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Optimizing the Covalent Cationization Method for the Mass Spectrometry of Polyolefins



Sheng Lin-Gibson, L Brunner, David L. VanderHart, Barry J. Bauer, B M. Fanconi, Charles M. Guttman, William E. Wallace


Previously a new method was introduced for the mass spectrometry of polyolefins whereby an organic cation is covalently bonded to the polymer to produce the necessary ionization for the creation of intact gas?phase macromolecules by matrix-assisted laser desorption/ionization (MALDI). In this paper that methodology was further optimized to produce mass spectra for higher molecular mass materials than had been achieved previously. Comparison is made between conventional copper metal cationization of end-functionalized polybutadiene and the same material hydrogenated and subsequently covalently cationized. Excellent agreement is found when the molecular mass distributions of these two materials are compared. NIST Standard Reference Material polyethylenes were also studied and found to give molecular masses systematically below the values determined classically by about two-thirds. Reasons for this discrepancy are explored and discussed.
No. 18


covalent ctionization, MALDI, modification, molecular, polyolefin, weight characterization


Lin-Gibson, S. , Brunner, L. , VanderHart, D. , Bauer, B. , Fanconi, B. , Guttman, C. and Wallace, W. (2002), Optimizing the Covalent Cationization Method for the Mass Spectrometry of Polyolefins, Macromolecules, [online], (Accessed June 20, 2024)


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Created July 31, 2002, Updated October 12, 2021