DE1181167B - Swelling and gelling of saturated and unsaturated hydrocarbons - Google Patents

Description

Swelling and gelling of saturated and unsaturated hydrocarbons It is known to use sugar esters of higher fatty acids as emulsifiers and swelling agents Water to use.

Surprisingly, it has been found that compounds of the general formula in which R and / or R2 are hydrogen or a lower alkyl radical, which can also be halogenated, and R3 is an acyl radical of a higher saturated or unsaturated fatty acid, particularly good swelling and gelling agents are for saturated and unsaturated hydrocarbons with at least 5 C Atoms and, more generally, for those compounds that contain a longer saturated or unsaturated hydrocarbon radical with at least 5 carbon atoms.

Compounds of the above general formula can be found in simple way to produce by one of a monosaccharide and a Carbonyl compound Sugar derivative initially obtained in a known manner by transesterification Esterified with esters of higher saturated and unsaturated fatty acids. For the transesterification reaction can fatty acid esters of lower as well as higher or polyhydric alcohols be used.

The transesterification reaction can be carried out in a known manner in a solvent be performed. But it can also be used in particular with the isopropylidene compounds perform in the melt, due to the low melting point of this Products has the advantage that compared to the transesterification of other sugar derivatives can work at much lower temperatures. Generally temperatures are favorable between 100 and 200 ° C. The isopropylidene compounds are at these temperatures of the monosaccharides resistant and do not suffer any significant discoloration during the reaction, so that the transesterification products are obtained in pure form without any particular difficulty will.

The products obtained in this way show exceptional behavior, by being able to swell with hydrocarbons. So show for example 1,2-isopropylidene glucofuranosido-6-stearate, 1,2-isopropylidene glucofuranosido-6-oleate, 1,2-isopropylidene glucofuranosido-6-palmitate, 1,2-chloralosido-6-stearate excellent swelling and gelling properties for compounds such as petroleum ether, Gasoline, paraffin oil, spindle oil, higher fatty acid esters, oleic acid esters, edible oil.

When pouring over the said sugar ester derivatives with the hydrocarbons These swell slowly within a few days, releasing the hydrocarbon is completely absorbed. The process can be compared to the swelling of glue in water, where the sugar ester derivative takes the place of glue and the hydrocarbon or the compound containing a hydrocarbon radical takes on the role of water. If the sugar ester derivative is dissolved in the hydrocarbon in the heat, it solidifies the solution turns into a gel on cooling. The amounts of the sugar ester derivative that necessary to obtain a gel with a hydrocarbon are included 3 to 20 percent by weight. Compounds that have a longer saturated or well Contain, hold, and behave similarly to unsaturated hydrocarbon radicals. In some cases, e.g. B. in cooking oil, the effect is achieved by adding a little water favored.

The following table shows the amounts of sugar ester derivative in percent by weight that are necessary to obtain a gel that just no longer flows with a solvent at room temperature (23 ° C.): Gelability of various sugar ester derivatives Solvent 1,2-isopropylidene- 1,2-isopropylidene- 1,2-isopropylidene- glucofuranosido-6-stearate glucofuranosido-6-palmitate glucofuranosido-6-oleate Petrol 0.748 .............. 10.2 13.2 12.3 Spindle oil 0.915. . . . . . . . . . . 3.5 3.8 - Petroleum ether 0.655 ... ....... 19.3 24.2 9.7 Paraffin oil 0.876. . . . . . . . . . . 3.7 3.1 29.0 Oleic acid methyl ester 0.872 ... 4.1 6.2 10.7 Cooking oil 0.925 (contains about 5% 1120) ... 3.1 4.3 - The values for the chloralosido-6-stearate are in the same order of magnitude as for the 1,2-isopropylidene glucofuranosido-6-stearate.

If more sugar ester derivative is dissolved, then form accordingly gels firmer on cooling. The strength or stiffness of the gel depends on the applied Amount of sugar ester derivative.

When using sugar ester derivatives as swelling agents emulsifiers are also used, so that correspondingly pasty emulsions or Suspensions arise.

For example, a stiff paste or ointment is obtained when one the ingredients listed below are stirred together in the heat and then under Stir slowly to cool.

60.5 paraffin oil, 32.0 water, 4.3 tech. Emulsifier, 3,2 1,2-isopropylidene glucofuranosido-6-palmitate or 54.3 liquid paraffin, 40.0 water, 2.85 sugar monostearate, 2.85 1,2-isopropylidene glucofuranosido-6-palmitate.

The gels produced according to the invention can be used for the most varied of purposes Purposes use, in particular, they can depending on the hydrocarbon or the compound containing a longer hydrocarbon radical for all of those Find purposes for which these compounds are also used. Included the gels offer the advantage that the hydrocarbon or a longer hydrocarbon residue containing compound are fixed in the gel form and lost their liquid form to have. An easy flowing hydrocarbon, such as. B. Oetan, relies on this Way into a non-flowing form, at the same time also its evaporation rate is reduced. It can also be used in this form for all purposes for which it is otherwise used in its liquid form.

The gels can also be used as cleaning agents, such as z. B. as a floor care product or shoe care product.

Example 1 I 1 g of 1,2-isopropylidene glucose are heated in vacuo with 14.9 g of methyl stearate and 0.1 g of potash, which had previously been freshly calcined and finely powdered, to 180 ° C. in a vacuum bath while stirring. The still hot liquid mass is poured into 120 ml of ethyl acetate. After standing for 20 minutes, it is filtered off and the solution is concentrated in vacuo. The residue is a brown, waxy mass, from which 1,2-isopropylidene-glucofuranosido-6-stearate is obtained as a colorless crystalline substance with a melting point of 46 ° C. by recrystallization from ethanol. Yield: 18.1 g = 74.5% of theory.

Example 2 I 1 g of 1,2-isopropylidene glucose are heated with 14.5 g of methyl ester and 0.3 g of potash, which had previously been freshly calcined and finely ground, in a vacuum with stirring in an oil bath at 180 ° C. for 1 hour and 20 minutes. It is then poured into 100 ml of ethyl acetate. After 20 minutes of standing, it is suctioned off and the solution is concentrated in vacuo. The 1,2-isopropylidene glucofuranosido-6-oleate is obtained as a pale yellow colored waxy mass. Yield: 19 g = 77% of theory.

Example 3 I 1 g of 1,2-isopropylidene glucose are heated with 14.5 g of methyl palmitate and 0.15 g of potash, which had previously been freshly calcined and finely ground, in a vacuum with stirring at 180 ° C. for 2 hours. The still warm melt is then poured into 100 ml of ethyl acetate. After 20 minutes of standing, it is suctioned off and the solution is concentrated in vacuo. The 1,2-isopropylidene glucofuranosido-6-palmitate is obtained as an almost colorless, waxy mass. Yield: 13.9 g = 58.1% of theory.

Example 4 23.2 g of β-chloralose are dissolved in 150 ml of dimethylformamide and the solution with 20 g of methyl stearate and 1 g of freshly calcined and finely ground Potash offset. The mixture is heated to 80 ° C for 12 hours and under a Maintained vacuum of 80 mm Hg. The catalyst is then filtered off and the dimethylformamide is distilled off in vacuo. The residue is extracted with acetone and recrystallized twice from methanol. The ß-chloralosido-6-stearate is obtained as a colorless crystalline substance with a melting point of 38 to 39 ° C.

Example s 11g 1,2-isopropylidene glucose, 15.7g previously dried Cooking oil and 0.8 g potash, which was freshly annealed and finely powdered beforehand, will heated together for 3 hours in an oil bath at 180 ° C. During this Time the mixture is stirred and kept under vacuum. Then the The melt is poured into 150 ml of ethyl acetate, the solution is briefly boiled with a little charcoal and filtered at room temperature. Then the ethyl acetate is distilled off. To drying in vacuo leaves 19.2 g of the sugar ester derivative in the form of an amber-yellow obtained waxy mass. V Z 66.3.

Example 6 22.0 g of 1,2-isopropylidene glucose, 29.0 g of lard and 0.2 g of potash, which was previously freshly annealed and finely powdered, are put together heated with vigorous stirring in a vacuum of 20 mm Hg for 3 hours in an oil bath at 180 ° C. The melt is then poured into 150 ml of ethyl acetate, the resulting solution decolorized with activated charcoal and filtered. On standing the filtrate for one hour A small amount (about 2 g) of unreacted 1,2-isopropylidene glucose still falls in the refrigerator which is filtered off. The filtrate from it is evaporated in vacuo and the The residue was dried in vacuo at 50.degree. This gives 23.5 g of the sugar ester derivative obtained in the form of a colorless waxy mass. The substance has good gelling properties in hydrocarbons. Example ? 2 g 1,2 - isopropylidene glucofuranosido - 6 - 8 ml of petrol (white spirit, petroleum ether 50 to 70 ° C) are poured over stearate and left to stand in a sealed jar at room temperature. After this The petrol is completely absorbed by the sugar ester derivative after standing for 20 minutes, whereby a gelatinous gel-like mass has formed. This can be done by heating liquefy and solidify from it after cooling to room temperature a stiff translucent gel-like mass.

Example 8 2 g of 1,2-isopropylidene glucofuranosido-6-stearate, with 8 ml Paraffin oil treated in the same way as in Example 6 are after 33/4 hours swollen to a gel-like mass, while with 8 ml of cooking oil the swelling process Takes 8 hours.

EXAMPLE 9 2 g of 1,2-isopropylidene glucofuranosido-6-palmitate swell in 8 ml of gasoline (white spirit, petroleum ether 50 to 70 ° C.) in 23 hours to form a gel-like mass, while with 8 ml of edible oil it is no longer at room temperature after 7.5 hours flowing gel-like mass is obtained. Example 10 If 2 g of sugar ester derivative obtained from 1,2-isopropylidene glucose and edible oil are treated with 8 ml of gasoline (white spirit, petroleum ether 50 to 70 ° C.) or with 8 ml of edible oil as in Examples 6 and 7, are the times that the 2 g of the sugar ester derivative need to swell and to form a gel-like mass that just no longer flows at room temperature, with 8 ml gasoline 13/4 hours and with 8 ml cooking oil 1/2 hour.

Example 11 If the gel-like mass obtained by swelling 200 mg 1,2-isopropylidene glucofuranosido-6-stearate was obtained in 3 g of paraffin and 7 g of white spirit is left to stand for 24 hours, during this time 98 mg of white spirit evaporate, while a mixture of 3 g paraffin and 7 g white spirit in 24 hours 820 mg white spirit loses. This shows quite impressively that in gels obtained in this way as here z. B. the gasoline is not just mixed in as a solvent, but similar the z. B. swelling processes known from bentonite in the molecular structure of the sugar ester derivative must be included.

The production of the sugar esters described is not claimed here.

Claims (1)

Claim: Use of sugar ester derivatives of the general formula in which R1 and / or R2 are hydrogen or a lower alkyl radical, which can also be halogenated, and R3 is an acyl radical of a higher saturated or unsaturated fatty acid, as a swelling and gelling agent for saturated and unsaturated hydrocarbons with at least 5 carbon atoms and for those compounds which contain a longer saturated or unsaturated hydrocarbon radical with at least 5 carbon atoms. Older patents considered German Patent No. 1091687.