RU2039087C1 - Method for production of emulsifiable compositions for greasing leather - Google Patents

Abstract

FIELD: processing leather. SUBSTANCE: proposed compositions are prepared at 65-105 C within 0.5-1.0 h by liquid phase oxidation with the help of oxygen. Mixture of synthetic or natural fats and oil is oxidized in the presence of catalyst, its quantity being 0.001-0.01 of mass of oxidizing mixture. The process is followed by treatment thus prepared oxidant with 20 aqueous solution of sodium sulfate. Mentioned above mixture represents mixture on the base of products of oxidation of cyclohexane, products of dehydration of cyclohexanol and of polycondensation of cyclohexanone having high boiling point. Mixture of copper, chromium and barium salts of fatty acids is used as mentioned above catalyst, mass ratio of metals in said catalyst being 10:10:1. EFFECT: improves efficiency of the method. 3 cl, 2 tbl

Description

 The invention relates to the leather industry, namely the production of fatliquoring materials and emulsifiers for the leather industry.

 A known method of obtaining an emulsifiable composition for fatliquoring of the skin by sulfonation of fish oil or by digesting with concentrated sulfuric acid [1] The disadvantage of this method is the multi-stage process and large amounts of toxic waste.

Another known method for obtaining the composition of the fatliquoring by sulfonation pre-oxidized natural fats and oils with sodium bisulfite [2] The disadvantage of this method is the high temperature of the process (90-95 ° ^C) and its significant length (up to 10 hours).

The closest in technical essence to the claimed invention is a method for producing the composition of the fatliquoring leather by non-catalytic air oxidation of the mixture of fish oil and butter AML components at a mass ratio of 4: 1 and a temperature of 75-105 ^{° C,} followed by treatment with oxidate 20% aqueous solution sodium sulfite at a temperature of ²⁰ ° C, and a weight ratio oxidate solution of sodium sulfite 10 4 for 20 min [3]
The disadvantage of this method is its low productivity, due to the long duration (3 hours) of the stage of producing fish oil co-oxidate with oil.

 The aim of the present invention is to increase the productivity of the method of obtaining a composition for fatliquoring.

This goal is achieved in that the oxidate is produced by passing air for 0.5-1.0 hours through a heated mixture of fat and oil based on a mixture of high-boiling products of oxidation of cyclohexane, dehydrogenation of cyclohexanol and polycondensation of cyclohexanone (AML oil) with an AML oil content of a mixture of 4-19 wt. wherein the oxidation is carried out at a temperature of 65-105 ^{° C} in the presence of a catalyst mixture of copper, chromium and barium salts of fatty acids at a weight ratio of metals in the catalyst of 10: 10: 1 and the amount of catalyst 0,001-0,010% by weight of fat of the initial mixture with oil AML and animal fats, vegetable oils, synthetic fats, fatty acid esters or mixtures thereof are used as fat.

 Characteristics of the raw materials used.

 Technical fish oil 1-3 grades (GOST 1304-76) "Technical fats of fish and marine mammals."

 Animal fats 1-3 grades (GOST 1045-73) "Technical animal fat".

 Non-food sunflower oil (GOST 1129-81).

 Flaxseed oil (GOST 5791-81).

 Synthetic fat (GOST 11010) "Synthetic fat for the leather industry".

Esters methyl fractions C ₁₀ -C ₁₈ according to TU 38.100727-78.

 Oil POD TU 113-03-476-82 "POD oil (a mixture of high-boiling products of the oxidation of cyclohexane, dehydrogenation of cyclohexanol, polycondensation of cyclohexanone)."

 Technical sodium sulfite (GOST 5644-75) "Sodium sulfite anhydrous."

The catalyst, which is a mixture of a copper salt of the formula CuA ₂ (M _cp -673), chromium salt CrA ₃ (M _cf -967) and barium salt BaA ₂ (M _cf -747), where A is an anion of unsaturated fatty acid with an average molecular weight (M _cf ) 306, obtained by the method of exchange decomposition in organic media. The mass ratio of metals in the catalyst is Cu: Cr: Ba 10: 10: 1.

 Obtaining a composition for fatliquoring of the skin of the claimed method is as follows.

 A mixture of fat, AML oil and a catalyst in the required mass ratio is loaded into an oxidizer equipped with a jacket and a bubbler for air supply, after which the reaction mixture is heated. Upon reaching the operating temperature, an air current is supplied to the oxidizer and oxidation is carried out at a given temperature for 0.5-1 hours, controlling the completeness of oxidation by taking samples of the oxidate and then checking them for sulfonation.

 The finished oxidate is loaded into a container equipped with a mechanical stirrer, in which a 20% aqueous solution of sodium sulfite was previously prepared. Stirring is continued for 20 minutes until a homogeneous mass is obtained.

PRI me R 1. 620 kg of fish oil, 155 kg of oil, and the catalyst in an amount of 0.005% of the total mass of fat and oil is loaded into an oxidizer equipped with a jacket and a bubbler for air supply, and start heating. When the temperature reached 85 ^C. oksidator fed into the flow of air and oxidize the mixture at the same temperature for 30 minutes. The obtained oxidate is pumped into a container equipped with a mechanical stirrer, where 250 l of a 20% aqueous solution of sodium sulfite were previously prepared, after which the reaction mixture was stirred for 20 minutes until a homogeneous mass was obtained. The finished product is a moving cherry-red transparent or translucent mass with a basic substance content of 78%. The 5% aqueous emulsion of the product has a milky white or cream color and is stable for 72 hours; A 1% emulsion of the product in an electrolyte solution is stable for 12 hours.

 PRI me R s 2-13. The dependence of the properties of the final product on the mass ratios of the starting components, the amount of catalyst used and on the conditions of the oxidation process are given in table. 1.

 As follows from examples 1-3, a decrease in the mass fraction of AML oil in the oxidate is below 4 wt. leads to an unacceptable decrease in the stability of aqueous emulsions of the product obtained by the claimed method. On the other hand, increasing the mass fraction of POD oil to 20% and higher is unacceptable due to the appearance of a strong unpleasant odor in the product, which is transmitted during the fatliquoring process to the skin and thereby reduces its quality.

 From examples 4-6 it is seen that a decrease in the amount of catalyst used below the level of 0.001% by weight of the initial reaction mixture does not allow to obtain a well emulsifiable product for the oxidation time indicated in the application. An increase in the duration of oxidation is impractical, since it is the intensification of the stage of co-oxidation of fats with AML oil that is the purpose of the claimed invention.

 On the other hand, an increase in the proportion of catalyst over 0.010% does not give a noticeable improvement in the emulsifiability of the product obtained by the claimed method (examples 7.8), and does not allow to further reduce the duration of oxidation (examples 7.8.9).

From examples 10-13 it follows that a decrease in the temperature of oxidation to 55 ^about With even for the maximum time claimed in the invention does not allow to obtain a product that gives sufficiently stable emulsions. As was established by additional research, for qualitative oxidate at said temperature required time of about 4-7 hours. On the other hand, the upper temperature limit is limited to 105 ^{° C,} because at higher temperatures the processes of thermo-oxidative degradation of oil and fat components from AML occur intensely the release of large quantities of low molecular weight highly toxic substances with concomitant gum formation, which not only leads to environmental pollution, but also to a significant degree It reduces audio quality of the product, including the ability to form a stable emulsion with water.

 PRI me R s 14-22. Table 2 shows the properties of products obtained from fat co-oxides of various chemical nature with AML oil.

 It is clearly seen that all the compositions obtained using the starting fats given in Table 2 satisfy the requirements of the leather industry with regard to the stability values of their aqueous emulsions (at least 1 hour for a 10% product emulsion in water).

 Laboratory studies on the "worker" installation have confirmed the possibility of using each of the resulting compositions as a fatliquoring material for the manufacture of chrome tanned leathers, both individually and in a mixture with other fatliquoring materials.

 The composition based on complex fish oil cooxidate with mesher oil and AML oil (Example 21) was the basis for the new fatliquoring preparation “RPM”, which has successfully passed production tests and is currently preparing for large-scale production.

Claims (3)

METHOD FOR PRODUCING EMULTIABLE COMPOSITIONS FOR FATING SKIN by liquid-phase air oxidation of a mixture of fat and oil based on a mixture of high-boiling products of cyclohexane oxidation, dehydrogenation of cyclohexanol and polycondensation of cyclohexanone at an elevated temperature, followed by treatment of the obtained oxidate with sulfate / aqueous 20% sodium hydroxide solution sodium sulfite 10 4 and a temperature of 20 ^o C for 20 min, characterized in that the oxidation is carried out at 65 - 105 ^o C for 0.5 to 1.0 h in the presence of cat an analyzer of a mixture of copper, chromium and barium salts of fatty acids with a mass ratio of metals in the catalyst of 10 10 1 and the amount of catalyst of 0.001 0.01% by weight of the oxidized mixture of fat with oil.  2. The method according to claim 1, characterized in that animal fats, vegetable oils, synthetic fats, fatty acid esters or mixtures thereof are used as fat.  3. The method according to claim 1, characterized in that the oil content based on a mixture of high-boiling products of the oxidation of cyclohexane, dehydrogenation of cyclohexanol and polycondensation of cyclohexanone in the initial reaction mixture is 4 to 19%

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