SE190652C1 - - Google Patents

Description

Inventors: JD von Mikusch-Buchberg, KH Mebes and MR Mills Priority asked Iran on 30 November 195 and 7 October 19 (Great Britain) The present invention relates to new condensation products and in particular those arising from the treatment of fatty acids on such salt, that the products obtained will be usable in technical compositions. When the starting materials are unsaturated, the products obtained become particularly suitable as drying agents in paints, varnishes, essential oils, linoleum and similar products in whole or in part as a substitute for drying oils. If the starting materials are matte, the resulting products become useful, for example, as hard oils or plasticizers and the like.

According to a previous report, hydroxylated oils or fatty acids or unsaturated fatty oils or fatty acids, which were first converted to hydroxylated fatty oils or older fatty acids by an oxidation treatment, are heated in the presence of a few percent boric acid under vacuum to a temperature of 260 and 300 ° C. .- The products thus obtained consist mainly of esters.

According to another previous proposal, fatty oils are heated in a mixture with a small amount of fatty acids under similar conditions in order to effect an interesterification and to remove the short-chain fatty acids which are not present in the oil by destination. The products thus obtained constitute glycerides.

It has now been found that new condensation products can be obtained by heating non-hydroxylated fatty acids or mixtures containing a substantial amount of non-hydroxylated fatty acids in the presence of a small amount of a catalyst to a temperature of 220-330 ° C. during simultaneous separation of formed reaction water, Dupl. at 12 o: 11; 22 g: 3 until the product contains a substantial amount of non-digestible material having an average molecular weight according to the calculated molecular weight of a condensation product of at least three moles of fatty acid. For practical purposes, it is most appropriate to use a temperature between 250 and 300 ° C.

The reaction which takes place in carrying out this process consists essentially of a condensation of free fatty acids. The reaction conditions are such that the fatty acids in alit are substantially retained in or returned to the reaction mixture, if it is not desired to distill a fraction of lower molecular weight fatty acids to obtain a more unsaturated end product. The reaction is carried out during such Pang time that a substantial part of the fatty acids is converted into non-digestible material, as specified above.

It has further been found that similar products are obtained if the starting material mile-hailer a substantial amount of ketones obtained from fatty acids. Such ketones constitute an intermediate in the condensation of fatty acids according to the invention.

The fatty acids used may be saturated but are preferably unsaturated.

The heating can be carried out under atmospheric pressure, whereby a stroll of inert gas, e.g. nitrogen gas, is passed through the reaction mixture, but is preferably carried out under vacuum.

If the reaction is carried out under high vacuum, it is possible that the reaction temperature immediately reaches the range 220-330 ° C, since the mixture during the first stage of the reaction can boil at a temperature lower than 220 ° C, with fatty acids transitioning to the vapor phase together with volatile reaction 2— - products. As the reaction proceeds, the fatty acid concentration in the mixture is lowered and the boiling point of the mixture increases, so that the temperature can gradually rise.

Due to the evaporation of the fatty acids which takes place during the reaction, the heating is suitably carried out under reflux of the fatty acids and the more boiling compounds. In this way, a larger part of the starting material can be transferred to the final condensation product.

The starting material may be a fatty acid or a mixture of fatty acids, e.g. the mixture obtained from a fatty oil or a mixture of such. oils. Pine oil fractions, obtained by fractional distillation of tall oil and consisting essentially of pine fatty acid, are also useful as starting materials. It has been proposed to heat tall oil or tall fatty acid to a temperature above 830 ° C in the absence of catalysts. Products obtained in this way have lower iodine numbers than the starting material, while the products obtained from tall oil fractions according to the present process, in contrast, have higher iodine numbers than the starting material.

The starting material may also be a mixture of one or more ketones obtained from fatty acids with one or more fatty acids. In such mixtures, the ketones may be derived from the same or different fatty acids from the present ones.

The ketones mentioned above can be prepared on each per se edge salt.

The starting material may finally contain other constituents, e.g. mono-, di- or triglycerides, or resin acids. In this case, the mixture should contain a substantial or appropriate amount of fatty acids and / or ketones prepared from fatty acids. The other constituents have a tendency to slow down the rate of the desired reaction, so that an excessively high content thereof in the starting material should be avoided. Although the additional constituents themselves have sufficient drying properties or few such properties during heating, the amount thereof should not exceed the combined weight of fatty acids and ketones obtained from fatty acids.

When used, the fatty acids suitably have the form RC OOH, van in R represents an unsubstituted, long-chain, saturated or preferably unsaturated alkyl group, which for example contains 9 to 25 and preferably 17 to 21 carbon atoms. In the same way, it is most convenient to use ketones of the formula R-C ---- R ', 0 van in R have the meaning given above and R' has the same meaning as R. Since R represents one. unsaturated alkyl group, this may contain at least one double bond, as in oleic acid.

In order to obtain products with good drying properties, the reaction should be carried out in the presence of at least some unsaturated alkyl groups with two or more double bonds. As an example of. Such unsaturated alkyl groups may be those which occur in linoleic acid, linolenic acid or in the highly unsaturated acids which occur in fish oils.

The percentages given below are calculated on the amount by weight of the starting material used, unless otherwise stated.

The temperature and heating time used, as well as the amount of non-digestible material that can be obtained, depend to some extent on the type of fatty acids used as the starting material. When using fatty acids with a relatively high iodine value, the heating can be carried out at a high temperature for a long time while simultaneously forming a large amount of non-digestible material, e.g. 70 to almost 100%. When using fatty acids with Mgt iodine content, e.g. Above 150, on the other hand, it may be necessary to interrupt the heating at an earlier time, as gelatinization may take place. The amount of non-selectively hard material formed can in this case be lower, e.g. 40-60%. For the same reason, in many cases it is convenient to mix fatty acids of different types before they are reacted, so that a complete condensation of highly unsaturated acids can be achieved in one step. on the other hand, when using fatty acids which contain individual acids of different types, it may be appropriate to fractionate the original mixture, for example by distillation, or to distill off the most volatile and least unsaturated acids during the condensation reaction (which can be done by refilling the reflux condenser). a temperature extremely suitable for this purpose), whereby a better drying product is obtained.

The degree to which the free fatty acids are converted to non-digestible material with the stated properties may vary widely depending on the conditions for which the condensation products of the invention are to be used. For some purposes a conversion rate of 20-30% may be sufficient, while in other cases 30-40% may be lamp-high.

As a starting material, use the fatty acids can in some cases be advantageously purified according to usual methods.

The catalyst used in the present process may be boron or preferably an oxygen-containing boron compound. Suitable inorganic boron compounds are boric acid and boron oxide. Salts thereof, e.g. alkali or lampium ammonium pentaborate, can also be used to advantage. However, borax has little catalytic activity and boron compounds with oxidizing properties are not suitable. As organic boron compounds, it is most convenient to use esters of boric acid, e.g. boric acid trimethyl ester, boric acid triethyl ester, boric acid mannitol ester, the mixed anhydride of boric acid and attic acid or the mixed anhydride of boric acid and higher fatty acids, which are obtained, for example, from a fatty oil, e.g. peanut oil.

The catalyst can be used on a suitable carrier, such as silica, e.g. in the form of diatomaceous earth, diatomaceous earth or silica gel. If a supported catalyst is used, the catalyst can be loosened or suspended in water and the barrier added, after which the resulting mixture is dried in an oven.

The amount of catalyst used can vary widely, for example between 0.1 and 10% by weight. In general, it is most appropriate to use a catalyst amount of air nagra Id proeent, e.g. 2-6 weight percent.

The process is conveniently carried out in a stainless steel reaction vessel equipped with a backflow cooler. Deana can either be heated or cooled, so that fatty acids and other high-boiling products are caused to reflux, while reaction water and other volatile products and gases distill off. The water and the other volatile products can be condensed in a cooled trap together with any entrained, high-boiling products.

The mixture in the reaction vessel used is heated to a temperature between 220 and 3 ° C. It is desirable to keep the reaction mixture at a temperature between 250 and 300 ° C at least during the latter part of the reaction time. The reaction can be carried out at atmospheric pressure, e.g. in a stream of air an inert gas, such as nitrogen gas, but is preferably carried out either under vacuum or in the presence of an inert, water-immiscible solvent.

The catalyst can be mixed with the starting material or added during heating in the reaction vessel. It can also be placed in the radiator.

The backflow cooler can, for example, be packed with spirals, Raschig rings or the like. It can also be regulated in such a way that some of the fatty acids can be distilled off.

After heating, any unchanged fatty acid in the reaction mixture can be extracted with a suitable solvent, e.g. alcohol. Alternatively, the reaction mixture may be distilled in vacuo to separate unchanged fatty acid. The residue after the solvent treatment or distillation constitutes the desired product. The reaction mixture is suitably subjected to filtration, washing with hot water to separate the catalyst and drying in vacuo before or after the solvent treatment or distillation.

If the reaction is carried out in the presence of an inert, water-immiscible solvent, the boiling point of the solvent should suitably be higher! 130 ° C and not higher than 300 ° G. During heating, the solvent entrains water released during the reaction and the vapors consisting of solvent and entrained water are fed to a condenser, which is combined with a suitable trap. The condensed water and solvent are separated from each other in the trap, after which the condensed solvent is returned to the reaction vessel.

Suitable solvents are xylene, which boils between 135 and 145 ° C and which allows heating to 260 ° C, tetralin (tetrahydronaphthalene) with a boiling point of 205-215 ° C, which allows heating up to 295 ° C, and decalin (decahydronaphthalene) with boiling point 184-191 ° C, which allows heating to 290 ° C. Petroleum carbonate fractions with a boiling point above 200 ° C also constitute suitable solvents.

The distillate or alcohol extract obtained in carrying out the present Further can be used as starting material for a further treatment, since it consists essentially of unchanged starting material. If the reaction is allowed to proceed to a stage at which only a small amount of unchanged starting material is present in the reaction mixture, it is not necessary to read off its starting material.

The residue obtained under the reaction conditions described is the main product. If the starting material contains unsaturated fatty acids, the residue has better drying properties than the corresponding triglycerides, low volatility and Rad viscosity compared to the fatty acids which form the starting material. The changes in these properties become clearer with similar heating time and / or temperature. Analysis results show that the reaction results in the formation of a significant amount of non-digestible material, which differs from the known fatty acid ketones. It has been found that this non-digestible material is mainly responsible for the good drying properties and shows unique film-forming properties when insulated.

The invention also includes the novel condensation products obtained by these processes, such as spidane or in admixture with unchanged fatty acids.

The condensation products according to the invention are distinguished by a. essential content, preferably at least Vo, non-digestible material, added acid and preselection number, Rat iodine number according to Wijs, j amfort with the starting material and a. high average molecular weight. The average molecular weight of the non-digestible moiety is roughly estimated to be equal to or higher than that. calculated the molecular weight of a theoretical condensation product of three molecules of fatty acid. If the iodine value is determined according to Wijs' method and turns out to be 100 or higher, the condensation products have drying properties. They also have a molecular structure, the corn contains at least three alkyl chains, which are similar to those which do not. in the fatty acids of the unsaturated oils.

The invention also includes the use of the above-mentioned products with an iodine value according to Wijs' method of 100 or higher, as a replacement material for drying materials, e.g. drying oils, oil paints or alkyd resins in paint, lacquer, linoleum and for sanded andamal.

The new products can be mixed with ordinary leaks, based on cobalt, lead or manganese, and can be diluted to the desired viscosity with turpentine, light kerosene and / or other volatile solvents.

As an example of the use of the new products may be mentioned that for a product obtained from soybean oil fatty acids according to the present process in a yield of 75.4%. This product had an acid number of 8.6, a preselection number of 44.2, an iodine number according to Wijs' method of 175.3 and a content of non-digestible material of 82.5%. This product gay following results when used as a barer for paint or as a clear coat. The viscosity was 37 pois at 20 ° C, i.e. same as for a thin stand oil. A substituted product for linseed oil is obtained by mixing 57 g of the new condensation product with 33 g of a 1: 1 mixture of turpentine and latte kerosene. To replace the oil paint, a mixture of 90 g of the condensation product and 10 g of the 1: 1 mixture of turpentine and latte kerosene was prepared. A small amount of leachate was sufficient to obtain a shorter drying time than with good quality boiled linseed oil. With, for example, 0.1% cobalt, shaved on the condensation product, 240 minutes were required for drying to dry state and 3011 minutes for drying to hard condition. The weight gain obtained during air drying of the undiluted condensation product was higher than for linseed oil with gamma viscosity, which indicates a high affinity for oxygen, although the product is obtained from soybean oil fatty acids with much lower iodine content than linseed oil. The hardness of the obtained film was tested according to Sward's method and was found to be substantially harder than a film of boiled linseed oil and as high as a maleinate resin lacquer, containing 2.3 liters of oil per kg of resin. The film was Miter best spirit against water and diluted sulfuric acid than films of linseed oil and many oil paints.

Zinc white enamels, produced from the condensation products, showed no signs of thickening.

What hotly hits dehydrating oils, e.g. herring oil, cottonseed oil, peanut oil or rapeseed oil, even if the more saturated acid constituents were removed and the remaining unsaturated acids were converted again: to triglycerides the resulting products have the same drying properties as products according to the invention, produced from corresponding acids. A film which is Midas of the product obtained from linoleic acid, as described in the following Example 4, is harder than a film of conventional linoleic acid glyceride, and its hardness is about as high as the hardness of a film of a linolenic acid glyceride.

The invention is further illustrated by the following examples. In the laboratory scale challenge experiments described in Examples 1 to 8, 12, 13, 16 and 17, the temperature of the metal bath surrounding the reaction vessel is indicated. In these examples, the temperature of the reaction mixture was lower, e.g. between 20 and 30 ° lower during the initial stages and approximately 10 ° C lower during the final stages of the reaction.

The temperatures given in the following examples denote the temperature of the reaction mixture.

Example 1. 110 g of fatty acids obtained from Norwegian herring oil according to the Twitchell method (acid number of fish oils 182.7 and iodine number 132.7) and 2.75 g of crystalline boric acid are introduced into a 250 ml flask, over which a fractionation column is arranged in a vertical layer. This column is connected to a vacuum pump via an air-cooled radiator, which is connected in parallel with the fractionation column, and a source at the other end of the radiator. The fractionation column is packed with spirals of stainless steel, llaschigings of glass or the like.

After evacuating the apparatus to about 2-3 mm Hg, the flask was slowly heated in a metal bath until the bath temperature was 290 ° C. The heating was performed within 60 minutes until the bath temperature was 210 ° C. It was then continued for another 150 minutes, raising the bath temperature. frail 210 to 290 ° C. The bath is kept at the latter degree for 3 hours. The fractionation column was heated to about 175 ° C by electric resistance heating. At a bathing temperature of about 210 ° C and above, some material began to distill to the publisher. Materials that entered the fractionation column began to condense at a lower bath temperature no. After heating for 3 hours at 290 ° C, the reaction mixture was allowed to cool. 31.3 g of fatty acids and a small amount of water and boiling boiling partitioning products were distilled off, while 64.4 g of erhollose which remained in the reaction vessel. The solid boric acid, which was part of the residue, was filtered off, while the residue was still hot. Some material limped to the filling in the backwater column and was recovered by extraction with latte kerosene. The viscous residue, which had an acid number of 10 and contained 81.3% of non-digestible material, was diluted with latte kerosene. 0.3% Pb and 0.066% Mn were added in the form of naphthenate siccatives. When a thin layer of the thus produced lacquer was exposed to the action of the air, it dried to a tack-free state in less than a day. - —a The fatty acids of sardine oil and tran gay in treatment according to the examples described above varying amount (50 to 80%) of atherosclerosis in the form of oily water shoes with good drying properties.

In a similar experiment, which is, however, challenged with the use of only 0.3% by weight of boric acid, a large part of the reaction mixture was distilled off, so that only about 38% of the residue remained in the reaction vessel.

This residue had an acid number of 16.5, and dried after leaching for 6 hours to a non-sticky and hard film.

The product obtained was suitable as a starting material for paints and varnishes in that the Toro siccatives were built on the basis of cobalt, lead and manganese compounds.

Example 2. 110 g of herring oil fatty acids (acid number 182, iodine value 142.7) and 6.6 ammonium pentaborate were heated for 60 minutes in the apparatus described in Example 1 to a bath temperature of 210 ° C, darpa 150 minutes to a bath temperature of 290 ° C and finally 60 minutes at a bath temperature of 290 ° G. After cooling, 55.5 g of residue were recovered in the reaction vessel. This residue had the same consistency as a high viscosity stand oil a.

After dilution with light kerosene, the residue was filtered to separate the solid catalyst, after which the residue was washed with hot water to separate loose boric acid compounds. When the resulting product was treated according to Example 1, a composition having good drying properties was obtained. A thin film of this composition was under normal temperature and light conditions dry to the touch for 3.5 hours and almost free of stickiness after 24 hours.

The product obtained was suitable as a starting material for lacquers and varnishes, while the sealants therefor were built on the basis of cobalt, lead and manganese compounds.

Example 3. Technical, distilled linseed oil fatty acids (iodine value 165) were slowly heated in the apparatus of Example 1, until the bath temperature was 290 ° C, together with 6% by weight of boric acid. Heating was continued until about 25% of the original material had distilled off as water (approximately 7%) and fatty acids (approximately 18%). The residue dried after the addition of siccative and dilution for 3.5 hours to a substantially tack-free and colorless film and was suitable as a substitute for boiled linseed oil in the manufacture of paint paints or for use as clearcoat.

In a similar experiment, prey was taken out while heating the reaction mixture at a bath temperature of 215, 245, 260, 275 and 290 ° C. The iodine value for these samples was 167.2, 177.8, 179.9, 179.7 and 179.7, respectively. 190.5 and refractive index 1.1674, 1.4700, 1.4730, 1.4793 respectively. 1.9405. The last sample had a viscosity of 3.4 pois while the nearest enemy had a viscosity of 0.9 pois. The largest part of the air distillate with lower iodine value resigned during the earlier part of the heating period, which caused the residual iodine value to increase to about 180. After another approximately one hour of heating at a bath temperature of 290 ° C, the residue had gelatinized. Such gels can be used to advantage in the paint industry and closely related industries, e.g. in the production of linoleum and certain paint colors.

Example 4. Upon treatment with a linoleic acid concentrate of safflower fatty acids according to Example 1, a residue is obtained in a yield of about 65% in the form of a relatively viscous oil, which after addition of desiccant gays a tack-free film of about 7 hours. 01-Jan had an acid number of 30.7, a preselection number of 6.1, 20% carbonyl acid, determined according to Knight and Swern, Journal of the American Oil Chemists Society, 26, 366-370 (1949), a hydroxyl number of 0 and contained 73.4% of non-biodegradable material with a molecular weight of approximately 900, determined according to Mattiello, Protective and Decorative Coatings, Part V p. 194-195, John Wiley and Sons, New York (1947). It was largely insoluble in ethyl alcohol, acetone and acetic acid but soluble in aliphatic and aromatic hydrocarbons, e.g. lattfotogen or bens en.

The product showed a remarkably high iodine value increase. Prior to heating, the concentrate had an iodine value of 180 both according to Wijs 'and Woburn's method, while the product after heating had an iodine value of 211 according to Wijs' method and 234 according to Woburn's method. The non-selectable part of the product (73.4%) had an even higher iodine value, namely 224 according to Wijs' and 250 according to Woburn, and a cliental according to Ellis-Jones of 10.3.

The non-digestible portion of the residue, obtained by extraction with solvents after pre-digestion, had even better drying properties in the product as a whole, in that after the addition of siccative and after dilution it dried to a very hard film, which was as hard as a Chinese film. trawl oil and had good water and alkali resistance.

The fatty acid distillate, which had been recovered in the publishing house and made up about 22% by weight of the material, consisted for the most part of unchanged but contaminated linoleic acid and could be re-hydrated. The distillate had an acid number of 143.0, a preselection number of 190.6 and an iodine number of 170.8. About 6% water had accumulated in a cooled trap in the vacuum line.

The product obtained was suitable as a starting material for lacquers and varnishes, while the sealants therefor were built on the basis of cobalt, lead and manganese compounds.

Example 5. 110 g of cottonseed oil fatty acids obtained by technical distillation of fatty acids obtained by preselection of cottonseed oil were treated in a round bottom flask. The fractionation column was arranged over the flask and packed as described in Example 1. It also contained 6.6 g of boric acid in the form of pieces obtained by applying high pressure to a slurry of finely powdered, crystalline boric acid and a small amount of water in a tablet press with subsequent drying. at about 70.0 C, in an oven. After evacuation of the apparatus, the reaction vessel was heated as in Example 2. This gave a residue which weighed 47 g and which, after the addition of diluent and desiccant for 3.5 hours, dried to a hard, elastic and tack-free film with good surface coating properties.

The product obtained was suitable as a starting material for lacquers and varnishes insofar as the leachates therefor were built on the basis of cobalt, lead and manganese compounds.

Example 6. 110 g of a 97% purity oleic acid, containing 2 to 3% saturated fatty acids, were treated with 6.6 g of boric acid, distributed in a fractionation column as in Example 5. The heating time and temperature were the same as in Example 2. In addition to 6.4 g of a fatty acid distillate, which had the iodine value 52 and which consisted mainly of a mixture of oleic acid and palmitic acid, 7.7 g of an aqueous distillate were recovered. The bulk of the material remaining in the flask was washed with hot water to separate loose boron compounds. After this purification, the residue had a refractive index of 1.4776, an acid number of 58.1, a preselection number of 85.6, an iodine value of 132.9 and an average molecular weight of 661, while oleic acid has a refractive index of 1.4580, an acid number of 198.5, a preservative number of 199.3 and an iodine value of 88. , 0. Although the oleic acid before treatment was free of non-digestible material, the residue contained 44.7% of such material. The residue was soluble in ether and light kerosene but insoluble in alcohol and acetic acid. In total, a weight loss of 2% occurred, based on the starting material. This weight loss was due to the formation of gaseous particulate products.

The product obtained was suitable as a starting material for lacquers and varnishes, while the sedatives were built on the basis of cobalt, lead and manganese compounds.

Example 7. 110 g of petroleum fatty acids (acid number 197.6, iodine value 98.7) were heated under vacuum in a flask equipped with a carbon black containing Raschig rings together with pieces of boric acid obtained by pressing and drying moistened powdered boric acid. An air-cooled backflow cooler was arranged above this column. The fractionation column was electrically heated to 200 ° C and a vacuum was applied from time to time for a moment so that distillates which may have accumulated in the upper part of the heated column could flow back to the flask. This was slowly heated in a bath, the temperature of which was raised to 296 ° C and kept at this degree for one hour. Due to the use of a reflux condenser, no distillate other than an aqueous fraction weighing about 8 g and condensing in a cooled trap was obtained in the vacuum line. The remainder was about 90%, including the samples taken from time to time to monitor the increase in the content undeliverably. After that, the residual iodine number and the decrease in the acid number, caused by the increase in the completed experiment, had the iodine number 123.8 and the acid number 70.6. It contained 20.6% of a fatty acid fraction (iodine number 94.4, acid number 175.5), which could be separated by one hour heating under vacuum at 290 ° C. The residue, which had good drying properties, was obtained under these conditions in the form of a polymer , non-volatile product.

A similar result was obtained when pieces of smolt boron oxide of approximately species size were distributed in the filling in the fractionation column.

The product obtained was suitable as a starting material for lacquers and varnishes savida sickatives dad & were built up ph base of cobalt, lead and manganese compounds.

Example 8. A mixture of 40% neutral oil and 60% free fatty acids, obtained under alkali refining of rapeseed oil and having an acid number of 112 and an iodine value of 126.8, was treated with 6% boric acid in the apparatus and in the manner described in Example 2. The residue, which accounted for 77% by weight of the original fat compound, was a viscous oil with an iodine value of 146.1. After the addition of diluents and metal desiccants, a film after 19 hours of drying showed only low tack.

The product obtained was suitable as a starting material for tacks and varnishes insofar as the siccatives were therefore built up of ph base of cobalt, My and manganese compounds.

Example 9. 500 g of separated fish oleic acids were heated at 240-260 ° C with 2% boric acid and 80 ml of xylene in a three-necked flask equipped with a mechanical stirrer, thermometer and a waterfall. The rate at which the water was released and the effect on the analytical constants are shown in the following table: Heating- Collection time lat water Acid number in Um.imi 0 0 183.8 184 1.4659 61/2 8.0 160 , 7 181 1,468 13/4 11.2 135.7 159 1.4734 21 1/2 14.7 108.4 138 1.4783 28½ 17.1 91.9 11.4818 36 18.76.8 107 1, 4852 Water from the catalyst: 4.3 ml Reaction water = 14.2 ml = 2.8%.

The product thus obtained was freed from xylene, filtered, washed and dried under vacuum at 90 ° C and extracted with ethyl alcohol. Properties of the extract and the residue Toro: Saponification number Refractive index at 25 ° C Residue - 190 Extract Original acids Yield GO% 40% Acid number 194 152,183.8 Saphoration number 56 176 184 Iodine number 148,114.2 131, Non-digestible material 37.5% 652 -7 The product obtained was suitable as a starting material for lacquers and varnishes, while the leachates were built on the basis of cobalt, lead and manganese compounds.

Example 12. 220 g of peanut oil fatty acids and 6.6 g of boric acid were heated for 16 hours in an evacuated flask at 220 ° C. A column, equipped with Raschig rings, was placed over the flask and the lower part of the column was heated to 175 ° C. served as a backflow condenser for the fatty acids but allowed water and other probing products to distill off. The product thus obtained had the preselection number 163.5, the iodine number 110.6 and the refractive index n = 1.4720. The product was heated for three hours with the still present boric acid at atmospheric pressure in a round bottom flask at 290 ° C, allowing a weak stream of carbon dioxide to pass through the reaction mixture simultaneously. The final product had the preselection number 83.3, the iodine number 127.1 and the refractive index n g 1.4812. It had drying properties.

The product obtained was suitable as a starting material for lacquers and varnishes, and the sedatives were therefore built on the basis of cobalt, lead and manganese compounds.

Example 13. 12.4% fatty acids of peanut oil, consisting mainly of matte ones, were distilled off in vacuo. 248 g of the residue, which had an acid number of 191.8, a preselection number of 195.8 and an iodine number of 122.9, were heated for hours in the presence of 20 g of magnesium oxide at 330 ° C, whereby the corresponding ketone was obtained. The ketone was washed with dilute sulfuric acid to probe the magnesium whey and then subjected to a final watering with water until it reacted neutrally. It had an acid number of 3.0, a preselection number of 3.5, an iodine number of 126.8 and a carbonyl number of 86.1. 70 g of this ketone and 40 g of petroleum fatty acids were heated with 2% boric acid for 3 hours up to 290 ° C in a refill column. The mixture was milled for 4.5 hours at this temperature, then the fat condensate was refluxed and the reaction water was removed. The mixture was then heated for another hour without reflux with collection of the condensate in a multilayer. The residue obtained, after separation with the boric acid, weighed 97 g and had an acid number of 1.5, a preselection number of 14.1 and an iodine number of 168.5. It dried with the help of a siccative to an elastic film in 2 days.

The product obtained was suitable as a starting material for paints and varnishes insofar as the siccatives were built on the basis of cobalt, lead and manganese compounds.

Example 14. 20 kg of sunflower fatty acids, obtained by preselection of sunflower oil, and having the acid number 160, the preselection number 196 and the iodine number 127, were heated with 0.4 kg of technical grade boric acid under a vacuum of 15 to 25 but Hg in an apparatus consisting of rust- The product obtained was suitable as a starting material for paints and varnishes, insofar as the sedatives were therefore built on the basis of cobalt, lead and manganese compounds.

Example 10. 180 g of distilled coconut oil fatty acids from waste mixtures obtained in margarine production were heated with 3.6 g of boric acid and 20 ml of xylene at 240 DEG-260 DEG C. in an apparatus of the same kind as that used in the previous example. The experiment was continued for 63 hours without deduction of prey for analysis. The total amount of water released was 12.5 ml, corresponding to 10.8 ml or 6.0% reaction water. The product was purified in the usual manner and had the following properties: Original acids After the treatment Iodine number (Wijs) 16.2 38.8 Refractive index (25 ° C) 1.4438 1.4763 Acid number 241.2 37.7 Pre-digestion number 242 58, OfFardable 0% 47% The product obtained was suitable as a starting material for lacquers and varnishes, while the sedatives were therefore built on the basis of cobalt, lead and manganese compounds.

Example 11. 750 g of peanut oil fatty acids were treated with 16 g of boric acid and 120 ml of the tetrahydronaphthalene in the apparatus described in Example 9, the temperature being between 260 and 290 ° C, until water no longer escaped. After 46 hours, 56.5 ml of water had been recovered, corresponding to 6.0 reaction water.

The product was purified on the usual salt and the following analytical constants were determined: Original acids After the treatment Acid number 197.7 6.2 Sampling number 198 12 Refractive index (25 ° C) 1.4603 1.499 Iodine number (Wijs) 98.6 124.9 Non-digestible material 85% Whole the product was diluted with half its weight of light kerosene and continued with 0.5% lead and 0.05% cobalt in the form of naphthenates. The resulting product dried on. 24 hours for a continuous film with a low lasting stickiness. 8— - MU. steel and was of the same type as the apparatus used in the manufacture of icing oil and alkyd resins. It consisted of a gas-heated boiler, which held 50 liters and was equipped with a stirrer, a device for taking samples under vacuum and a reflux condenser, arranged above the boiler and connected to a tube cooler, which was inclined towards a publisher. The heating was carried out for 3 hours, until the temperature was raised to 260 ° C, continued for a further 4.5 hours at a temperature of 290 ° C and then for a further 4 hours at 290 ° C. 5.5 kg of fatty acid and 0.8 kg of water were recovered. in the publisher.

The resulting residue weighed 13.7 kg and was washed repeatedly with boiling water. After drying at 100 ° C under vacuum and filtration on a filter press, the residue had the following properties: Acid number7, Prevalence number86 Iodine number (Wijs) 143 Non-digestible material32% Viscosity165 pois at 20 ° C After addition of 0.3% My and 0.02% manganese in in the form of naphthenate, the residue was dried to a tack-free state for 90 minutes and continuously for 150 minutes to a good, water-resistant, leak-like film.

The product obtained was suitable as a starting material for lacquers and varnishes, insofar as the leachates were therefore built on the basis of cobalt, lead and manganese compounds.

Example 15. In the apparatus described in Example 14, 20 kg of a fraction, obtained from soybean oil fatty acids (acid number 203.5, preselection number 206.3, iodine number according to Wijs 140.2 and non-digestible material 2.8%) and 0.4 kg were heated. technical boric acid under a vacuum of 13-20 mm Hg to 260 ° C for 10 hours and to 290 ° C within a further 2 hours. The fatty acids which distilled off during this heating were continuously returned to the reaction vessel. The heating was continued for 4 hours at a temperature between 260 and 290 ° C, however, the distillate obtained was collected in a publishing house. This contained 0.6 kg of 0.6 kg of a fatty acid distillate and 17.4 kg of a residue, which had the same character as stand oil: After cooling the residue to about 100 ° C, the still present boric acid was removed by repeated boiling with a few kg of water and separation of the wash water. The residue had a viscosity of 194 pois at 120 ° C, an acid number of 7.3, a preselection number of 17.9, an iodine number of 154.1 (according to Wijs) and contained 86% of non-digestible material.

After adding a lead / manganese naphthenic desiccant (0.3% lead and 0.02% manganese) and diluting with a mixture of turpentine and latte kerosene (1: 1) to a consistency of 1.5 pois at 20 ° C, a product with good drying properties, which were useful for the production of paint paints. A film of this product was dry to the touch after about 5 hours and completely dry after 7.5 hours.

The product obtained was suitable as a starting material for lacquers and varnishes, and the leachates were therefore built on the basis of cobalt, lead and manganese compounds.

Example 16. 100 g of peanut oil fatty acid having an acid number of 197.7 and an iodine value of 99.6 were heated with 3.5 g of boric acid trimethyl ester. The latter compound had been prepared from 1 mole of boric acid anhydride and 6 moles of methyl alcohol and was purified by distillation. The reactants were heated in a 250 ml round bottom flask made of Jena glass, on which a reflux condenser which could be heated and filled with V2A steel coils was placed. The heating was carried out at atmospheric pressure up to 140 ° G for 30 minutes. The flask was then evacuated to 2-3 mm Hg for 40 minutes, ie. sit fast as the distillation of the methyl alcohol allowed.

When the flake methyl alcohol was no longer released, the mixture was subjected to the following treatment: First, the bath was heated to 200 ° C within 20 minutes and then to 290 ° C for 150 minutes, kept at this temperature for 270 minutes and finally for 30 minutes, during which the fatty acid condensed in the backflow condenser, did not lick return to the reaction flask but was fed to a publisher connected to the other end of the backflow condenser. During the whole treatment a vacuum of about 2-3 mm Hg is established. The reflux condenser was initially heated to a temperature of 200 ° C and to 225 ° C during the distillation of the fatty acids.

Den erhallna aterstoden vagde 54, g. In the presence of lead manganese desiccant (0.3% lead and 0.02% manganese in the form of naphthenate), a film of this residue dried to a dry state of contact for 4.5 hours and with a slight stickiness of 24 hours. The residue had an acid number of 29.6, a preselection number of 63.9, an iodine number (Wijs) of 131 and a content of non-digestible material of 73.5%.

With the exception of a few crystals at the upper edge of the flask, the residue was free from solid boric acid. It could be completely freed from this acid by washing with water, but this was not necessary, since the presence of soluble boric acid compounds does not substantially affect the properties of the residue as a drying material. A similar product is obtained when using boric acid mannitol ester as a catalyst instead of boric acid trimethyl ester.

The product obtained was suitable as a starting material for lacquers and varnishes in that the sizing agents were therefore built on the basis of cobalt, lead and manganese compounds.

Example 17. 27 g of peanut oil fatty acids having an acid number of 197.7 and an iodine value of 99.6 were heated to -9 with 6.6 g of boron triacetate in the apparatus to be used for it. subsequent treatment. The mixture was heated one. hour at 100 to 140 ° C, after which the liberated attic acid was distilled off. In this sail, about 28 g of the mixed anhydride of boric acid and the peanut oil fatty acids were obtained. A mixture of this product and 73 g of linoleic fatty acid having an acid number of 198.6 and an iodine value of 137.1 was heated to 200-290 ° C according to Example 16 except that the distillation time had to be shortened from 30 to 10 minutes, since the product appeared to be highly viscous already. before distillation. The residue had an acid number of 43.9, a preselection number of 70.2 and an iodine number (Wijs) of 173.2.

Due to the high viscosity of the product, it was impossible to determine the exact content of non-digestible material. Upon air drying after the addition of a lead-manganese siccative, the product was found to be touch dry in 60 minutes and completely dry in 80 minutes.

The product obtained was suitable as a starting material for lacquers and varnishes, while the sedatives were built on the basis of cobalt, lead and manganese compounds.

Example 18. 165 g of peanut oil fatty acid (acid number 197.7, iodine number 99.7). and 10 g of boron triacetate were heated for 2 hours at 150 ° C in a 500 ml flask in a standardized water determination apparatus using an oil bath. The released attic acid was distilled off and removed from the water separator. 50 ml of decalin was filled through the reflux condenser. Since 16 ml was required to fill the water separator, 34 ml of decalin was added to the reaction vessel.

This mixture was boiled under reflux and atmospheric pressure. The liberated water collected in the water separator, while the decal returned. During separation of 11 ml of water and a total of about 15 ml of decalin, the boiling point of the mixture rose slowly, so that the temperature of the heating bath was 250 ° C after 2 hours, 260 ° C for one hour and 270-280 ° C for 30 hours. At the end of the treatment, 140 g of residue were obtained, which contained 9.8 ml of decalcine. This Residue consisted of a solution and both falling properties. Vardena mom parentes denote the properties of the residue in the absence of decal Acid number 9.8 (10.4) Prevalence number 16, (17.5) Iodine number (according to Wijs' method) 106, (113.1) Non-digestible material 79.0% (83, 8%) After the addition of 0.3% lead and 0.02% manganese in the form of naphthenate leachate, the residue became dry to the touch in 6 hours and completely dry in 24 hours. The product obtained was suitable as starting material for paints and varnishes as far as leaching were built on the basis of cobalt, lead and manganese compounds.

Example 19. 20 kg of distilled tall oil fatty acids having an acid number of 194.3, a prefalling number of 196.9, an iodine value (according to Wijs) of 131.5 and a resin content of 2 Vo were heated with 0.4 kg of technical grade boric acid in the apparatus described in Example 14, with mechanical agitation under a vacuum of 4-12 mm Hg. The temperature was raised for 2 hours to 230 ° C, for a further 10 hours to 260 ° C and kept between 260 and 290 ° C for 14 hours. The fatty acids which distilled off were reintroduced into the vessel. Towards the end of the reaction, only a small amount of fatty acids distilled off. After completion of heating, 17.5 kg of residue were recovered, which was washed with 5x20 kg of hot water until the boric acid was removed. The residue was then dried in vacuo and filtered with a filter press.

The product thus obtained had an acid number of 6.0, a preselection number of 13.2, an iodine number (Wijs) of 155.9, a content of 92.1% and a viscosity of 91.5 pois at 20 ° C.

After addition of 0.3% lead and 0.02% manganese in the form of naphthenate desiccant and dilution with light kerosene to a viscosity of 1.5 pois at 20 ° C, a film of this product became dry to the touch in 6 hours and completely dry in 8 hours.

The product obtained was suitable as a starting material for paints and varnishes, insofar as the siccatives were built on the basis of cobalt, lead and manganese compounds.

Claims (5)

Patent claim: A process for the preparation of condensation products, wherein fatty acids with form. COOH, van in R represents an unsubstituted saturated or preferably unsaturated alkyl group containing 9-25, preferably 17-21 carbon atoms, heated to a temperature of 220-330 ° C while condensing in the presence of an oxygen-containing boron compound at atmospheric pressure or under reduced pressure with removal of water formed during the condensation, characterized in that the reaction mixture is melted at a temperature of at least 250 ° C during the latter part of the reaction time, and that the fatty acids evaporated on heating are returned to the reaction mixture and heating is continued until the reaction product formed contains at least 40% by weight. an average molecular weight corresponding to that calculated by a condensation product with at least 3 molecules of the corresponding fatty acids, after which unreacted fatty acids per se were removed from the reaction mixture by extraction or distillation. 2. A process according to claim 1, characterized in that the fatty acids are ketone-containing. - 3. A method according to claims 1-2, characterized in that the heating is carried out under reduced pressure or at atmospheric pressure in the presence of a stream of an inert gas. 4. A method according to any one of claims 1-3, characterized in that the heating is carried out in the presence of an inert solvent boiling under the condensation conditions. 5. A process according to any one of claims 1-4, characterized in that the condensation catalyst consists of boron oxide or boric acid or a salt thereof with a volatile resin or of organic, oxygen-containing boron compound. Request publications: U.S. Patent Nos. 2,298,270, 2,298,916, 2,569,420.