Nielen M W, Buijtenhuijs F A
General Analytical and Environmental Chemistry Department, Akzo Nobel Central Research, P.O. Box 9300, 6800 SB Arnhem, The Netherlands.
Anal Chem. 1999 May 1;71(9):1809-14. doi: 10.1021/ac981141a.
Hyphenation of liquid chromatography (LC) techniques with electrospray ionization (ESI) orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry (MS) provides both MS-based structural information and LC-based quantitative data in polymer analysis. In one experimental setup, three different LC modes are interfaced with MS: size-exclusion chromatography (SEC/MS), gradient polymer elution chromatography (GPEC/MS), and liquid chromatography at the critical point of adsorption (LCCC/MS). In SEC/MS, both absolute mass calibration of the SEC column based on the polymer itself and determination of monomers and end groups from the mass spectra are achieved. GPEC/MS shows detailed chemical heterogeneity of the polymer and the chemical composition distribution within oligomer groups. In LCCC/MS, the retention behavior is primarily governed by chemical heterogeneities, such as different end group functionalities, and quantitative end group calculations can be easily made. The potential of these methods and the benefit of time-of-flight analyzers in polymer analysis are discussed using SEC/MS of a polydisperse poly(methyl methacrylate) sample, GPEC/MS of dipropoxylated bisphenol A/adipic acid polyester resin, LCCC/MS of alkylated poly(ethylene glycol), and LCCC/MS of terephthalic acid/neopentyl glycol polyester resin.
液相色谱（LC）技术与电喷雾电离（ESI）正交加速飞行时间（oa - TOF）质谱（MS）联用，在聚合物分析中可同时提供基于质谱的结构信息和基于液相色谱的定量数据。在一种实验装置中，三种不同的液相色谱模式与质谱联用：尺寸排阻色谱（SEC/MS）、梯度聚合物洗脱色谱（GPEC/MS）以及吸附临界点液相色谱（LCCC/MS）。在SEC/MS中，可基于聚合物本身对SEC柱进行绝对质量校准，并从质谱图中确定单体和端基。GPEC/MS可显示聚合物详细的化学不均匀性以及低聚物组内的化学组成分布。在LCCC/MS中，保留行为主要由化学不均匀性决定，如不同的端基官能团，并且可以轻松进行端基的定量计算。使用多分散聚甲基丙烯酸甲酯样品的SEC/MS、二丙氧基化双酚A/己二酸聚酯树脂的GPEC/MS、烷基化聚乙二醇的LCCC/MS以及对苯二甲酸/新戊二醇聚酯树脂的LCCC/MS，讨论了这些方法的潜力以及飞行时间分析仪在聚合物分析中的优势。
