Desorption electrospray ionisation mass spectrometry of stabilised polyesters reveals activation of hindered amine light stabilisers

Paine, M. R. L., Gryn'Ova, G., Coote, M. L., Barker, P. J., & Blanksby, S. J. (2014) Desorption electrospray ionisation mass spectrometry of stabilised polyesters reveals activation of hindered amine light stabilisers. Polymer Degradation and Stability, 99(1), pp. 223-232.

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Abstract

The use of hindered amine light stabilizers (HALS) to retard thermo- and photo-degradation of polymers has become increasingly common. Proposed mechanisms of polymer stabilisation involve significant changes to the HALS chemical structure; however, reports of the characterisation of these modified chemical species are limited. To better understand the fate of HALS and determine their in situ modifications, desorption electrospray ionisation mass spectrometry (DESI-MS) was employed to characterise ten commercially available HALS present in polyester-based coil coatings. TINUVIN® 770, 292, 144, 123, 152, and NOR371; HOSTAVIN® 3052, 3055, 3050, and 3058 were separately formulated with a pigmented, thermosetting polyester resin, cured on metal at 262 C and analysed directly by DESI-MS. High-level ab initio molecular orbital theory calculations were also undertaken to aid the mechanistic interpretation of the results. For HALS containing N-substituted piperidines (i.e., N-CH3, N-C(O)CH3, and N-OR) a secondary piperidine (N-H) analogue was detected in all cases. The formation of these intermediates can be explained either through hydrogen abstraction based mechanisms or direct N-OR homolysis with the former dominant under normal service temperatures (ca. 25-80 C), and the latter potentially becoming competitive under the high temperatures associated with curing (ca. 230-260 C). © 2013 Elsevier Ltd. All rights reserved.

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ID Code: 68923
Item Type: Journal Article
Refereed: Yes
Additional URLs:
Keywords: Hindered amine light stabiliser, Mass spectrometry, Mechanism, Polyester, ARC
DOI: 10.1016/j.polymdegradstab.2013.10.026
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000)
Divisions: Current > QUT Faculties and Divisions > Science & Engineering Faculty
Funding:
Copyright Owner: Elsevier
Deposited On: 20 Mar 2014 00:17
Last Modified: 05 Feb 2016 05:33

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