Equilibrium Constants and Activation Rate Coefficients for Atom Transfer Radical Polymerizations at Pressures up to 2 500 Bar
✍ Scribed by Michael Buback; Joachim Morick
- Publisher
- John Wiley and Sons
- Year
- 2010
- Tongue
- English
- Weight
- 352 KB
- Volume
- 211
- Category
- Article
- ISSN
- 1022-1352
No coin nor oath required. For personal study only.
✦ Synopsis
Abstract
Equilibrium constants, K~ATRP~, and activation rate coefficients, k~act~, have been measured up to 2 500 bar and used for estimating reaction volumes, Δ__V__~R~, and activation volumes, Δ__V__^‡^~act~, respectively. Quantitative analysis of binary copper‐ligand–alkyl bromide initiator systems, without monomer being present, has been carried out in a solution of acetonitrile by high‐pressure online‐FT‐NIR/VIS spectroscopic monitoring of the Cu^II^ ligand species. The numbers for Δ__V__~R~ and Δ__V__^‡^~act~ are close to each other and reflect the characteristics of ligand complexation. Whereas Δ__V__~R~ is almost insensitive to the type of initiator, the absolute K~ATRP~ clearly depends on this alkyl bromide species.
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