lea-Marie Vogt, Holger Frey. 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 shu

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

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

Corresponding author: Holger Frey, hfrey@uni-mainz.de
Received Date: 12 April 2019
Revised Date: 16 May 2019
Available Online: 4 July 2019

The monomer-activated anionic ring-opening copolymerization (AROP) of ethylene oxide (EO) and epichlorohydrin (ECH) using tetraoctylammonium bromide as an initiator and triisobutylaluminum (i-Bu₃Al) as an activator was studied. The properties of the copolymers as well as the microstructure have been analyzed in detail via an 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., r_EO = 9.2 and r_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.
- Epichlorohydrin,
- Polymerization,
- Ring-opening,
- Copolymerization,
- Reactivity ratios,
- Epoxide
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