Equilibrium Constants and Activation Rate Coefficients for Atom Transfer Radical Polymerizations at Pressures up to 2 500 Bar | Zendy

Buback Michael | Zendy; Morick Joachim | Zendy

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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.

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