Carbon charge fractions

Ny lon-6 (108 g) carpet backed with calcium-carbonate-filled latex and polypropylene was charged to a 1000-mL three-neck round-bottom flask (equipped with a condenser) with 6 mL of 85% phosphoric acid. Superheated steam was injected continuously during a 45-min period. The vapor temperature of the reaction medium was 250-300°C. The volume of distillate collected was 1065 mL. The distillate contained 1.9% e-caprolactam (as determined by GC), which corresponded to a crude yield of 37.5%. The distillate was fractionated in a distillation column and the nonaqueous phase removed. The remaining aqueous phase was treated with 2% potassium permanganate at 40-50°C for 2 h. Evaporation of... 

During the vacuum fractional distillation of bulked residues (7.2 t containing 30-40% of the bis(hydroxyethyl) derivative, and up to 900 ppm of iron) at 210-225°C/445-55 mbar in a mild steel still, a runaway decomposition set in and accelerated to explosion. Laboratory work on the material charged showed that exothermic decomposition on the large scale would be expected to set in around 210-230°C, and that the induction time at 215°C of 12-19 h fell to 6-9 h in presence of mild steel. Quantitative work in sealed tubes showed a maximum rate of pressure rise of 45 bar/s, to a maximum developed pressure of 200 bar. The thermally induced decomposition produced primary amine, hydrogen chloride, ethylene, methane, carbon monoxide and carbon dioxide. 

The gas chromatographic analysis of the unreacted monomers in the experiments from Table II discloses a constant C5/C8 ratio comparing the starting comonomer composition to the final composition. This means that monomer conversion is the same for 1,5-cyclooctadiene and cyclopentene in the copolymerization so that copolymer compositions are equal to the charge ratios. This result is consistent with the product analysis by 13C NMR spectroscopy where the copolymer composition is nearly identical to the starting comonomer composition. 13C NMR is used to determine the composition of the cyclopentene/1,5-cyclooctadiene copolymers as part of a detailed study of their microstructure (52). The areas of peaks at 29-30 ppm (the pp carbon from cyclopentene units) and at 27.5 ppm (the four ap carbons from the 1,5-cyclooctadiene) are used to obtain the mole fractions of the two comonomers (53, 54, 55). 13C NMR studies and copolymer composition determinations are described by Ivin (51, 56, 57) for various systems. 

B. 3-Cyclopentene-1 -carboxylic acid. A 250-mL, one-necked, round-bottomed flask is charged with 35.8 g of 3-cyclopentene-1,1-dicarboxylic acid and then fitted with a reflux condenser capped with a rubber septum and connected to a Nujol-filled bubbler by means of a syringe needle. The contents of the flask are heated in an oil bath at 170-175°C until carbon dioxide evolution is complete (ca. 2 hr) and then allowed to cool to room temperature. The resulting oil is transferred to a 50-mL flask and vacuum distilled without fractionation to provide 23.0 g (89% or 82% overall from dimethyl malonate) of 3-cyclopentene-1-carboxylic acid as a clear, colorless oil, bp 88°C (2 mm) (Note 7). 

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