title: Evaluation of atmospheric solid analysis probe ionization coupled to ion mobility mass spectrometry for characterization of poly(ether ether ketone) polymers.
abstract: Recently, the interest of the coupling between atmospheric solid analysis probe (ASAP) and ion mobility-mass spectrometry has been revealed in the field of polymers. This method associates a direct ionization technique with a bi-dimensional separation method. Poly(ether ether ketones) (PEEK) belong to the family of the poly(aryl ether ketones) (PAEK) which are high performance aromatic polymers usually used in aerospace, electronics and nuclear industries. PEEK are important commercial thermoplastics with excellent chemical resistance and good mechanical properties. Because of their low solubility, few structural characterization studies of PEEK have been reported. In mass spectrometry, only MALDI-TOF analyses for polymer synthesis monitoring have been described with the use of strong acids such as sulfuric acid. This work demonstrates that ASAP is particularly efficient for analysis of PEEK in a solvent free approach with the production of intact small oligomers (n≤2). Five types of PEEK oligomers with different end-groups were evidenced. With MALDI-TOF, the same end-groups with almost the same relative abundance were obtained which support the hypothesis that the oligomers detected in ASAP are intact small oligomers and not fragments or pyrolysis products. This is particularly interesting as generally the ASAP analysis of polymers yields pyrolysis products with the loss of end-group information. The end-groups assignments have been confirmed by tandem mass spectrometry (MS/MS) experiments on the M(+) molecular ions, which allowed highlighting some specific neutral or radical losses as well as two diagnostic product ions. Thus, ASAP-IM/MS/MS proves to be a fast and efficient alternative way to characterize low solubility polymers such as PEEK.
authors.affiliation: Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex, France.
authors.forename: Emilie
authors.initials: E
authors.lastname: Cossoul
authors.affiliation: Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex, France.
authors.forename: Marie
authors.initials: M
authors.lastname: Hubert-Roux
authors.affiliation: Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex, France.
authors.forename: Muriel
authors.initials: M
authors.lastname: Sebban
authors.affiliation: Arkema, Centre d'Etude de Recherche et Développement, 27470 Serquigny, France.
authors.forename: Florence
authors.initials: F
authors.lastname: Churlaud
authors.affiliation: Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex, France.
authors.forename: Hassan
authors.initials: H
authors.lastname: Oulyadi
authors.affiliation: Normandie Université, COBRA, UMR6014 and FR3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF, 1 rue Tesnière, 76821 Mont-Saint-Aignan Cedex, France. Electronic address: carlos.afonso@univ-rouen.fr.
authors.forename: Carlos
authors.initials: C
authors.lastname: Afonso
keywords: Atmospheric solid analysis probe ionization; Desorption; Ion mobility; Mass spectrometry; Poly(ether ether ketone) polymers