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This review article describes preparations and properties of various types of water-soluble cutting fluids additives derived from various materials. It is concerned with synthetic additives classified according to their functional groups: carboxylic acids, esters, dibasic acids, ethers, amides, substituted fatty acids and others for iron materials. Testing methods for water-soluble cutting fluids are described on ways for laboratory and practical tests for factory.

Fatty acid distillates (FADs) produced during physical refining of vegetable oil contains large amount of free fatty acid. A mutant of Candida tropicalis (M20) obtained after several stages of UV mutation are utilized to produce dicarboxylic acids (DCAs) from the fatty acid distillates of rice bran, soybean, coconut, palm kernel and palm oil. Initially, fermentation study was carried out in shake flasks for 144 h. Products were isolated and identified by GLC analysis. Finally, fermentation was carried out in a 2 L jar fermenter, which yielded 62 g/L and 48 g/L of total dibasic acids from rice bran oil fatty acid distillate and coconut oil fatty acid distillate respectively. FADs can be effectively utilized to produce DCAs of various chain lengths by biooxidation process.

Examination was made of the preparation and properties of new types of water-based cutting fluids additives derived from various materials. Attention was directed to synthetic additives classified according to their functional groups : carboxylic acids, esters, dibasic acids, ethers, amides, substituted fatty acids and others. Methods for examining water-soluble cutting fluids additives for laboratory and practical use are described in detail.

Lauryl-imino-diacetate (LIDA) is an amphoteric surfactant useful as a base for human body detergents. Owing to its stable dibasic acid moiety, application is possible over a wide pH range.In this study, assessment was made of the cytotoxicity of LIDA and other surfactants by NR, WST-1, leakage in LDH and hemolysis. All those methods are alternatives to animal experiments such as the Draize test. Membrane fluidity change of human epidermal keratinocytes by surfactants was detected by polarized light measurement of probe molecules in the cell membrane.LIDA and lauryl-imino-dipropionate (LIDP) showed low cytotoxicity in all cases. Membrane fluidity scarcely changed for LIDA and LIDP, whereas for lauryl-amino-acetate (LAA) and lauryl-amino-propionate (LAP), change was quite clear. The change in fluidity by LAA and LAP may have been related to the induction of cytotoxicity.

Residual sterylglycosides (SG) and octacosanedioic acid (DA 28) in commercial sesame oil were investigated for 17 brands of 12 manufacturers. A sensitive and precise method was developed to determine DA 28 content in oil. DA 28 was derived from 9-anthryldiazomethane in the presence of triacylglycerol and determined by HPLC equipped with a fluorescence detecter. This method was rapid and applicable to routine analysis.SG and DA 28 content differed considerably according to brand, from 1 to 300 ppm and 0 to 1500 ppm, respectively. The steps in oil processing would thus appear to markedly affect SG and DA 28 residue content

Preparation of dimethyl dodecanedioate in two steps was studied. The first step is the formation of methoxycyclohexyl peroxide by reaction of cyclohexanone with hydrogen peroxide and methanol in the presence of acid catalyst.The second is the dimerization of the resulting methoxycyclohexyl peroxide through the action of iron (II) sulfate to obtain the dimethyl dodecanedioate. In the first step, sulfonic acid in 0.01010.015 mol per mol of cyclohexanone is used as the catalyst. In the second step, the resulting methoxycyclohexyl peroxide can be used for the dimerization without purification. Various iron (II) salts, such as iron (II) sulfate, iron (II) ammoniumsulfate and ferrous chloride, are effective as the reducing reagents. The reaction can be conducted at a temperature below 10°C. Water should be used in excess in the redox reaction, if it is desired to obtain branched dibasic acid dimethyl esters. Cyclopentanone, cycloheptanone and 2-methylcyclohexanone gave the corresponding dibasic acid dimethyl esters, respectively.

Metal (II) ion-exchanged 5A, Y, and X type zeolites were screened to find effective catalysts for oxidative cleavage of palm stearin into mono- and dibasic acids with middle carbon chains.The formation of carboxylic acids was followed by 1H NMR spectrometry. When one reaction was recognized to form volatile material more than the others, it was carried out on a larger scale to collect the volatile material. This material was submitted to GC-MS spectral analysis for identification of individual components.The formation of carboxylic acid was confirmed in the case of products obtained by catalysts such as Mn (II) -5A and Co (II) -Y, but the amount of each was quite small. Analytical results on the volatile materials showed Mn (II) -5A and Co (II) -Cu (II) -Y to contribute to the formation of carbo-xylic acids and aldehydes, respectively.

Reaction of vinylmagnesium chloride with aliphatic carboxylic acid methyl ester gives a mixture of vinylketone and divinylcarbinol. From methyl pentanoate, a mixture of n-butyl-3-hydroxyl-1, 4-pentadiene and 5-oxo-1-nonene is obtained. While reaction of linear α, β-unsaturated methyl esters with vinylmagnesium chloride yields vinylketones as the main product, the reaction of substituted α, β-unsaturated methyl esters yields triethylenic carbinols. Reaction of acid anhydrides and dibasic acid diesters with vinylmagnesium chloride yields mixtures of alkenones, hydroxy-alkenones and alkenols as the main products. Reaction of acid chloride with excess vinylmagnesium chloride at -40°C to -45°C gives 2-allyl-1, 3-diketones. From propanoyl chloride, a mixture of 4-allylheptane-3, 5-dione (33% yield), 6-heptene-3-one (0.5% yield) and 3-ethyl-1, 4-pentadiene-3-ol (2% yield) is obtained. Reaction of vinylmagnesium chloride with a fatty acid methyl ester in the presence of cuprous chloride gives a 1, 6-diketone. From methyl n-valerate, a mixture of n-tetradecane-5, l0-dione and 5-oxo-1-nonene is obtained.

The authors synthesized two series of dibasic acids containing ether linkages, oxadiacetic acids and oxadipropionic acids, which were respectively obtained from polyethylene glycols by the air oxidation and from water or formaldehyde or ethylene glycol by the cyanoethylation and subsequent hydrolysis. Disodium salts of dibasic acids were prepared and compared to the sodium tripolyphosphate (STPP) and sodium citrate with their detergency building action. The detergency tests were carried out on naturally soiled cotton fabrics and the comparison was made by Scheffe's method. The builders employed were sodium tripolyphosphate (STPP) or disodiumsalts of dibasic acids, or sodium citrate, or the mixture of STPP and disodiumsalts of dibasic acids, or the mixture of STPP and sodium citrate. As a result, the oxadiacetic acid series achieved better building performance than oxadipropionic acid series, and in each series, the smaller molecular weight of the test builder showed the better building power. The reason of these results can be explained that oxadiacetic acid formed a five membered ring with calcium, while oxadipropionic acid probably formed a six membered ring and stability difference between the two chelate ring systems caused the difference of their building actions. Another reason is the difference of the molecular weight. This is interpreted as the “Chelating value” or C.V.. To chelate a given amount of metal it requires less quantity of the minor molecular weight builder than that of the higher.

α, ω-Type amphoteric surfactants containing bisbetaine groups were synthesized by reactions of alkanedioic acids with N, N-dimethyl-1, 3-propanediamine, followed by quaternization of the resulting bisaminoamides with sodium chloroacetate. The latter process was carried out in water or a mixture of isopropyl alcohol and water using sodium hydrogencarbonate or sodium hydroxide as the catalyst.The properties of the α, ω-bisamidobetaine in aqueous solution were studied. α, ω-Bisamidobetaines derived from hexadecanedioic and icosanedioic acid showed good catalytic activity for the halide displacement reaction and a excellent ability to bring about lime soap dispersion.

A series of bis (aminimides) (BAI) with a general formula, [RCH (OH) CH2NMe2NCO] 2Y, (R : n-C4n-C10, Y : - (CH2) n-and p-phenylene, n : 08) were prepared by the reactions of diesters of aliphatic and aromatic dibasic acids with aminimines derived from 1, 2-epoxyalkanes and 1, 1-dimethylhydrazine. The yields were 3040% for the aliphatic series and 7080% for the aromatic series. For the aromatic series, it was found that BAI and half aminimide esters were selectively obtained in high yields by the control of molar ratio of aminimide/carboxylic diester. Some surfactant properties of these products were examined and compared with those of corresponding monoaminimides (MAI), RCH (OH) CH2NMe2 NCOR'. BAI without methylene bridge between two aminimide groups have a high Krafft point and are insoluble in water at room temperature, while no Krafft point is observed for BAI with n=28. BAI except for the lower members show a characteristic cloud point in analogy with poly (oxyethylene) type nonionic surfactants. The cloud point decreases linearly with increasing n, but no appreciable effect of n on cmc, aqueous surface tension (γcmc) and molecular area (A0) of adsorption film at air/ water interface are observed. The cmc and γcmc of BAI are slightly higher than those of MAI (4, 5). A0 of BAI is about twice as large as that of MAI. BAI are generally inferior to MAI (4, 5) in wetting and foaming abilities.

N-Substituted glycine-, alanine- and betaine-type amphoteric surfactants containing long chain alkylthio group were synthesized, and their growth inhibitory activities against Gram positive, Gram negative baccili and some fungi were studied. The effect of the alkylthio group on their antimicrobial and surface activities was compared to that of the alkoxy group of the corresponding N-substituted amino acid amphoterics containing alkoxy group. The obtained N-substituted amino acid amphoterics containing alkylthio group generally, have large antimicrobial powers and excellent surface activities except alanine type derivatives. Dibasic amino acid-type amphoterics having an alkylthio group in the molecule were also tested. Their antimicrobial activities were less than those of the corresponding monobasic amino acid-type amphoterics. Furthermore, N-substituted glycine- and alanine- type amphoteric surfactants, which contained the ether and thioether linkages in the long chain were synthesized and their antimicrobial and surface activities were studied. It is found that the antimicrobial powers of N-substituted amino acid type amphoterics containing alkoxy group is enhanced by introducing an additional thioether group in the molecule.The relative position of ether and thioether group apparently affected their antimicrobial activities.

The inhibitive properties of sodium or amine salts of monobasic and dibasic acids for mild steel specimens have been examined in humidity cabinet at 40°C or 50°C and relative humidity 95100%The monobasic and dibasic acids used were monocarboxylic, dicarboxylic, alkylphosphoric, dialkylthiophosphoric, n-octylphosphonic and n-octylmalonic acids, etc. About the almost same length of carbon chain, the sodium salts of dibasic acids with polar group at both ends have most inhibitive efficiency and those of no branched monobasic acids have more efficiency than those of dibasic acids with two polar groups near one end or those of branched monocarboxylic acids. It seems that the inhibitors with the chain length of about 8 carbon atoms are most effective among the homologous series. The influence of pH in sample solution on corrosion greatly increased with increase of pH, especially more than pH 10.Results of indoor exposure test for mild steel indicate that sodium salts of n-octylphosphonic and n-octylphosphonic acid have good inhibitive property, and do not correlate always with results of humidity cabinet test.

From the discovery of higher dibasic acids in Japan wax, many investigations were carried out about the structure of the glycerides of dibasic acids. However, these investigations were mainly concerned with the separation of dibasic acid glycerides from Japan wax, and no definite conclusion has yet been established whether it would be monomolecular type or bimolecular type.The purpose of this investigation is determining the structure of higher dibasic acid glycerides synthetically prepared. Synthesis of dibasic acids (C12C22) was carried out according to four different methods and pure C22 dibasic acid was obtained.The paper chromatography of the dibasic acids has been carried out by the reversed phase method using several kinds of stationaly phases, and a linear relationship was observed between Rf value and the carbon number of the acids.By applying this analytical method to the dibasic acid which was separated from Japan wax according to the Tsujimoto's method, it was found that arachidinic acid was also present besides C20 and C22 acids which were previously known, and the ratio of those three acids was determined by molecular distillation.

Condensable volatile decomposition products and free fatty acid in the deteriorated oils were examined to know what kind of reaction may play the main part of deterioration during deep fat frying in the absence or the presence of air.Steam distillated materials from soybean oil under the continuous water-spraying and heating system with and without air blowing, were collected as shown in Fig.-1. Collections were continued during 014, 1428 and 2842 hr respectively. The quantities of acidic, carbonyl and alcoholic fractions of the volatile products at various intervals were determined, and the methyl ester of acidic fractions was gas chromatographed using succinate polyester column and each peak was identified by the tentative method (Fig-3, 6, Table-4, 5). The free fatty acid was isolated from the final deteriorated oils by means of ion-exchange resin and fractionated into monomer, dimer and secondary products by silica gel chromatography mentioned by Frankel et al., and the methyl ester of monomer acid was gas chromatographed (Table-2, 3, Fig.-2). Acid value, viscosity increasing ratio, carbonyl value and iodine value of the deteriorated oils were deteamined every 14 hr heating (Table-1).In the absence of air, free fatty acid in the final deteriorated oil was recovered with the yeald of 99.0% with ion-exchange resin and 93.5% of this acid fraction was monomeric. The composition of monomer acid was practically similar to the constituent acid of original soybean oil. Also, in the volatile products, acidic compound was main product and its composition was almostly similar to that of soybean oil. These results indicate that the free aftty acid increased in the deteriorated oil in the absence of air, was produced by the hydrolysis of triglyceride.In the presence of air, free fatty acid was removed 90.5% by ion-exchange resin and 82.3% of this acid fraction was monomeric. Acidic materials which cannot be removed by ion-exchange resin, was considered as that combined with glyceride. The composition of monomer acid was similar to that of soybean oil. These results indicate that, even in the case of presence of air, the free fatty acid increased in the deteriorated oil was produced mainly by hydrolysis. On the other hand, volatile products were the mixture of acidic, carbonyl and alcoholic compounds, and acidic compounds contained short chain fatty acids, dibasic and keto acids.

Present research was carried out with the intention of finding the kinds of compounds formed by the action of 30% H2O2 on di-basic fatty acid esters.The sample used was di-methyl ester of succinic-, adipic- and sebasic acid, and reacted without catalyst. By reacting 0.1mol of ester with 2.2mols of 30% H2O2 under the condition of 105° C and 30 hours, it was recognized that the various lower mono- and di-basic fatty acids and lower carbonyl compounds were produced.Fixed quantity of carbon dioxide that produced by these reactions, and from these values, it was recognized that the lower esters were readily reactive than the higher homologue, and di-basic fatty acid esters were more readily oxidized than the mono-basic fatty acid esters.

It has already been reported that Japan wax contains higher dibasic acids such as docosanedioic and eicosanedioic acids, but no detailed reports including the lower dibasic acids have been found yet.The purpose of this investigation is to determine accurately the fatty acid and dibasic acid compositions of the wax by gas-liquid chromatography using a hydrogen flame ionization detector.Gas chromatographic analyses were performed on a gas chromatograph of Shimadzu GC-1 B type equipped with a flame ionization detector. U-shaped stainless steel columns of 150cm×4mm i.d., and another 75cm×4mm i.d. for the specified analysis of higher dibasic acid dimethyl esters, were packed with 10% polyethyleneglycol adipate on Diabase B (Kotaki-seisakusho Co., Ltd.), 80-100 mesh. The flow rates of helium as the carrier gas, hydrogen and air for the detector were approx. 60ml/min, 40ml/min and 1.0l/min, respectively. The inlet heater was kept at 280°C, the column temperature was at 215°C for the analysis of fatty acid methyl esters and lower dibasic acid dimethyl esters, and at 220°C for the long-chain dibasic acid dimethyl esters.As a result, different dibasic acids (C5, C6, C7, C8, C9, C10, C11, C12, C14, C16, C18, C20 and C22), various fatty acids (less than C10, C14, C15, C16, C17 C18, C20 and C22) and considerable amounts of unknown materials were found in the free acids responsible for the high acid value (21.5) of the wax.In addition, the methyl esters, obtained by direct methanolysis of the wax and subsequent removal of the free acids, contained small amounts of C14-, C16-, and C18- as well as C20- and C22- dibasic acids.The thin-layer chromatography on silica gel was also applied to the analysis of the wax; namely, it was observed that the dibasic acids were separable from the fatty acids and other materials and that each constituent can be examined in detail.

Di- (1, 2 : 5, 6-diisopropylidene-D-glucose) dicarboxylate was prepared from 1, 2 : 5, 6-diisopropylidene-D-glucose and dimethyl ester of dibasic acid (i.e. adipic, pimelic azelaic and sebacic), by transesterification in dimethylformamide. The same ester was also obtained by acylation of 1, 2 : 5, 6-diisopropylidene-D-glucose with the chloride of the above dibasic acid.The ester thus obtained was converted into di- (D-glucose) dicarboxylate by sulfuric acid. After evaluation studies, a fairly promising emusifying property was found for the latter ester.

Various alkyl benzoic acids and half esters of dibasic acids were prepared. Corrosion test for cutting fluids characterization of these compounds were examined. Triethanol amine salts of mono oleil phthalate and acids alkyl (methyl, butyl, pentyl, hexyl and octyl) benzoic acids have excellent properties.

Dinitrile is prepared from dibasic fatty acid and ammonia by using dehydrating catalyst at elevated temperature. Authors investigated the amidation reaction of azelaic acid by blowing ammonia gas at comparatively low temperature ranging 150 to 200°C.As a result, order of this reaction was found to be secondary, approximately, to the concentration of the azelaic acid, where the effect of ammonia gas is minimized, and the activation energy was 9.7 5 kcal per mol and frequency factor was 40.26. The reaction velocity was expressed as : kc=40.26e-3.966×103/T at 150 to 200°C

Several dibasic acid esters containing oxyalkylene units (-OCH2-, -OC2H4-, unit number; 15) were treated with aminimines derived from alkyl (C8C12) glycidyl ethers and 1, 1-dimethylhydrazine, giving a new series of bis (aminimides) with the yields of 3040%. The introduction of ether linkage caused a decrease in melting point and Krafft's point of the bis (aminimides). The lower members regarding m (m