Conditions for preparation of methyl ricinoleate by methanolysis of castor oil and its acetylation with acetic anhydride to acetyl methyl ricinoleate, an efficient cold-resistant plasticizer, were investigated, and following conclusions were obtained.For methanolysis of 1 mol castor oil, it was necessary to use above 10 mols of methanol, the requirement of NaOH was at least 0.1% of the total weight and using of above 0.2% gave better results.Although the strong alkali, such as Ba (OH) 2, could be replaced for NaOH it could not be substituted by ammonia.The reaction was unfavorable at 15°C but it was satisfactory by heating at above 24°C.The reaction was completed in 30 minutes or more.The acetylation of methyl ricinoleate was completed by boiling for a short time with acetic anhydride in a slight excess and there was only a slight increase in yield by use of acetic anhydride in large excess.It was not necessary to use sulfuric acid as a catalyst in this reaction.
Systematic syntheses of esters of pentaerythritol and trimethylolpropane with lower fatty acids have been made and the properties of them as a low temperature lubricating oil and the stability against irradiation of γ-ray from Co60 have been investigated. The results indicated that the products from pentaerythritol type compound had higher pour point than those of trimethylolpropane system, that with straight chain fatty acid had lower pour point than that of branched chain fatty acid, and the longer the size of molecule, the higher was the pour point of product.Pentaerythritol ester from using of caproic acid or trimethylolpropane ester from using caproic and caprylic acid showed suitable properties as the lubricating oil to be used at low temperature from the standpoint of viscosity, viscosity index and pour point.Also, these products seemed to have good property to be used as the plasticizer.The stability against the irradiation of γ-ray was notso good and it seems that using them for atomic furnace epuipments cannot be anticipated.
The effects of metal catalysts for oxidation of acetaldehyde in ethyl acetate with oxygen to simultaneous formation of acetic acid and acetic anhydride have been investigated. The oxidation activities of the catalysts for acetaldehyde were in order of Co > Mn > Ni > Cr > no catalyst, Fe, Ag, and Cu. The decomposition activities of the catalysts for peracetic acid were in order of Ni, Co > Cr, Mn > Cu, Ag, Fe. and no catalyst. A parallel relation was qualitatively found between the orders of these activities. The activities of catalysts for formation of acetic anhydride were in order of Co > Mn > Ni > Cr; Co > no catalyst. The catalyst of Co with Cu had a maximum oxidation activity when the addition of Cu was 0.075 (atomic ratio of Cu/Co); and, the activity for formation of acetic anhydride was increased proportionally up to the addition of 0.5. The tendency of this efficiency was attributed at least in part to the action of suppressiong of hydrolysis of acetic anhydride by the catalyst in the reacting solution.