Using apparent molecular weight from SEC in controlled/living polymerization and kinetics of polymerization

被引:65
作者
Guillaneuf, Yohann [1 ]
Castignolles, Patrice [1 ]
机构
[1] Univ Queensland, Ctr Nutr & Food Sci, St Lucia, Qld 4072, Australia
关键词
chain length distribution method; gel permeation chromatography; living polymerization; Mark-Houwink-Kuhn-Sakurada parameters; molecular weight distribution; polydispersity index; transfer constant; SIZE-EXCLUSION CHROMATOGRAPHY; FREE-RADICAL POLYMERIZATION; HIGH-THROUGHPUT EXPERIMENTATION; CHAIN-GROWTH POLYCONDENSATION; EVALUATED RATE COEFFICIENTS; BAND-BROADENING PROBLEM; LASER-LIGHT SCATTERING; LIVING POLYMERIZATION; INTRINSIC-VISCOSITY; PERMEATION CHROMATOGRAPHY;
D O I
10.1002/pola.22433
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Apparent molecular weights from size exclusion chromatography, that is molecular weights relative to standards of a nature different to that of the polymer sample being studied, are frequently used. We use calculations corresponding to realistic cases to provide guidelines for situations when, and to what extent, apparent molecular weights (MWs) can be meaningful. In controlled polymerization, we show how, without due care, use of apparent MW, could lead to the incorrect conclusion that the reaction was not controlled, whereas the true MWs would be close to theoretical values. We show here that the quality of the eluent as a solvent for the standard and the polymer sample is a good indication of the accuracy and the significance of the apparent polydispersity index. Accurate Mark-Houwink-Sakurada parameters are of limited availability, but the data about solvent quality available in handbooks or available from static light scattering measurements. Apparent M-n is of no use in controlled polymerization if simple simulations as performed in this work do not validate their use. The determination of transfer constants by the Mayo plot can be performed using apparent M-n without introducing any significant error, contrary to apparent weight-average molecular weight M-w or apparent In number distribution. (C) 2007 Wiley Periodicals, Inc.
引用
收藏
页码:897 / 911
页数:15
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