JPH04500686A - Method for directly producing fatty acid amides from raw fats and oils - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Method for directly producing fatty acid amides from raw fats and oils The present invention produces natural oils by directly converting raw fats and oils with amide forming agents. The present invention relates to a method for producing acid amides of fatty acids.

Oils and fats of plant and animal origin have traditionally been used for human nutritional and chemical purposes. Basic materials: textile finishing agents, paints, cosmetics, candles, soaps, surfactants, Lubricants, fluxes, softeners, cement and asphalt additives, plastics and It has been used in the production of free fatty acids and other products.

Considering the decline in stored raw materials, such as petroleum, for example, natural fats and oils will become more important in the future. It is thought that it will become of industrial importance.

However, there are problems when producing chemical basic substances industrially from fats and oils. This is not to say that there are no problems.

Raw material fats and oils obtained from oils often contain many interfering substances, such as phosphorus Contains salts, gums, pigments and odorous substances or hydrocarbons. like this These accompanying substances interfere with direct processing of raw fats and oils. and (contains a lot of unsaturated fatty acids) Otherwise, the starting material will decompose or turn into a resin, which will severely limit the yield. will be done.

For these reasons, raw fats and oils are processed into basic substances that can be used chemically. Before removing viscous substances, deacidifying, decolorizing and deodorizing to remove such inclusions. Oleochemistry processes fats and oils chemically, at a cost of For example, in oil and fat industries such as oil extraction, products are usually refined in advance. The starting material is triglyceride. In this case, the oil refinery equipment handles a large amount of oil types. Therefore, it is impossible to process oil types that use only a small amount of solder. Therefore , such as “high oleic” sunflower or Euphoria latheilis. The oil of the newly cultivated oil species has a high content of special fatty acids and is the starting material of oleic acid. Although suitable in terms of quality, they are not economical and are excluded from industrial-scale refining processes. . Other disadvantages of some oil fruits, besides the accompanying substances already mentioned, are often nutritional contains dangerous and toxic substances, so even if edible oil can be obtained, refining it is extremely expensive. Therefore, it is not suitable for processing within the device.

Therefore, the problem of the present invention is to solve the problem of raw materials with low utilization of oil types or difficulties with associated substances. oils and fats can be used directly as starting materials without expensive purification steps That's true.

Surprisingly, amides of fatty acids are now produced directly by amide-forming substances in raw compressed oils. A method has been found that allows high purity to be obtained by conversion.

Even oleic oil with a large number of double bonds can be changed without any problem according to the method of the present invention. Can be exchanged. The invention is therefore directed to the method of claim 1.

The process of the invention can essentially start from any fats and oils.

Fats and oils in this case are mixtures of substantially higher fatty acids of vegetable and animal origin. is an encerine ester. It consists primarily of triglycerides, but monoglycerides Contains unspecified amounts of natural fatty acid esters such as lido, diglyceride, and more. It is.

The method of the invention is carried out in one conventional cold press, for example with a helical or spindle press. , for converting raw fats and oils obtained by hot press or squeeze extraction. I'm leaving behind. For example, using functional or special fatty acids such as pencitric acid. High-yield, high-purity products can be easily obtained from fats and oils that are abundant in This is a particularly excellent method.

The proportion of normal functional fatty acids is small with respect to the total number of fatty acid molecules at any given time. Advantageously, the amount of special fatty acids is at least 50%, and the special fatty acids are at least 10%.

Particularly preferred oils are Euphorbia lateralis, linoleic or oleic. sunflower oil with a high content of hydrogenated, non-hydrogenated castor oil, oleic oil, rapeseed oil, especially rapeseed oil high in erucic acid, buzz seed oil, olive oil or Marine animal oils such as fish oil and whale oil are used.

In some cases, solid inclusions present in the starting material, such as wood or plant residues, may Preferably, the slag is separated and removed before conversion.

Fats and oils are directly converted by amide-forming substances. As an amide forming substance is, for example, ammonia, formamide or primary or secondary aliphatic or alicyclic compounds. , aliphatic and aromatic amines, especially mono- or Examples include diamines.

This also includes difatty acids from natural fats and oils. In the case of diamine , between both amino groups of the hydrocarbon chain, or additional elements of alicyclic or aromatic residues or, for example, an ether group, an amino group, a diamide group, a keto group or a sulfone group. Functional groups such as may be present.

Preferred amino compounds are methylamine, ethylamine, diethyluane, morpho- Phosphorus, pentylamine, naphthylamine, phenylethylamine, aniline, trichloride Luidine, 1.2 diaminoethane, 1,3 diaminopropane, 1.6 diamino group Xane, 1.8 Diaminooctane, Piperazine, 4.7.10 Trioxatride Kan, -1,13,-diamine, 3,3°diaminodiphenylsulfone, 3.3 °-Dimethyl-4,4'-diaminodicyclohexylmethane, ethanolamine , 3-aminopropanol and commercially available ethyldiamine of the formula below.

CH3 HJ-CI(CHt(QC)(mcH)-NHsCH8 Here, n is an integer from 1 to 200.

Particularly preferred compounds are 1,2-diamidoethane and 1,6-diamithexa It is. Amines are used in stoichiometric amounts with respect to the amino groups of fatty acids and the number of fatty acids. However, even if there is a slight excess or shortage of amino groups, the reaction yield will not be substantially affected. do not have.

In some cases, the transformation is also carried out in a suitable solvent to ensure a homogeneous reaction. Ru. Generally non-polar solvents, especially toluene, xylene or betrol ether is used. Conversion is between 20”C and 300°C, preferably 50”C and 200°C Temperature ranges between are preferred. In this temperature range, it is necessary to carry out the present invention. This is because a reaction time of 1 to 6 hours is still not too long.

The reaction is carefully carried out in a closed system, for example in an autoclave. Not in the air Even if it is best to carry out in a vapor of argon, nitrogen or an inert solvent, this As a result, undesirable side reactions such as oxidation of starting materials are suppressed.

For example, ammonium chloride or p-toluenesulfonate may be added to the reaction mixture if necessary. Catalysts such as phosphoric acid can also be added. At an appropriate temperature, esterase It is also possible to add biological catalysts such as Similarly, for example ascorbine Usual supplements and additives such as polymerization inhibitors and antioxidants such as acids or glucose Additives may also be used.

After the reaction is complete, the reaction product is precipitated after removing the solvent that may exist. and then recrystallized in a suitable solvent. This includes Polar solvents and strongly polar solvents such as sulfoxides are suitable. Methanol or in ethanol, in some cases e.g. cold methane. For reaction mixtures that may be easily washed with alcohol or toluene, e.g. Other purification means such as hot steam extraction may also be employed. In that case, the acid amide is the same It is obtained in crystalline form.

After separating fatty acids as acid amides, the alkaline mother liquor is concentrated with oil-associated substances. A form of glycerin remains. Some of this oil-associated substances are e.g. min and glycerin, all of which are of industrial interest. This kind of dark Since it is very easy to separate the condensates, their production is also easy using this method. Ru.

The acid amide obtained in this way does not contain harmful accompanying substances, and the selection of raw material oil is easy. If appropriate, a product of very high purity can be obtained, and the processing requires no ultra-high purity for any time. There are no fatty acid amides - sometimes also as mixtures - or additives. For example, it is also used as a flux additive, but the next stage of products is of even more interest. is converted into.

An interesting product that was previously unavailable or very expensive to produce is now available. For example, it can be obtained from difatty acid amides formed when fats and oils are replaced with diamines. . Fatty acids with functional groups such as carbon-carbon-double bonds or OH groups are predominant. Obtained from diamides of fats or oils. In this way, according to the present invention, A highly concentrated diole using diamine from the raw material oil of Euphorbia lateralis seeds. Obtain high concentration of silitin silitin diamide from inic acid amide and raw material castor oil be able to.

Patent application filed at the same time [396-16/(3)/9/89/RI-UM As also described in the specification of AJ, suitable difunctional compounds such as di- Socyanates replace fatty acid amides, forming prepolymers, plastics and and plastic additives, such as adhesives, backings, plastic blowing agents, Lubricants and many other industrial auxiliaries can be produced. From fatty acid amides, Free fatty acids (such as pencitric acid) can also be extracted using conventional saponification methods. It is a feature of the present invention that special fatty acids can be obtained. fat obtained in this way If the acid has a functional group, it can be recycled as a base material or additive for plastics. You can also use it.

The present invention provides a method for processing fats and oils that could not be used as raw materials in the past. At the same time, interest in the chemical industry, which until now could only be obtained at high cost, It has the advantage of being able to produce basic materials for processing.

The present invention will be explained in detail by the following examples.

Example 1: 1. Conversion of euphorbia oil with 2-diaminoethane 100 g of euphorbia oil was mixed with 9.4 g of 1,2-diaminoethane in an oven under nitrogen atmosphere. 1, which was reacted in a totoclave at 180°C for 3 hours and then at 100°C for an additional 3 hours. The reaction product was recrystallized twice from methanol. N, N obtained in this way '-Ethylene bisoleodiamide has purity (melting point 114-116℃, yield near 3 g).

Example 2: Conversion of castor oil with 1,2-diaminoethane 5.1 g of castor oil and 1,2-dia Stir 015g of minoethane at 120℃ for 5 hours in an autoclave under nitrogen atmosphere. did. The reaction product was then recrystallized from methanol. obtained in this way N,N-ethylene bisritinol diamide has a purity of >90% (melting point of 83-85 ℃, yield: 2.6 g).

Example 3: Conversion of castor oil with 1.6-diaminohexane 51 g of castor oil and 1.6-diaminohexane The reaction product obtained by stirring 9.7 g of tsuhexane at 100°C for 5 hours in a nitrogen atmosphere was It was recrystallized from 150 ml of methanol. Hexamethylene thus obtained bisritinoleic acid amide, purity >90% (melting point 86-88°C, yield: 32 g )Met.

Example 4: 1. Conversion of hydrogenated castor oil with 2-diaminoethane 153 g of hydrogenated castor oil and dia 15 g of minoethane was stirred at 140°C for 5 hours in an autoclave under nitrogen atmosphere. The 0 reaction product was recrystallized from 150 ml of methanol. obtained in this way Bis(12-hydroxystearic acid)-N,N'-ethylenediamide is Purity>90% (melting point 142-145°C, yield: 106.5 g).

Example 5: 1. Conversion of hydrogenated castor oil with 6-diamithexane 5.1 g of hydrogenated castor oil and 0197 g of 1,6-diamithexane were placed in an oven under a nitrogen atmosphere. The reaction product was stirred for 5 hours at 150°C in a reactor and dissolved in methanol. It was subjected to medium heat steam extraction. The bis(12-hydroxysteel) thus obtained (Alic acid)-1,6-N,N°hexamethylene diamide has a purity of >90% (melting point 135-136°C, yield: 3.7g).

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Special table Hei 4-500686 (5)

Claims (13)

[Claims] 1. raw fats and oils as starting materials, optionally in a suitable solvent. This is directly carried out by the amide-generating compound by adding a suitable catalyst and antioxidant. Fats and fats characterized by conversion into fatty acid amides and further purification if necessary. A method for producing amides of natural fatty acids from vegetable oil. 2. Claim 1 characterized in that the raw material fat and oil contain a large amount of functional fatty acids. the method of. 3. The method according to claim 1, characterized in that the raw fat and oil contain special fatty acids. . 4. The raw material fat and oil is euphorbia oil, linole oil or castor oil with high oil acid content. Sesame oil, especially high-olefin rapeseed oil, especially high-erucic acid rapeseed oil, Sour rapeseed oil, mustard seed oil, castor oil, or hydrogenated castor oil, oleic Characterized by the use of oil, olive oil or marine animal oil such as fish or whale oil A method according to any one of claims 1 to 3. 5. As an amide production reaction, primary and secondary fatty acids, cycloaliphatic, aliphatic-aromatic or aromatic Claims 1 to 4, characterized in that aromatic monomers or diamines are used. The method described in either section. 6. As an amide production reaction, 1,2 diaminoethane or 1,6 diaminohexa 6. A method according to claim 1, characterized in that a method is used. 7. Toluene, xylene or petrol ether is used as solvent 7. A method according to any one of claims 1 to 6, characterized in that: 8. The starting material is modified with the amide at 20-300°C, preferably 50-200°C. 8. A method according to any one of claims 1 to 7, characterized in that: 9. It is characterized by being carried out in an inert gas atmosphere consisting of nitrogen or argon. 9. A method according to any one of claims 1 to 8. 10. Ammonium chloride or p-toluenesulfonic acid is used as a catalyst A method according to any one of claims 1 to 9, characterized in that: 11. Characterized by the use of ascorbic acid or glucose as an antioxidant 11. The method according to any one of claims 1 to 10. 12. Purification of fatty acid amides by recrystallization from methanol or ethanol 12. A method according to any one of claims 1 to 11, characterized in that: 13. The fatty acid amide is purified by solvent hot steam extraction. A method according to any one of claims 1 to 11.