JPH04501284A - Method of manufacturing plastic from raw material oils and fats - 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 producing plastics from raw material oil It relates to a method for producing additives for plastics and plastics.

Oils and fats are not only useful for human nutrition, but also for the production of many basic substances of industrial importance. used as a starting material. However, up until now, oils and fats have only been available under certain conditions. It has been used as a starting material for the production of polymers and plastics only to the extent that Ta.

Natural fats and oils containing hydroxy fatty acid triglycerides and their derivatives are particularly Suitable for manufacturing industrial products. For example, 2 per triglyceride molecule Certain fats and oils containing predominantly 1 or more alcohol groups can be treated with suitable reactive compounds, e.g. By reaction with diisocyanates, polymers are formed via these hydroxyl groups. Structures can be formed, advantageously thermosetting plastics being produced.

Suitable materials for these transformation reactions include, for example, castor oil or hydrogenated There are castor oils and they can be used directly as triglycerides. But this The scope of application of the method is extremely limited by the number of hydroxyl group-containing fats and oils available. It will be done. Further disadvantages are the production of undesirable by-products, especially undesirable color components. In order to remove them, the fats and oils must be purified before the reaction.

It is an object of the present invention to convert oils and fats, which have hitherto been of low industrial importance, into complexes that are expected to result in considerable losses. for the production of plastics and plastic comonomers without the need for complex purification steps. The purpose is to provide a method that can be used as a starting material.

The present invention relates to a plastic comonomer and an unsaturated fat as defined in claim 1. This is a method of manufacturing plastics from oils and fats consisting of acids.

Pure unsaturated fatty acids and their derivatives react with organic peracids to form epoxy compounds or It is known to produce hydroxy compounds.

Surprisingly, even unrefined triglycerides, such as those expressed in raw oils and fats, This method allows for problem-free oxidation and eliminates accompanying substances that are always present in the starting material. It has been found that oxidation can be carried out without problems even without prior removal. another unexpected effects that have undesirable adverse effects on product quality and therefore subsequent reactions The colorants and fragrances are completely destroyed by this reaction, leaving a completely colorless reaction product. That's what you get.

Basically, any type of raw material oil or fat that contains glycerides of unsaturated fatty acids can be used with this product. It is suitable for the method according to the present invention. However, with this type of fat, the amount of fatty acids It is advantageous if the proportion of saturated fatty acid residues is known and amounts to at least 50%.

Desirable oils are among them. Particularly desirable are spurge oil and fresh It is a "high oleic" sunflower oil.

Raw material fats and oils can be prepared using conventional methods such as screw extruders or spindle presses, or or by pressure extraction. Contains materials such as wood or plant residues that may contain After removing the solid components, it can be used directly.

According to the present invention, the raw oil or fat is prepared using a suitable solvent such as formic acid or acetic acid. Preferably, by reacting with performic acid or peracetic acid at a temperature between -5°C and +80°C. , converted to oxidized triglycerides.

The reaction mechanism is that the double bonds of fatty acid residues first react to form an epoxide, and then Produces diols at high temperatures.

At low temperatures between -5°C and +20°C and short reaction times, epoxides are predominantly generate. Diols, on the other hand, have several double bonds, the presence of polyols, and advantageously It forms at temperatures between -5°C and +80°C.

How much peracid is used depends on the degree of unsaturation of the starting triglyceride. and the degree of oxidation desired. Especially in the case of polyunsaturated triglycerides , is selectively influenced by the number of oxidized groups, so low amounts are desirable.

In this case, undesired concomitants are always removed before oxidizing the triglycerides. Even if the double bond is only partially oxidized, undesirable adhesion can occur. No color component remains in the reaction mixture.

Instead of adding peracid directly, triglycerides can be dissolved in acetic or formic acid. The fats and oils can be oxidized by adding hydrogen peroxide dropwise, advantageously in the form of a commercially available 30% solution. Both are possible. In this case, the reaction between hydrogen peroxide and the solvent forms a peracid; This reacts with the fats and oils to be further oxidized.

Once the reaction is complete, excess peracid or hydrogen peroxide can be removed by conventional methods, e.g. is removed by a reducing agent. Most of the water and solvent in the reaction mixture are then removed under reduced pressure. removed.

All accompanying colorants are destroyed in the oxidation process of the raw oil and fat, so the resulting The oxidation products can be isolated in high yields as clear aqueous solutions or colorless viscous solutions.

Oxidized triglycerides can be purified without additional purification steps by removing excess peracid, water, and solvent. As a crosslinking agent or comonomer, ready for use after simple removal of the medium, For example, those used in classic polyester and polyurethane systems Because it changes the properties of the stick, it is very expensive in its pure form and used in the form of pressurized oil. It is a low-cost alternative to castor oil.

For example, in the case of polyurethane resins from diols or diisocyanates, A portion of the oxidized triglycerate is added to the oxidized triglycerate prior to reaction with the diisocyanate. replaced by the id. This produces polymers, but in the process, diols and and oxidized triglyceride are both attached via a urethane group.

Additionally, oxidized fats and oils have the ability to directly react with hydroxyl or epoxy groups. transparent polymers and plastics by reacting with di- or polyfunctional compounds. obtain.

of unsaturated fatty acids, such as tallow, which has about 50% oleic acid in its fatty acid composition. When using approximately 50% fat and oil, triglycerides that do not contain even a single unsaturated fatty acid residue Although the proportion of lyceride molecules is relatively low, this is the case for most fully oxidized triglycerides. This is because the ceride molecule contains at least 2111 OH groups. In this way acid The converted fats and oils are fully reacted and actually contain the entire amount of triglycerides.

The oxidation according to the present invention basically does not cause the splitting of unsaturated fatty acids, so the total fat content reacts with polymer formation. This is an important advance in technology.

Difunctional or polyfunctional for reacting with hydroxyl-containing triglycerides Compounds include, for example, di- or polyisocyanates known for plastics production. There is a

Hexamethylene diisocyanate, methylene diphenyl diisocyanate (MD I) is preferably used, for example under the trade name Desmodur E14 or T2O Desmodur class diisocyanates or polyisocyanates available under the name When using cyanate, use other suitable secondary agents, none of which will cause any problems. Functional compounds include dicarboxylic acids or their active derivatives, such as acid chlorides, acid chlorides, etc. There are stellate and anhydrous. A desirable representative of such difunctional compounds is the lid adipic dichloride, maleic dichloride, phos It's Gen. When such compounds are used, triglycerides are bonded to urethane. , are bonded to each other via ester bonds.

Epoxy group-containing triglycerides include, for example, diols, diamines, aminoalcohols, Combined via call. Suitable diamine or aminoalcohol for this reaction - and secondary aliphatic, cyclic, preferably having 2 to 44 carbon atoms. aliphatic, aliphatic-aromatic and aromatic diamines, or amino alcohols. Ru. Also included are amines from dimeric fatty acids, among others.

Additional components or other functional groups, such as ether groups, diamide groups, amino groups, etc. , a keto group, or a sulfone group connects two amino acids of the diamine in the hydrocarbon chain. may be coordinated between functional groups or attached to cycloaliphatic or aromatic residues. may have been done.

Preferred diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1 ．． 6-diamithexane, 1,8-diaminooctane, piperazine, diethylene triamine, 4,7.10-trioxatridecane-1,13-diamine, 3, 3°-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diami Nodicyclohexylmethane and a commercially available ether diamine with the formula: el+2-diaminoethane, where n is an integer from 1 to 2000, and 1.6-diamithexane is particularly preferred; preferred amino alcohols include 2-alcohols. minoethanol and 3-aminopropanol.

Suitable diols for this reaction include -class and -class diols, preferably having 2 to 44 carbon atoms. and secondary aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic diols. advantageous contains glycol, 1.4-butanediol, 2-butyne-1,4diol, 2-butanediol, Thene-1,4-diol, 1,5-bentanediol, 1,6-hexanediol 1.10 decanediol, neopentyl glycol, N,N-diethylamide Nopropanediol-2,3, or neopentyl glycylate hydroxybivaric acid It is a coal ester. Particularly desirable are 1.4 butanediol and 1. 10-decanediol.

The reaction is advantageously carried out in a temperature range between 20°C and 200°C. Usually made of plastic Catalysts and stabilizers, such as those used in is carried out either in the melt. It is convenient to carry out under an inert gas.

The plastics obtained by the method according to the invention are transparent and thermosetting. their gender The quality depends essentially on the type of starting fat, the degree of oxidation and crosslinking, and the difunctionality used. types of functional or polyfunctional compounds, their oxidized triglycerides Depends on the molar mixing ratio.

Quite generally, the rules of classical polymer chemistry should be considered here.

The desired amount of difunctional or polyfunctional compound is determined by the proportion of reactive groups in this compound. 0.5 to 1. The one between 5 is selected.

Horseradish oil or sunflower with a high oleic acid content of 85% Using highly oxidized triglycerides, such as those obtained from oils, The properties of the stick can be easily changed. Because in this case, bifunctional or polyfunctional Possible polymer-forming mixing ratios of oxidized triglycerides to functional compounds This is because the range of abilities is particularly wide.

Therefore, the degree of oxidation should be higher and the proportion of di- or polyfunctional content should be higher. The more minutes there are, the stronger the bond will be. Furthermore, the hydrophilicity and adsorption capacity are It increases as the number of xyl groups increases. This is plastic material, glass, This means that it is better suited for adhering to surfaces and other materials such as metals.

The method according to the invention eliminates the use of such fats and oils for traditionally undesirable accompaniments. To make it easier to use oils and fats that cannot be used in plastic processes. In this way, the present invention Industrially useful products and intermediates can be processed easily and at low cost. Make it.

international search report -1, -Kenichi=-11-mPcT/EP 90101259 International Investigation Report

Claims (8)

[Claims] 1. The raw unsaturated fat is treated with performic acid or peracetic acid, preferably with formic acid or as a solvent. is oxidized to an epoxy or hydroxy compound in acetic acid, then plastic difunctional, which can react with epoxy or hydroxy groups in known ways for the production of Or unsaturated fatty acids characterized by converting them into polymers with polyfunctional compounds. A method for producing plastic comonomers and plastics from the oils and fats they contain. 2. Contains at least 50% unsaturated fatty acid residue fraction with respect to the total number of fatty acid residues. 2. The product according to claim 1, characterized in that a raw material oil or fat is used as a starting material. Construction method. 3. Horseradish or castor beans that are particularly high in oleic acid Claim 1 or Claim 1, characterized in that a raw material oil is used as starting material. The manufacturing method according to claim 2. 4. Formic acid or acetic acid and hydrogen peroxide and performic acid or peracetic acid are used as solvents. Claims 1 to 3 are characterized in that they are produced in a reaction mixture by the reaction of 3. The manufacturing method according to any one of 3. 5. claim, characterized in that the oxidation is carried out at a temperature between -5°C and +80°C. The manufacturing method according to any one of claims 1 to 4. 6. The difunctional compound to be converted into oxidized fats and oils is a diisocyanate or polymer. Any one of claims 1 to 5, characterized in that it is a liisocyanate. The manufacturing method described in Crab. 7. The difunctional compound to be converted into oxidized fats and oils is a dicarboxylic acid or its Claims 1 to 5 characterized in that it is a derivative, in particular a dichloride. The manufacturing method according to any one of. 8. Difunctional compounds to be converted into epoxy compounds include diols, diamines, or The alcohol according to claims 1 to 5, characterized in that The manufacturing method described in any of the above.