Degradation of RAFT polymers in a cyclic ether studied via high resolution ESI-MS: Implications for synthesis, storage, and end-group modification

Gruendling, T., Pickford, R., Guilhaus, M., & Barner-Kowollik, C. (2008) Degradation of RAFT polymers in a cyclic ether studied via high resolution ESI-MS: Implications for synthesis, storage, and end-group modification. Journal of Polymer Science, Part A: Polymer Chemistry, 46(22).

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Abstract

We report on the detailed mass spectrometric analysis of the degradation products generated during storage of poly(methyl methacrylate) (pMMA) and polystyrene (pSty) carrying cumyldithiobenzoate (CDB) endgroups. Samples were stored in either a cyclic ether (tetrahydrofuran) (THF) or an inert solvent (dichloromethane). The degradation process was followed over a period of 4-weeks. Degradation rate of the reversible addition fragmentation (RAFT) polymer strongly depends on the hydroperoxide-content of the solvent. Mass spectrometric evidence supports an unexpected radical degradation mechanism for the pMMA macroRAFT agent. Hydroperoxide functional pMMA was the single product after less than 7 days in high purity THF. No formation of the sulfine/thioester was observed. The identity of the hydroperoxide was unambiguously assigned using accurate mass measurements by Fourier-Transform ion-cyclotron-resonance mass spectrometry together with chemical identification reactions. The hydroperoxide end group formation proceeds efficiently as well as in high yields and thus constitutes a powerful method for end group modification. The degradation pathways of the CDB functional pSty in THF include mainly oxidation towards the sulfine/thioester, with little degradation via thermal elimination of dithiobenzoic acid and subsequent epoxidation. The shelf life of CDB functional polymers is limited even in inert solvent because of this inherent but slow thermal elimination reaction. Because of the short period necessary for the transformation of the functional dithiobenzyl endgroups, substitution of cyclic ethers as solvents for RAFT polymers in synthesis and analysis is strongly suggested. © 2008 Wiley Periodicals, Inc.

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ID Code: 99177
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :51
Export Date: 5 September 2016
CODEN: JPACE
Correspondence Address: Barner-Kowollik, C.; Institut für Technische und Polymerchemie, Karlsruhe Institute of Technology (KIT), Universität Karlsruhe (THJ, Engesserstr. 18, 76128 Karlsruhe, Germany; email: christopher.barner-kowollik@polymer.uni-karlsruhe.de
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Keywords: Degradation, Electrospray ionization mass spectrometry (ESI-MS), Ether peroxides, Living radical polymerization (LRP), Mass spectrometry, Poly(methyl methacrylate) (PMMA), Polymer endgroup degradation, Polystyrene (PS), ABS resins, Acids, Acrylic monomers, Chemical reactions, Dichloromethane, Electrospray ionization, Esters, Ethers, Fourier transforms, Free radical polymerization, Functional polymers, Group technology, High performance liquid chromatography, Living polymerization, Mass spectrometers, Monomers, Organic compounds, Oxidation, Photoresists, Polymers, Polystyrenes, Rate constants, Solvents, Spectrometers, Spectrometry, Spectrum analysis, Accurate mass measurements, Chemical identifications, Cyclic ethers, Degradation mechanisms, Degradation pathways, Degradation processes, Degradation products, Degradation rates, Elimination reactions, End groups, Fourier-transform, High purities, High resolutions, High yields, Hydroperoxide, Inert solvents, Mass spectrometric analysis, NO formations, Polies (methyl methacrylate), Reversible addition fragmentations, Shelf lives, Short periods, Single products, Tetrahydrofuran, Organic solvents
DOI: 10.1002/pola.23050
ISSN: 0887624X
Divisions: Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 28 Jun 2017 15:01

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