Detection and quantification of branching in polyacrylates by size-exclusion chromatography (SEC) and melt-state 13C NMR spectroscopy

被引：97

作者：

Castignolles, Patrice ^{[1
,2
]}

Graf, Robert ^{[1
]}

Parkinson, Matthew ^{[1
]}

Wilhelm, Manfred ^{[1
]}

Gaborieau, Marianne ^{[1
,2
]}

机构：

[1] Max Planck Inst Polymer Res, D-55128 Mainz, Germany

[2] Univ Queensland, Ctr Nutr & Food Sci, Brisbane, Qld 4072, Australia

来源：

POLYMER | 2009年 / 50卷 / 11期

基金：

澳大利亚研究理事会;

关键词：

Branching; NMR; Size-exclusion chromatography; FREE-RADICAL POLYMERIZATION; SEMIBATCH EMULSION POLYMERIZATION; PROPAGATION RATE COEFFICIENTS; N-BUTYL ACRYLATE; INTRAMOLECULAR CHAIN TRANSFER; LIGHT-SCATTERING; UNIVERSAL CALIBRATION; SOLID-STATE; POLY(TERT-BUTYL ACRYLATE); CROSS-LINKING;

D O I：

10.1016/j.polymer.2009.03.021

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Chain branching has been investigated in a homologous series of poly(n-alkyl acrylates) (methyl, ethyl, n-butyl, n-hexyl) obtained by radical polymerization. The total amount of chain branching was quantified using melt-state C-13 nuclear magnetic resonance (NMR) spectroscopy. It gave access to low degrees of branching in both soluble and insoluble polyacrylates, homopolymers; and copolymers. The lowest degree of branching was found for the ethyl member of the series with quantification by conventional solution-state NMR found to take a prohibitively long time. The method proposed here is compared to the ones published previously, and previous literature results are critically reviewed. The presence of long-chain branching (LCB) was selectively detected using multiple-detection size-exclusion chromatography (SEC), with LCB being found for all soluble homopolymers but the poly(n-butyl acrylate). This finding was confirmed by close examination of the Mark-Houwink parameters for the various polyacrylates studied in this work or those previously published. (C) 2009 Elsevier Ltd. All rights reserved.

引用

页码：2373 / 2383

页数：11

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