Maldi-Tof Mass Spectrometry of Synthetic Polymers

by Pasch, Harald; Schrepp, W.

• ISBN13: 9783540442592
• ISBN10: 3540442596
• Format: Hardcover
• Copyright: 2003-05-01
• Publisher: Springer Verlag

Summary

MALDI-TOF mass spectrometry is one of the latest and most fascinating new developments in the analysis of organic compounds. Originally developed for the analysis of biomolecules, it has developed into one of the most powerful techniques for the characterization of synthetic polymers. This book describes the fundamentals of the MALDI process and the technical features of MALDI-TOF instrumentation. It reviews the application of MALDI-TOF for identification, chemical and molar mass analysis of synthetic polymers. With many examples, this monograph examines in detail experimental protocols for the determination of endgroups, the analysis of copolymers and additives, and the coupling of liquid chromatography and MALDI-TOF.

Table of Contents

Introduction	p. 1
Molecular Heterogeneity of Polymers	p. 2
Determination of Molar Masses	p. 6
Light Scattering	p. 7
Analytical Ultracentrifugation	p. 9
Viscometry	p. 12
Size Exclusion Chromatography	p. 13
References	p. 17
Mass Spectrometric Instrumentation	p. 19
Ion Sources	p. 21
Gas Phase Ionization	p. 22
Spray Techniques	p. 22
Ionization from the Condensed Phase	p. 24
Field Desorption (FD)	p. 25
Fast Particles (Fast Atom Bombardment, FAB; Secondary Ion Mass Spectrometry, SIMS)	p. 25
Photons	p. 28
Mass Analyzers	p. 29
Quadrupole Analyzer	p. 29
Fourier Transform Analyzer	p. 32
Time-of-Flight Analyzer	p. 34
The Reflectron	p. 36
Time-lag Focusing	p. 37
Practical Consequences	p. 38
Detectors	p. 38
Data Processing	p. 40
Coupling of MS Techniques	p. 42
Classical Mass Spectrometry of Polymers	p. 44
Field- and Laser-Desorption Mass Spectrometry	p. 44
Pyrolysis MS of Polymers	p. 46
Secondary Ion Mass Spectrometry	p. 48
Electrospray Ionization (ESI) Mass Spectrometry	p. 50
References	p. 53
Fundamentals of MALDI-TOF Mass Spectrometry	p. 57
The MALDI Process	p. 57
Primary Ion Formation	p. 59
Secondary Ionization	p. 61
Gas Phase Proton Transfer	p. 61
Gas Phase Cationization	p. 62
Matrices and Sample Preparation	p. 62
Interpretation of Spectra	p. 67
Experimental Parameters	p. 70
Influence of the Matrix	p. 70
Influence of the Cationizing Agent	p. 71
Influence of the Laser Power	p. 73
Type of TOF Analyzer	p. 73
Molar Mass Distribution	p. 78
References	p. 82
Identification of Polmers	p. 85
Introduction	p. 85
Analysis of Homopolymers	p. 89
Identification of Low Molar Mass Homopolymers	p. 89
Polsulfones	p. 91
Polyester Diols	p. 93
Poly(oxymethylene)	p. 95
Emulsifiers	p. 96
Polysiloxane	p. 99
Copolymers	p. 100
Caprolactam-Pyrrolidone Copolymer	p. 100
Post Source Decay	p. 102
References	p. 104
Molar Mass Determination	p. 107
Introduction	p. 107
Analysis of Polymers with Narrow Molar Mass Distribution	p. 112
Oligomer Samples	p. 112
Hydrocarbon Polymers [12]	p. 115
Polymers with Varying Polydispersity [5]	p. 121
Analysis of Polymers with Broad Molar Mass Distribution	p. 123
Mixtures of Polyethylene Glycols	p. 123
Mixtures of Polystyrenes and Polymethyl Methacrylates [17]	p. 127
Further Applications	p. 133
References	p. 133
Analysis of Complex Polymers	p. 135
Introduction	p. 135
Determination of Endgroups	p. 136
Polyamides [5]	p. 138
Triazine-based Polyamines [6]	p. 143
Poly(methylphenyl silane) [8]	p. 150
GTP Polymerized PMMA [10]	p. 155
Poly-[epsilon]-Caprolactone [13]	p. 162
Further Applications	p. 168
Analysis of Copolymers	p. 168
Diblock Copolymers of [alpha]-Methylstyrene and 4-Vinylpyridine [45]	p. 169
Copolymers of Ethylene Oxide and Propylene Oxide [47]	p. 176
Modified Silicone Copolymers [50]	p. 181
Monitoring the Sulfonation of Polystyrene [52]	p. 185
Modified Phenol-Formaldehyde Resins [53]	p. 190
Polyurethanes	p. 199
Further Applications	p. 203
References	p. 204
Coupling of Liquid Chromatography and MALDI-TOF Mass Spectromety	p. 209
Introduction	p. 209
Need for LC-MALDI-TOF Coupling	p. 210
Off-line Measurement of LC Fractions	p. 213
Calibration of Size Exclusion Chromatography [29]	p. 214
Molar Mass Distribution of Polyester Copolymers [31, 32]	p. 219
Poly(ethylene oxides) [28]	p. 222
Block Copolymers of Ethylene Oxide and Propylene Oxide	p. 230
Epoxy Resins [37]	p. 233
Block Copolymers of L-Lactide and Ethylene Oxide [38]	p. 245
Further Applications	p. 250
Interfaces for Coupling LC and MALDI-TOF MS	p. 251
LC Transform Interface	p. 252
PROBOT Interface	p. 254
Measurement of LC Fractions Using a MALDI-TOF Interface	p. 256
SEC-MALDI-TOF Analysis of Poly (n-butyl methacrylate-block-methyl methacrylate) [72]	p. 257
Analysis of Calixarenes by LC-CC-MALDI-TOF [73]	p. 262
Analysis of Polycarbonate by [mu]SEC-MALDI-TOF [76, 77]	p. 266
SEC-MALDI-TOF and LC-CC-MALDI-TOF of Polypropylene Oxides [79]	p. 269
Direct Coupling of Liquid Chromatography and MALDI-TOF MS	p. 279
References	p. 284
Recent Developments and Outlook	p. 289
References	p. 293
Subject Index	p. 295
Table of Contents provided by Rittenhouse. All Rights Reserved.