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This chapter focuses on pyrograms and thermograms of 163 standard polymer samples, and MS data of the major pyrolyzates. The polymer samples were adopted as a set of representative ones to be utilized in versatile fields, which include representative synthetic polymers, such as polyolefins (homopolymers), vinyl polymers with ethylene units (copolymers), vinyl polymers with styrene units, vinyl polymers with styrene derivatives, acrylate-type polymers, chlorine-containing vinyl polymers, fluorine-containing vinyl polymers, the other vinyl polymers, diene-type elastomers, polyamides, polyacetals and polyethers, thermosetting polymers, polyimides and polyamide-type engineering plastics, polyesters, the other engineering plastics with phenylene skeletons, silicone polymers, and polyurethanes along with some natural polymers—cellulose-type polymers—and finally, the other natural polymers. The schematic flow diagrams of the measuring systems of the pyrolysis gas chromatography mass spectrometry (Py/GC/MS) and evolved gas analysis (EGA)–MS, respectively are illustrated. The resulting mass spectrometric data for all the peaks on the pyrograms stored as the total ion chromatogram, and the selected mass spectra for the top 10 major peaks at most are compiled, together with the retention index (RI) data of the main peaks on the pyrograms. The RI data for the components were estimated by comparison of the retention data for a series of hydrocarbon peaks with known carbon numbers appearing on the pyrogram of polyethylene observed under the same condition.

This chapter focuses on pyrograms for 33 condensation polymers and mass spectrometry (MS) data of the major pyrolyzates obtained in the presence of organic alkaline. It illustrates the schematic flow diagrams of the measuring systems of the reactive pyrolysis gas chromatography mass spectrometry in the presence of organic alkaline, tetramethylammonium hydroxide [(CH 3 ) 4 NOH, TMAH]. A methanol solution of TMAH was used as the organic alkaline reagent. Obtained mass spectrometric data for all the peaks on the pyrograms stored as the total ion chromatogram, and the selected mass spectra of the top 6 major peaks at most are compiled, together with the retention index (RI) data of the main peaks on the pyrograms. Under the pyrogram, the peak assignment table for the program together with molecular weight, RI, and relative peak intensity data are shown.