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Keywords:

  • copolymer composition and sequence;
  • copolymer molar mass;
  • block copolymers

Abstract

Table 1. 
   I.Introduction108
  II.Structural Analysis109
 III.Copolymer Composition111
 A. Composition by the Direct Method111
 B. Composition by the Method Based on Statistics111
 C. Copolymer Composition by the Hard-Ionization Method113
  IV.Copolymer Sequence114
   V.Molar Mass Determination115
  VI.MS as a Detector for Liquid Chromatography116
 VII.Composition Drift and the Compositional Distribution Histogram120
VIII.Quantitation and Methods to Correct Mass Spectral Intensities121
  IX.Copolymer Mixtures and Blends122
   X.Copolymers Obtained by Specific Synthetic Routes123
 A. Copolymers Produced by Enzymes or Occurring in Nature123
 B. Block Copolymers125
 C. Random Addition Copolymers126
 D. Random Condensation Copolymers128
  XI.Summary and Outlook133
Acknowledgments134
References135

Recent and older literature (covering the last 12–13 years) in the field of mass spectra of random and block copolymers is reviewed. A detailed description is given of the information on copolymer properties that can be recovered from the analysis of the low-mass region of the spectrum (the region below 500 Da) and the high-mass region. The features of mass spectra of copolymers obtained by different synthetic routes are discussed, such as free radical, condensation, ring-chain equilibration, microbial synthesis, ring-opening, simple anionic, cationic, Ziegler-Natta, and/or metallocene catalysis, along with some random and block copolymers that occur in Nature. The emphasis is on copolymer composition and average molar mass determination, and on the benefits of coupling mass spectrometry (MS) with separation techniques such as size-exclusion chromatography (SEC) and high performance liquid chromatography (HPLC). © 2002 Wiley Periodicals, Inc., Mass Spec Rev 21:108–144, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/mas.10021