Abstract
Branching in polymers is an important way to modify the materials properties, however the characterization of random branching in polymeric materials is a challenge in polymer analysis. In this work, liquid adsorption chromatography methods are developed for a commercially available hyperbranched polyester (BoltornTM). This chromatographic techniques was then coupled to offline MALDI-TOF MS analysis, a first in the analysis of randomly branched polymers. The coupling of these two techniques provides superior MALDI-TOF spectra, enabling the easy identification of structural subdistributons based on theoretical molecular weight. Detailed analysis of the MALDI-TOF spectra shows that these chromatographic conditions separate cyclic Boltorn polymers (with no core molecule) from non-cyclic polymers (with core molecule), and these are the only two architectures observed. MALDI MS also confirms that the chromatographic separation mode is adsorption, but further analysis is needed to determine if there is a separation by degree of branching.
Access provided by Autonomous University of Puebla. Download to read the full chapter text
Chapter PDF
Similar content being viewed by others
Keywords
References
Numata K, Srivastava RK, Finne-Wistrand A, Albertsson A-C, Doi Y, Abe H (2007) Branched Poly(lactide) Synthesized by Enzymatic Polymerization: Effects of Molecular Branches and Stereochemistry on Enzymatic Degradation and Alkaline Hydrolysis. Biomacromolecules 8 (10):3115-3125.
Žagar E, Žigon M (2011) Aliphatic hyperbranched polyesters based on 2,2-bis(methylol)propionic acid—Determination of structure, solution and bulk properties. Prog Polym Sci 36 (1):53-88.
Hawker CJ, Lee R, Frechet JMJ (1991) One-step synthesis of hyperbranched dendritic polyesters. J Am Chem Soc 113 (12):4583-4588.
Wyatt PJ (1993) Light scattering and the absolute characterization of macromolecules. Anal Chim Acta 272 (1):1-40.
Podzimek S (1994) The use of GPC coupled with a multiangle laser light scattering photometer for the characterization of polymers. On the determination of molecular weight, size and branching. J Appl Polym Sci 54 (1):91-103.
Simon PFW, Müller AHE, Pakula T (2001) Characterization of Highly Branched Poly(methyl methacrylate) by Solution Viscosity and Viscoelastic Spectroscopy. Macromolecules 34 (6):1677-1684.
Gaborieau M, Nicolas J, Save M, Charleux B, Vairon J-P, Gilbert RG, Castignolles P (2008) Separation of complex branched polymers by size-exclusion chromatography probed with multiple detection. Journal of Chromatography A 1190 (1–2):215.
Weidner SM, Trimpin S (2010) Mass Spectrometry of Synthetic Polymers. Anal Chem 82 (12):4811-4829.
Wolf FK, Frey H (2009) Inimer-Promoted Synthesis of Branched and Hyperbranched Polylactide Copolymers. Macromolecules 42 (24):9443-9456.
Weidner SM, Falkenhagen J, Knop K, Thünemann A (2009) Structure and end-group analysis of complex hexanediol-neopentylglycol-adipic acid copolyesters by matrix-assisted laser desorption/ionization collision-induced dissociation tandem mass spectrometry. Rapid Commun Mass Spectrom 23 (17):2768-2774.
Falkenhagen J, Weidner SM (2005) Detection limits of matrix-assisted laser desorption/ionisation mass spectrometry coupled to chromatography – a new application of solvent-free sample preparation. Rapid Commun Mass Spectrom 19 (24):3724-3730.
Biela T, Duda A, Rode K, Pasch H (2003) Characterization of star-shaped poly(l-lactide)s by liquid chromatography at critical conditions. Polymer 44 (6):1851-1860.
Al Samman M, Radke W, Khalyavina A, Lederer A (2010) Retention Behavior of Linear, Branched, and Hyperbranched Polyesters in Interaction Liquid Chromatography. Macromolecules 43 (7):3215-3220.
Malmström E, Hult A (1996) Kinetics of Formation of Hyperbranched Polyesters Based on 2,2-Bis(methylol)propionic Acid. Macromolecules 29 (4):1222-1228.
Žagar E, Žigon M (2002) Characterization of a Commercial Hyperbranched Aliphatic Polyester Based on 2,2-Bis(methylol)propionic Acid. Macromolecules 35 (27):9913-9925.
Acknowledgment
Bianka Manger (HPLC) and Rosemarie Laging (MALDI-TOF MS) are thanked for their assistance in data acquisition. This work was partially funded by an Adolf Martens Postdoctoral Fellowship from BAM (to J.N.H.).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2014 Springer International Publishing Switzerland
About this chapter
Cite this chapter
Hoskins, J.N., Falkenhagen, J., Weidner, S.M. (2014). Characterization of Randomly Branched Polymers Utilizing Liquid Chromatography and Mass Spectrometry. In: Udomkichdecha, W., Böllinghaus, T., Manonukul, A., Lexow, J. (eds) Materials Challenges and Testing for Manufacturing, Mobility, Biomedical Applications and Climate. Springer, Cham. https://doi.org/10.1007/978-3-319-11340-1_14
Download citation
DOI: https://doi.org/10.1007/978-3-319-11340-1_14
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-11339-5
Online ISBN: 978-3-319-11340-1
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)