NO138949B - STARTING MATERIALS FOR THE PREPARATION OF THERAPEUTICALLY ACTIVE LINCOMYCINS AND PROCEDURES FOR THE PREPARATION - Google Patents

Description

Process for the production of surfactant sulfuric acid -

derivatives of higher molecular weight organic compounds.

The invention relates to a method for the production of surface-active sulfuric acid derivatives of higher molecular weight organic compounds by bringing sulfuric acid, oleum, sulfur trioxide or pyridine-sulfuric acid adducts into action on oxidation products of unsaturated organic materials at a reaction temperature of 10 to 40°C, preferably 15 to 35°C in an amount of 8 to 20 per cent, referred to the oxidation product, and optionally neutralizes the sulphation products formed, and the method is characterized in that unsaturated animal, vegetable or synthetic oils, fats or waxes are used as oxidation products of unsaturated organic materials, which is epoxidized and which has an epoxy-oxygen content of up to 3 per cent, preferably between 0.5 and 1 per cent.

By epoxidation products of high-remolecular unsaturated compounds, as it should be understood according to the invention, which as such are known and can be obtained by known methods, is meant e.g. epoxidates of higher molecular weight unsaturated hydrocarbons, alcohols, ethers, carboxylic acids, esters, amides and the like. The basis for these epoxidation products can, for example, include olefinic hydrocarbons, such as octane, dodecene, octadecene, squalene, esters of unsaturated higher molecular weight alcohols such as unsaturated fatty alcohols with 14-20 C atoms, especially of oleyl alcohol or other monounsaturated or polyunsaturated alcohols of arbitrary low or higher molecular weight mono- or polybasic carboxylic acids, as well as ethers of such alcohols. Furthermore, the epoxidation products may be based on esters and amides of unsaturated higher molecular fatty acids, such as above all naturally occurring glycerides, whose fatty acid part may be one or more times unsaturated, such as e.g. soybean oil, cottonseed oil, rapeseed oil, linseed oil, castor oil, sunflower oil, olive oil, clove oil as well as unsaturated waxes and cod liver oil such as sperm oil, herring oil, cod oil, hake oil or whale oil, or their transesterification products. Furthermore, epoxidates of esters of unsaturated fatty acids with mono- or polyhydric alcohols from the aliphatic, cycloaliphatic, aromatic or heterocyclic range, i.e. of esters of ethyl-, n-butyl-, tertiary amyl-, 2- ethylhexyl, octadecyl, cyclohexyl, methylcyclohexyl, naphthenyl and benzyl alcohol or of ethylene glycol, 1,2-propylene glycol, butanediol-1,4, dodecanediol-1,12, pentaerythritol, of polyalkylene glycols such as e.g. . of diethylene glycol. Also epoxidation products of esters of unsaturated carboxylic acids and alcohol mixtures as well as of mixed esters of polyhydric alcohols and various unsaturated carboxylic acids, such as e.g. the mixed ester of ethylene glycol with oleic acid and linseed oil fatty acid is applicable. Furthermore, epoxidates of esters are also usable, where both the acid and the alcohol part have a mono- or multiple-unsaturated hydrocarbon residue. Finally, esters or amides of unsaturated carboxylic acids or alcohols, which are obtained by condensation of higher-molecular unsaturated fatty acids or fatty alcohols of the above-mentioned type with lower-molecular, polybasic carboxylic acids such as e.g. maleic acid, citric acid, adipic acid, phthalic acid, etc. and/or polyhydric alcohols such as glycols, glycerin, pentaerythritol, sorbitol, etc. The epoxidation products of amides can be e.g. lie unsaturated fatty acid amides, which are derived from ammonia, dimethylamine, dodecylamine, oleylamine, ethylenediamine, cyclohexylamine, benzylamine, etc.

With regard to the starting materials used, it can be mentioned that the preferred chain length for the higher molecular weight unsaturated compounds lies at C12-C24. With chain lengths of C10—<C>14, you get predominantly products that have a moisturizing effect, with higher chain lengths of Cl2—C20, you get predominantly products that have a washing and cleaning effect. Particularly favorable products are obtained when the starting materials are only anepoxidized, as products with an epoxy oxygen content of 0.5-1.5 per cent are preferred. For stronger unsaturated compounds, such as cod liver oil and the like, an epoxy oxygen content of between 0.5 and 1 is preferred, 0% epoxy. The less highly unsaturated compounds, such as trioleinglycerine ester, oleic acid cetyl ester, clove oil, rapeseed oil and the like, are most appropriately brought to a content of 1.0-1.5 percent epoxy oxygen.

Epoxidates of epoxidizable compounds of a non-aliphatic nature are also usable as starting materials, especially those of unsaturated cycloaliphatic or heterocyclic compounds, such as e.g. epoxidation products of tetrahydrobenzoic acid and -phthalic acid derivatives or condensation products according to Diels-Alder of diene components with at least two conjugated double bonds and philodiene components with at least one double bond as well as of sterins, such as e.g. cholesterol.

It is known that epoxidation products of higher molecular unsaturated compounds are polymerized in the presence of acid-reactive substances such as e.g. sulfuric acid under the influence of the epoxide group to higher molecular products, which have the character of lubricants or virtually similar substances. Compared to this, it seems surprising that such epoxidation products under the sulfonation conditions show a completely different relationship, as they form monomeric sulfonation products. This effect is not limited to sulfuric acid, but can be carried out in an analogous way with other sulphurizing agents, such as sulfur trioxide, deum and pyridine-sulphuric acid adducts.

The reaction of the epoxidized high-remolecular compounds with sulfuric acid or its derivatives takes place, depending on the consistency of the reaction mixture, in stirring vessels or mixers, possibly with the mixing of indifferent diluents, such as e.g. carbon tetrachloride, sulfur dioxide, etc. The reaction usually takes place at temperatures below 40°C, preferably at 15-35°C. The amount of mineral acid used depends on the desired degree of effectiveness, since the attack on the epoxide group and also on a still-present double bond can take place.

As the reaction usually proceeds exothermically, it is appropriate to provide for heat removal, because too much heating of the reaction mixture can lead to side reactions and unwanted resin-like products. Usually, the reaction is considered to have ended after the end of the exothermic reaction, however, it is appropriate to continue stirring the reaction mixture for a few hours.

The resulting reaction products are freed in the usual way by washing for excess inorganic acid parts. The reaction mixture can then be completely or partially neutralized in the usual way by adding inorganic or organic bases, such as sodium or potassium hydroxide, sodium carbonate, ammonia, dimethylamine, triethanolamine, etc.

Particularly useful products are obtained when such epoxidized oils, fats or waxes are used as starting materials, which have an epoxy oxygen content of up to approx. 3 per cent, where the iodine number has dropped to approx. 20-50 percent of the original value. Since the epoxidation leads to products with a light color and a pleasant smell, relatively inferior, dark-colored substances, especially cod liver oil or wax, can also be used as starting material for the process, and still end up with light-colored, odorless sulfonation products.

The resulting new impact products are easily soluble in water and/or dispersible products. As such or in the form of their water-soluble neutralization products, they have surface-active properties and have a partially Turkish red oil-like character. They can therefore be used for all purposes for which such substances are usually used, i.e. as wetting, dispersing, emulsifying and cleaning agents. Furthermore, they can be processed together with other surfactants and common organic or inorganic additives and solid processing products can also be produced from this, such as e.g. powder, flakes, shavings, slices or pieces.

The produced sulfonation products or their salts have a wide range of technical interest. Due to their emulsifying and dispersing effect, they can be used in the textile, washing or cleaning agent industry, as washing active substances, as cleaning enhancers, as preparation, lubrication and smoothing agents, as agents for antistatic equipping of fiber material, fabrics and foils , further in the plastics industry as emulsifiers and in petrochemicals as lubricants or as lubricant additives, e.g. to reduce the mineral oil's stick point.

With regard to the differences that the products according to the invention have in relation to such sulfonation products and the like, which are not anepoxidized in advance, the following can be mentioned: 1. Strong reduction of the iodine number, and

thereby greater light resistance.

2. Especially with cod liver oil with a higher iodine number, but also with fatty vegetable oils, an eye-catching bleaching effect appears. 3. The noticeable bad smell and tendency to build up in cod liver oil - especially of inferior quality - disappears. The difference between cod liver oil of different invention disappears. 4. The hydrophilicity of all products increases.

Therefore, you can sulphate with smaller amounts of sulphating agent than usual. This results in lower salt products with greater shelf life and no salt excretion.

Examples.

1) A black colored waste herring oil with an unpleasant odor with the following characteristics: Acid value 17.2, iodine value 106.9, saponification value

120, OH number 21.9, is oxidized in a known manner

in the presence of acetic acid with hydrogen peroxide. After processing, a pale yellow, odorless fish oil with characteristic acid number 15.7, iodine number 70.7, epoxy oxygen content 1.0% is obtained. The epoxidized fish oil is sulphonated with 20% concentrated sulfuric acid at 25-28°C. Then stir again for approx. 2 hours at the same temperature. The resulting acidic sulfonation product is washed twice with 10% sodium

sulfate solution. It is then neutralized by adding potash. The resulting reaction product is a clear, yellowish, oil-like liquid, which is very easily dispersible in water.

2) A dark brown, deacidified walrus with

characteristics acid number 2.0, saponification number 154.8, OH number 17, iodine number 132.5, epoxied as stated in example 1. The light yellow whalebone epoxide that appeared after the epoxidation (acid number 0, saponification number 155.2, OH number 19, iodine value 84.0, epoxy oxygen content 1.3 per cent) is sulphonated according to the conditions stated in example 1 with 15 per cent concentrated sulfuric acid, then stirred

and washed. By adding triethanolamine, the acidic oil is adjusted to a pH of 6.5. By stirring in ten times the amount of water, a stable emulsion is obtained, which is stable over a longer period of time.

3) A soybean oil with a characteristic acid number

.

1.5 percent has been reached, which has an acid number of 0.17 and an iodine number of 80.5.

The produced epoxidate is sulphonated with 20% concentrated sulfuric acid at 25-28°C. After the subsequent stirring, wash with sodium sulfate solution. The resulting sulphonation product is brought to a pH value of 6.5 with concentrated aqueous ammonia. The neutralization product is a light-coloured, water-soluble oil. 4) Light yellow fish or sildetran mea Characteristics iodine number 70, saponification number 180, epoxy oxygen content 0.7 per cent, sulphonated with 13 per cent. 96 per cent sulfuric acid at 25°C during an inlet time of approx. 1 hour and subsequent stirring time approx. 1-1 ½ hours. The acidic ester is then continuously brought to flow into approx. 80 per cent of the stoichiometric amount of ammonia required for complete neutralisation, in the form of a 5 per cent solution. Thereby, the maximum temperature of 30 °C must not be exceeded. The batch is left at pH 4-5 until separation of the salt water layer at a temperature of approx. 50°C for 10-12 hours. After separation of the aqueous layer, neutralize completely with 25% ammonia until pH 6.8 to 7.0.

Consumption per 100 kg anepoxidized cod liver oil:

13 kg of 96% sulfuric acid

about. 75 kg 5% ammonia solution

about. 2 kg of 25% ammonia.

You get a brown, clear sulfonate, which with water gives well-resistant emulsions. 5) Light yellow haitran with characteristic iodine number 70, saponification number 155, epoxide content 1.0% is sulphonated with 18% 96% sulfuric acid. The sulfuric acid inlet time iyz to 2 hours at max. 28°C. Post-stirring time 1 to iy2 hours. The acidic ester is stirred in without stopping for approx. 80 per cent of the amount of alkali required for complete neutralization in the form of a 5-10 per cent KOH solution. Below that, a temperature of 30-35°C should not be exceeded. After mixing, the mixture has a pH value of between 4 and 5. The separation of the aqueous layer can take place after 2-4 hours. The remaining oil is neutralized with 50% KOH solution to pH 6.8 to 7.0. This gives a yellowish-brown, clear sulphonate. 6) 60 parts of the sulphonate according to example 5 and 40 parts of paraffin oil 5°E at 20°C give a clear, water-emulsifiable mineral oil mixture.

The emulsions are very resistant and can be used as textile, melting and preparation agents. 7) Light yellow sperm oil epoxide with characteristics acid value 0.6, saponification value 140, iodine value 51.7, unsaponifiable 37.2 per cent, epoxide content 1.34 per cent, sulphonated with 15 per cent sulfuric acid (96 per cent ig) at 28-30 °C. The mixing time of the sulfuric acid amounts to approx. 2 hours and the post-stirring time iy2 hours. The acidic ester is stirred into an ammonia quantity of approx. 80 per cent of what is required for complete neutralization in the form of a 5 per cent solution. (Consumption per 100 kg of oil approx. 55 kg of 5% ammonia solution). The temperature should not exceed 30-35°C. After a standstill of 8-10 hours, the salt water layer separates and the remaining sulphonate is completely neutralized to pH 6.8 to 7.0 with 25% ammonia. (Consumption approx. 3-3.5 kg of 25% ammonia). You get a brown, clear sulfonate. 8) Oleic acid decyl ester with characteristic acid number 0.4, iodine number 33.5, epoxide content 1.32%, is sulfated with 20% 96% sulfuric acid at 28°C. The sulfuric acid inlet time approx. 2y2 hours, post-stirring time approx. 1.5 hours. The washing and neutralization of the sulphonate takes place as indicated in example 7. In this way, a water emulsifier is obtained bare, highly moisturizing, brownish-yellow, clear oil, which can be used as a wetting agent and fiber protection agent in textile production. 9) A rapeseed oil with characteristics acid number 0.3, iodine number 103.2, saponification number 175.4, OH number 2.8, is anepoxidized according to the usual procedure. The following characteristics are then obtained, acid number 0.3, iodine number 80.2, epoxide content 1.54%. This an-epoxidized, light yellow rapeseed oil is sulphonated with 8% 96% sulfuric acid at 28-30°C during of 1 hour. The post-stirring time after the introduction of sulfuric acid also amounts to 1-1/2 hours. About. 80 per cent of the necessary neutralizing agent is placed in the form of a 5 per cent ammonia solution in a stirring vessel. The acidic ester is slowly stirred in with slight cooling so that the temperature does not rise above 30° C. The mixture is allowed to stand between pH 4.0 and 5.0 for approx. 10 to 12 hours at approx. 50°C and then removes the separated salt water. The sulfonation product is neutralized with ammonia to pH 7.0 to 7.5. You get a clear oil, which can easily be emulsified with water.

Claims (1)

Process for the preparation of surface-active sulfuric acid derivatives of higher molecular weight organic compounds by bringing sulfuric acid, oleum, sulfur trioxide or pyridine-sulfuric acid adducts into action on oxidation products of unsaturated organic materials at a reaction temperature of 10 to 40°C, preferably 15 to 35°C in an amount of 8 to 20 per cent, referred to the oxidation product, and optionally neutralizes the sulphation products formed, characterized in that unsaturated animal, vegetable or synthetic oils, fats or waxes which have been epoxidized and which are used as oxidation products of unsaturated organic materials has an epoxy oxygen content of up to 3 per cent, preferably between 0.5 and 1 per cent.