Mass spectra of copolymers

   I. Introduction 108   II. Structural Analysis 109  III. Copolymer Composition 111A. Composition by the Direct Method 111B. Composition by the Method Based on Statistics 111C. Copolymer Composition by the Hard‐Ionization Method 113   IV. Copolymer Sequence 114    V. Molar Mass Determination 115   VI. MS as a Detector for Liquid Chromatography 116  VII. Composition Drift and the Compositional Distribution Histogram 120 VIII. Quantitation and Methods to Correct Mass Spectral Intensities 121   IX. Copolymer Mixtures and Blends 122    X. Copolymers Obtained by Specific Synthetic Routes 123A. Copolymers Produced by Enzymes or Occurring in Nature 123B. Block Copolymers 125C. Random Addition Copolymers 126D. Random Condensation Copolymers 128   XI. Summary and Outlook 133 Acknowledgments 134 References 135Recent 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