Polymer characterization by combining liquid chromatography with MALDI and ESI mass spectrometry

Abstract

High-performance polymers are complex mixtures of materials of different size and chemical composition and with different end groups and architecture. To determine the molecular heterogeneity of such systems, hyphenation of several techniques is required. The value of coupling mass spectrometry (MS) with separation techniques has already been recognized - such methods have proved to be among the most powerful for molecular characterization of complex polymer systems. The review focuses on matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) MS coupled with liquid chromatography (LC). Such hyphenation has been used for most polymer analysis by mass spectrometry coupled with separation techniques. The advantages and/or limitations of these techniques for polymer characterization are discussed. Future prospects are briefly outlined.

LC-Multistage Mass Spectrometry for the Characterization of Poly(Butylene Adipate-co-Butylene Terephthalate) Copolyester

“…The combination of liquid chromatography with mass spectrometry (LC-MS) is often applied to polymer characterization in order to avoid effects such as ion suppression that lead to mass discrimination in the detection of higher-mass portions of the material. The online connection of gradient polymer elution chromatography (GPEC) [14,15] to MS separates the polymer distribution based on the differences in solubility among the polymer molecules with different chemical compositions.…”

Time of flight secondary ion mass spectrometric determination of molecular weight distributions of low polydispersity poly(dimethyl siloxane) with polyatomic primary ions

“…Matrix assisted laser desorption ionization (MALDI) mass spectrometry can provide molecular weight distributions of polymers up to 1.5 million Da. However, this can only be used for polymers with narrow polydispersity [2][3][4]. Electrospray ionization (ESI) mass spectrometry can be utilized to determine molecular weight distributions but this technique suffers from the need to dissolve the polymer in a suitable solvent [2].…”

“…However, this can only be used for polymers with narrow polydispersity [2][3][4]. Electrospray ionization (ESI) mass spectrometry can be utilized to determine molecular weight distributions but this technique suffers from the need to dissolve the polymer in a suitable solvent [2]. Secondary ion mass spectrometry (SIMS), especially with time of flight detection, offers the opportunity to determine MWD, and with the particular advantage of surface sensitivity, yielding MWD information from the surface of a solid polymer matrix [5][6][7].…”

An Overview of Analytical Applications of Time of Flight-Mass Spectrometric (TOF-MS) Analyzers and an Inductively Coupled Plasma-TOF-MS Technique

“…[36][37][38][39][40][41][42][43][44][45][46][47][48] Coupling of MALDI with liquid chromatography, capillary electrophoresis (CE) and gel chromatography is a way to extend its applicability. 32,[49][50][51][52][53][54][55][56][57][58] The possibility to attain the sensitivity of physical limits (a few atoms or molecules) by laser-assisted reflectron TOF-MS has been stated. 59 The precision of the detection and quantification of metal isotope ratios comparable to ICP-MS and thermal ionization mass spectrometry (TIMS) has been reported.…”