Conventional Oxyanionic versus Monomer-Activated Anionic Copolymerization of Ethylene Oxide with Glycidyl Ethers: Striking Differences in Reactivity Ratios.

6533b86ffe1ef96bd12cd53f

RESEARCH PRODUCT

Conventional Oxyanionic versus Monomer-Activated Anionic Copolymerization of Ethylene Oxide with Glycidyl Ethers: Striking Differences in Reactivity Ratios.

Johannes C. Liermann Daniel Leibig Holger Frey Jana Herzberger

subject

Polymers and Plastics Ethylene oxide Comonomer Organic Chemistry 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology Ring (chemistry)01 natural sciences 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound Monomer chemistry Polymer chemistry Materials Chemistry Copolymer Alkoxy group Chelation Reactivity (chemistry)0210 nano-technology

description

Detailed understanding of the monomer distribution in copolymers is essential to tailor their properties. For the first time, we have been able to utilize in situ 1H NMR spectroscopy to monitor the monomer-activated anionic ring opening copolymerization (AROP) of ethylene oxide (EO) with a glycidyl ether comonomer, namely, ethoxy ethyl glycidyl ether (EEGE). We determine reactivity ratios and draw a direct comparison to conventional oxyanionic ROP. Surprisingly, the respective monomer reactivities differ strongly between the different types of AROP. Under conventional oxyanionic conditions similar monomer reactivities of EO and EEGE are observed, leading to random structures (rEO = 1.05 ± 0.02, rEEGE = 0.94 ± 0.02). Addition of a cation complexing agent (18-crown-6) showed no influence on the relative reactivity of EO and EEGE (rEO = rEEGE = 1.00 ± 0.02). In striking contrast, monomer-activated AROP produces very different monomer reactivities, affording strongly tapered copolymer structures (rEO = 8.00 ±...

year	journal	country	edition	language
2022-05-26	ACS macro letters

10.1021/acsmacrolett.6b00701 https://pubmed.ncbi.nlm.nih.gov/35614746

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