Japanese ethylene production

Japanese ethylene production slipped below 6Mt in 1993, almost entirely based on naphtha... 

Cyclic Polyolefins (GPO) and Gycloolefin Copolymers (GOG). Japanese and European companies are developing amorphous cycHc polyolefins as substrate materials for optical data storage (213—217). The materials are based on dicyclopentadiene and/or tetracyclododecene (10), where R = H, alkyl, or COOCH. Products are formed by Ziegler-Natta polymerization with addition of ethylene or propylene (11) or so-called metathesis polymerization and hydrogenation (12), (101,216). These products may stiU contain about 10% of the dicycHc stmcture (216). 

A Japanese process developed by Taogosei Chemical Co. chlorinates ethylene directly in the absence of oxygen at 811 kPa (8 atm) and 100—130°C (32). The products ate tetrachlorethanes and pentachloroethane [76-01-7J, which ate then thermally cracked at 912 kPa (9 atm) and 429—451°C to produce a mixture of trichloroethylene, perchloroethylene [127-18-4] and hydrochloric acid. 

Lithium aluminium hydride reduction of 235 followed by mesylation afforded 236. The latter was oxidized with osmium tetroxide and sodium metaperiodate to yield the cyclobutanone 237. Treatment of 237 with acid afforded in 48% yield the ketoacid (238), which was esterified with diazomethane to 239. The latter was converted to the ketal 240 by treatment with ethylene glycol and /7-toluenesulfonic acid. Compound 240 was reduced with lithium aluminium hydride to the alcohol 241. This alcohol had been synthesized previously by Nagata and co-workers (164) by an entirely different route. The azide 242 was prepared in 80% yield by mesylation of 241 and treatment of the product with sodium azide. Lithium aluminium hydride reduction of 242 gave the primary amine, which was converted to the urethane 243 by treatment with ethyl chloroformate. The ketal group of 243 was removed by acidic hydrolysis and the resulting ketone was nitro-sated with N204 and sodium acetate. Decomposition of the nitrosourethane with sodium ethoxide in refluxing ethanol afforded the ketone 244 in 65% yield. The latter had been also synthesized previously by Japanese chemists (165). The ketone 244 was converted to the ketal 246 and the latter to 247... 

A rather interesting application of zeolite-based alkene oxidation catalysis has been demonstrated by Japanese workers (46, 47). In particular, a Pd2 +, Cu2 +Y zeolite was shown to be an active and stable heterogeneous oxidation catalyst which is analogous to the well-known homogeneous Wacker catalyst system containing PdCl2 and CuCl2 (48). Under Wacker conditions (i.e., alkene/02/H20) the zeolite Y catalyst was shown to convert ethylene to acetaldehyde and propylene to acetone with selectivities in excess of 90% with C02 as the major by-product. 

In the presence of Japanese acid clay ethanol decomposes mainly into ether at 200° C. with formation of only traces of aldehyde and ester. At 300° to 400° C. ethylene is the main product, alcohol and ether being almost absent in the liquid product which comprises 92-96 per cent water.470 With a clay catalyst, Hisamura47b has obtained a yield of ethylene of 83 per cent in a product that was 98 per cent pure ethylene at 400° C. 

French firm Adeka Palmarole, the European arm of Japanese polymer additives company Adeka Corp, introduced nucleating agent for poly (ethylene terephthalate), T-1465N. The examples of applications include glass-filled PET for injection molding and the production of PET bottles. The 200 ppm of T-1465N in the PET bottle application reduces the cycle time by half ... 

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