Pyrolysis—Hydrogenation—GLC of poly-α-olefins

Comparison of literature models for volatile product formation from the pyrolysis of polyisobutylene at mild conditions: Data analysis, free-radical mechanistic considerations, and simulation of initial product-forming pathways

“…4 to RS [6,21], several groups [3d, 3e,3g, 4,7,15,17,20,46] intimated or specifically assigned them to BB involving serial and/or long-range 1,x-shifts. Tsuchiya and Sumi [15] noted the disparity that RS is not consistent with the absence of larger alkane oligomers (see above), systematically outlined the products to be expected from 1,x-hydrogen shifts with x = 3, 5, or 7 for R p and 2, 4, or 6 for R t , but did not consider the dependence of k 1x on x. Kiran and Gillham [4] performed an enumeration of pathways with an even larger range of x (essentially Schemes 1 and 2).…”

“…Partial pyrolyses of PIB at lower T have typically been conducted in open systems under vacuum [3a-3c,3f,3g, [14][15][16] and/or with an inert sweep or cover gas [4,7,17,18], with post-reaction analyses of condensed volatiles. Exhaustive pyrolyses at higher T have typically involved coupled heated-filament flash pyrolysis-GC with inert carrier gas flow [6, [19][20][21] or flash pyrolysis-MS [22] modes. Occasionally hydrogenation, either in-line [20,21a] or post-reaction [7a, 15,16], has been used to simplify GC and NMR spectra of volatiles.…”

Thermal decomposition products of polyisobutylene

“…This finding agrees with experimental results that have been reported earlier. 2 The main volatile decomposition products of polyisobutylene obtained a t the three different pyrolysis temperatures are presented in Table IV. I n Figure 1 a pattern consisting of groups of peaks is noted.…”

Microstructural Characterization of Polypropylenes by High-Resolution Pyrolysis-Hydrogenation Glass Capillary Gas Chromatography

“…In addition to the spectroscopic work mentioned above, pyrolysis-gas chromatography (PGC) has been also demonstrated to be a simple, but powerful, technique for studying the microstructures of pp. [18][19][20][21][22][23][24][25][26][27] Noffz et al 20 adopted PGC and used a 100-m-long capillary column to separate the degradation products from various PP's without any hydrogenation. They suggested that qualitative distinction of the PP's differing in the stereoregularity was possible from the resulting diastereomeric olefins.…”