Copolymerization of propylene oxide with carbon disulfide was studied by using a catalyst consisting of diethylzinc (ZnEt2) and various electron donors. Tertiary amines, tertiary phosphines, and hexamethylphosphoric triamide were the effective donors for the copolymerization, but ZnEt2–water, alcohol, and primary or secondary amines having high activities for the homopolymerization of propylene oxide were not effective for the copolymerization of propylene oxide and carbon disulfide. The copolymers obtained were of low molecular weight and had a monomer unit ratio (CS2/PO) of 0.5–0.7. In addition, a considerable amount of 1,3‐oxathioran‐4‐methyl‐2‐thion was isolated as a by‐product.
Copper-iron-polyphthalocyanine shows catalytic activity on the oxidation of acetaldehyde ethylene acetal with oxygen at 30°C; this catalytic activity is remarkably dependent on the atomic ratio of copper to iron ions involved and on the activation energy of the electrical conductivity of copper-iron-polyphthalocyanine. The catalytic oxidation of acetaldehyde ethylene acetal with oxygen in the presence of copper-iron-polyphthalocyanine gives, selectively, ethylene glycol monoacetate as the main reaction product, together with small amounts of ethylene glycol diacetate, ethylene glycol, acetaldehyde, and acetic acid. This catalyst is also effective in the selective oxidation of cumene and benzaldehyde ethylene acetal.
Polymerization of epichlorohydrin (ECH) and copolymerization of propylene oxide–allyl glycidyl ether were studied by using a catalyst consisting of aluminum alkyl–strong phosphoric acid–Lewis base. This system showed high polymerization activity for alkylene oxides, and it was elucidated by x‐ray diffraction analysis that the resultant ECH polymer was completely amorphous. The polymerization was presumed to be of the coordinated anionic type. The physical properties of the vulcanized polymers were studied.
The role of the iron in copper-iron-polyphthalocyanine in the catalytic action in the oxidation of acetaldehyde ethylene acetal and cyclohexene was investigated on the basis of the inhibition of the reaction by the treatment of copper-iron-polyphthalocyanine with iron-binding agents and oxidizing agents. The catalytic action of copper-iron-polyphthalocyanine decreased or disappeared upon the addition of 2-phenylimidazole and pyridine to the reaction system, and upon the treatment with bromine or concentrated hydrochloric acid in the presence of air. However, the reduction of the oxidized copper-iron-polyphthalocyanine with ascorbic acid or sodium thiosulfate recovered the catalytic activity. Furthermore, the catalytic activities of iron-metalpolyphthalocyanines (metal; V, Cr, Mn, Co, Ni, Cu and Zn) and copper-metal-polyphthalocyanines (metal; V, Cr, Co, Ni and Zn) in the oxidation of acetaldehyde ethylene acetal were investigated. The former groups showed the catalytic actions, but no catalytic actions were observed in the latter groups. The catalytic activities of iron-metal-polyphthalocyanines increased with a decrease in the activation energy of the electrical conductivity of the polymer. From these results, it was presumed that the Fe(II) ions located in the conjugated system act as active sites for the activation of oxygen and for the decomposition of peroxide.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.