Investigating Cu(0)‐Mediated Polymerizations: New Kinetic Insights Based on a Comparison of Kinetic Modeling with Experimental Data. Issue 1 (3rd September 2012)

• Record Type: Journal Article
• Authors: Haehnel, Alexander P.; Fleischmann, Sven; Hesse, Pascal; Hungenberg, Klaus‐Dieter; Barner‐Kowollik, Christopher
• Is Part Of: Macromolecular reaction engineering. Volume 7:Issue 1(2013:Jan.)
• Page Start: 8
• Page End: 23
• Publication Date: 2012-09-03
• Subjects: Polymers -- Periodicals; Polymerization -- Periodicals; Reaction mechanisms (Chemistry) -- Periodicals; Electronic journals; 547.705
• DOI: 10.1002/mren.201200030
• Languages: English
• ISSNs: 1862-832X

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A kinetic model is developed mimicking experimental results obtained via detailed kinetic investigation of Cu<sup>0</sup>‐mediated LRP processes of butyl acrylate in variable solvents at 50 °C. In all polymerizations, a pronounced offset in the <tex-math notation="tex"><![CDATA[$\overline {M} _{{\rm n}} $]]></tex-math><inline-graphic xlink:href="ark:/27927/pgg1q7csdkt" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /> versus conversion profile is observed. The kinetic modeling predicts that conventional FRP is responsible for a high molecular weight fraction of terminated polymer. The initial <tex-math notation="tex"><![CDATA[$\overline {M} _{{\rm n}} $]]></tex-math><inline-graphic xlink:href="ark:/27927/pgg1q7csdmc" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /> offset is congruent with a relatively slow establishment of the controlling equilibrium. Kinetic modeling and experiments demonstrate that the conversion versus time data cannot be adequately described by a first‐order kinetic analysis. For selected rate coefficients (<italic>k</italic><sub>a</sub>, <italic>k</italic><sub>d</sub>, and <italic>k</italic><sub>dis_cu</sub>) a range is assigned, which affords a well controlled polymerization. <boxed-text content-type="graphic" position="anchor" orientation="portrait"><graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgg1q7csfzd" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></boxed-text></p> </abstract>