Effective pretreatment for thermally-assisted hydrolysis and methylation GC-MS of intractably cross-linked acrylate copolymers

Thermally-assisted hydrolysis and methylation-gas chromatography-mass spectrometry (THM-GC-MS) using tetramethylammonium hydroxide (TMAH) is an effective approach for the characterization of condensation polymers with ester linkages such as ultraviolet (UV)-cured acrylate resins. However, for intractably cured acrylic resins, reliable structural characterization is often difficult by conventional THM-GC-MS owing to insufficient THM reactions. In this study, a pretreatment to effectively improve THM efficiency was proposed, in which the resin sample was preliminarily soaked and dissolved in a TMAH-methanol solution in a microtube. An aliquot of the TMAH solution was then introduced into the pyrolyzer at 400 °C to produce THM-GC-MS. The effectiveness of the proposed pretreatment was demonstrated using a UV-cured acrylate copolymer consisting of bulky and high-molecular weight bifunctional acrylate (9,9-Bis[4-(2-acryloyloxy ethoxy) phenyl]fluorene) and monofunctional acylate (2-(9 H-Carbazol-9-yl)ethyl acrylate) monomers, for which THM reactions did not proceed efficiently in conventional THM-GC-MS. Conversely, by the modified THM-GC-MS process with a pretreatment involving immersion at room temperature for 24 h or at 60 °C for 30 min, the characteristic decomposition products for each monomer unit were clearly observed in the chromatograms, and the copolymer composition could be precisely estimated from the relative yields of the observed decomposition products. In addition, a methyl acrylate peak, formed from unreacted acrylate moieties in the photocured copolymer, appeared in the chromatogram. Its relative yields were correlated to the double bond conversion in the cured sample. The observed results were successfully interpreted to clarify the curing process of the photocured acrylate copolymer samples. [Display omitted] •A THM-GC-MS method applicable to intractable UV-cured acrylate was developed.•The cured resin sample was preliminarily immersed and dissolved into a TMAH solution.•The copolymer composition of the intractable acrylate resin was precisely determined.•The double bond conversion was estimated by the modified THM-GC-MS method.•The observed results were interpreted in terms of the photocuring reactions.