Premium
Equilibrium Constants and Activation Rate Coefficients for Atom Transfer Radical Polymerizations at Pressures up to 2 500 Bar
Author(s) -
Buback Michael,
Morick Joachim
Publication year - 2010
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201000265
Subject(s) - chemistry , bromide , ligand (biochemistry) , acetonitrile , alkyl , monomer , atom transfer radical polymerization , polymer chemistry , reaction rate constant , bar (unit) , kinetics , inorganic chemistry , organic chemistry , polymer , receptor , biochemistry , physics , quantum mechanics , meteorology
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.