HU192257B - Process for contineous production of cyclic-aluminiumcarboxilates /trimers/ - Google Patents

Abstract

The prods. are obtd. in continuous operation by reacting aluminum alcoholates with mono-chloro-carboxylic acids in the presence of water and solvent. The preheated reaction partners loose water in the form of steam which is mixed to the carrier gas and solvent, the aluminum-alcoholates are reacted with the chloro-carboxylic-acids, the byprod. alcohol is condensed from the carrier gas, and eliminated from the reaction mixt. The carrier gas is then returned to the start of the process, the reaction mixt. is stabilised and the solvent-diluted trimeric aluminum-oxide-carboxylate is sepd.

Description

The present invention relates to a process for the continuous production of cyclic alumina carboxylate trimers.

Aluminum-based gelling agents have long been known since the industry has used aluminum stearate, aluminum hydroxy stearate, palmitate, etc. for decades. for the preparation of various hydrocarbon gels. The rapid development of mechanical engineering and technologies over the past decade has made it necessary to produce high quality gel systems. This development is significant especially in aluminum complex grease production, but there is a similar trend in the cosmetics industry, canvas-skin impregnation, hardening oil, paint, etc. manufacturing.

These gel systems are mostly made with hydroxyaluminum dicarboxylates. Hydroxyaluminum dicarboxylates are prepared from aluminum alcoholates, most often in hydrocarbon-containing compositions.

Aluminum alcoholate, which in most cases is aluminum isopropylate, is generally reacted with an oleophilic and an oleophobic acid. The most commonly used oleophilic acids are: caprylic, capric, lauric, myristic, palmitic, stearic, 12-hydroxystearic, arachic, mellitic, oleic and linoleic acids. Oleophobic acids generally include benzoic acid, toluic acid, dimethylbenzoic acid, phenylacetic acid, phenylpropionic acid, salicylic acid, and the like. In these reactions, the addition of 2 moles of carboxylic acid to the alcoholate results in the release of 2 moles of alcohol which is distilled from the system.

II

- G - R 'removed. Hydrolysis of the formed dicarboxyl alcoholates produces the gelling hydroxyaluminum dicarboxylates. Considering that the aluminum content of the formed gel systems is less than 1% by volume and that the formed dicarboxylaluminum alcohol greatly increases the viscosity of the hydrocarbon, it is not surprising that the removal of alcohol from these systems is very costly, expensive and highly flammable. alcohol regeneration is generally not possible. Similar technological problems are encountered in carrying out hydrolysis, which, since the aluminum complex gels have a drop point above 210 ° C, can be carried out at high temperatures, and it is very difficult to homogenize relatively small amounts and recover the liberated alcohol.

Because of the problems outlined above, the development of hydroxyaluminum dicarboxylates is accomplished by the use of more advanced technologies from other base materials, the cyclic aluminum isopropylate trimers.

The preparation of the aluminum complex gel based on the cyclic aluminum isopyropyrate trimer produces 1 mol of alcohol per mole of aluminum. The process becomes considerably simpler because of its lack of hydrolysis and is also advantageous in terms of flammability, since only one-third of the alcohol released is liberated from the production of aluminum alcoholate.

We have developed a continuous process for directly producing a cyclic alumina carboxylate trimer. From this starting material, aluminum complex gels are formed according to the following reaction equation:

Al / \

0

R * is a cyclic alumina carboxylate trimer

II

- C - R '/

-> - 3 HO - Al \

- C - R 'II 0 hydroxyaluminum carboxylic acid

-2. 192 257

It can be seen that the preparation of the aluminum complex gel based on the cyclic alumina carboxylate trimer does not release alcohol. The process can be carried out in simple grease fryers.

Batch processes for the preparation of cyclic aluminum alcoholate trimers are disclosed in the literature. According to French Patent No. 1 277 308 (OA1OR) ₃ types of aluminum polymers can be prepared - C2 -C5 alkoxy group by heating the corresponding aluminum trialkoxide in the presence of water vapor (0.95 to 1.05): . No. 3 054 816. US Patent Specification equivalent amount of steam of 2-5 carbon number aluminum alkoxide is reacted with times _t _ gouge in the presence of a solvent or in alcohol, refluxoltatják the solvent or the alcohol, hot steam and distilled alcohol and 2 moles of aluminum per mole of product approx. It is cyclized at 150 ° C.

According to U.S. Patent No. 2,925,430, HO-C-Al-O-Ί-R

I x J ⁿ polymers can be prepared where R is C 1 -C 10 alkyl, X is carboxyl, n is a natural integer. According to the patent, for example, polyaluminium stearate is prepared by reacting 1 molar equivalent of aluminum isopropylate in anhydrous xylene with 1 molar equivalent of anhydrous stearic acid at 85-95 ° C for 1 hour, adding about 1 molar equivalent of water to the reaction product. Reflux at 95 ° C for 1 hour. The temperature is raised from 95 ° C to 140 ° C while isopropanol is distilled off. The xylene mixture is reacted at 140 ° C for 1 hour and finally maintained under vacuum.

U.S. Patent No. 2,979,497 describes reactions of aluminum alcoholates, monocarboxylic acids and water. They are reacted in various order to yield cyclic alumina polymers.

British Patent No. 825,878 discloses that 20% of the monocarboxylic acid can be replaced by di- or polycarboxylic acid and thus describes the preparation of various polymer-organic-aluminum compounds.

All of these processes produce cyclic alumina carboxylate trimers in batches with multiple operations, long reaction times and strong mechanical stirring.

We have developed a continuous process for the manufacture of cyclic (OA10OCR ') ₃ trimers. In the process, the aluminum alcoholates of formula A1 (OR) ₃ - R is a C3 -C5 alkyl group - are reacted together with water vapor and monocarboxylic acids in the presence of a solvent. The molar ratio of the reaction components include H ₂ O / A1 (OR) ₃ <1 R / COOH / A1 (OR) ₃ <1 R¹COOH monocarboxylic acids of the formula used are 8-22 carbon atoms, saturated or unsaturated fatty acids and these fatty acids mixtures. The reaction components and the solvent are preheated, the water is evaporated, and the water vapor is mixed with the solvent and the carrier gas. The reaction components, the solvent and the carrier gas are introduced into a reactor, whereby the carrier gas is fluidized into a phase in which the chemical reactions take place very rapidly. The residence time of the reaction mixture in the reactor is at least 20 minutes and the temperature of the reactor is at most 130 ° C. Along with the carrier gas, the alcohol vapors released during the reaction are completely removed, which are condensed and removed from the carrier gas and recycled to the beginning of the process. The reaction mixture is passed from the fluidized reactor to the stabilizing reactor. Depending on the solvent and the monocarboxylic acid used in this reactor, the reaction mixture is heated to a temperature such that the formation of the cyclic alumina carboxylate trimer compound is completed. A small amount of alcohol liberated during stabilization is introduced into the gas stream and the solvent diluted cyclic alumina carboxylate trimer is removed.

The process is illustrated in the accompanying figure. The aluminum alcoholate, water, solvent and carboxylic acid are heated in the preheater (1-4), and the water vapor is introduced into the reactor (5) together with the solvent and the carrier gas. Our reactor is a gas-liquid fluid-heated heated reactor, which is operated with sufficiently intensive stirring. The gas leaving the reactor carries with it the alcohol vapor which is discharged from the condenser (7). The gas is circulated through the pump (8). The reaction mixture passes from the reactor (5) to the stabilizing reactor (6) where trimer formation takes place and from which the product is drained. A small amount of alcohol liberated in the stabilizing reactor is introduced into the circulating gas stream.

Example 1

Into a 3 cm diameter 2 m high jacketed glass reactor, 874 g of 96% Al (iPrO) ₃ , 1068 g of hydrogenated Soviet heavy oil, 948 g of technical stearic acid and 60 g of water are fed per hour. The feed materials were preheated to 120 ° C. The gas circulation rate is 800 l / h.

The reactor temperature was brought to 125 ° C and the stabilizing reactor temperature was 147 ° C. Anhydrous isopropyl alcohol (571 g) and product (2380 g) were withdrawn per hour. Our product is an oil-free, aluminum hydroxide-free material with an aluminum content of 4.7% by weight.

Example 2

850 g of Al (iPrO) ₃ , 1072 g of oleic acid, 1250 g of spindle oil and 66 g of water are fed to the above reactor. The feed materials were preheated to 125 ° C and the water was evaporated. Circulation was performed at 600 l / h. The reactor temperature was brought to 120 ° C and the stabilizing reactor temperature was 142 ° C. From the system, 720 g of isopropyl alcohol and 2516 g of product were withdrawn per hour. The aluminum content of our product was 4.3%.

192 25 ⁷ .

Example 3

944 g of acid mixture was introduced into the reactor of Examples 1 and 2 preheated to 130 ° C, which was 20% by weight linoleic acid, 20% by weight caprylic acid, 10% by weight palmitic acid, ⁵ 40% by weight stearic acid, 5% by weight laurylic acid and 5% by weight It was prepared by mixing erucic acid and 1150 g of 98% aluminum amylate, 68.5 g of water and 1180 g of cosmetic vaseline oil per hour. The reactor was stirred by circulating 1000 L of gas. The reactor tem- ^one stopping, was cooled to 130 ° C, the reactor temperature was stabilized at 180 ° C. 960 g of amyl alcohol was discharged from the condenser and 2380 g of product from the stabilizing reactor. Products did not contain aluminum hydroxide, alumíniumtartal- ¹ m was 4.4% by weight.

Claims (6)

Claims A process for the continuous production of cyclic trimer (OA10OCR ') ₃ - R' is a C8-C22 alkyl or alkenyl group Al (OR) ₃ aluminum alcoholate R is a C3-C5 alkyl group and R'COOH saturated or unsaturated fatty acids, R 'as defined above, or mixtures thereof and water in the presence of a solvent, characterized in that the reaction components and the solvent are preheated, the water is evaporated, the water vapor is mixed with the solvent and the carrier gas; to reactor at a molar ratio of H ₂ O: A1 (OR) ₃ <1, R'COOH: A1 (OR) ₃ <1, with inert carrier gas A fluidized phase is formed at 90-130 ° C, the volume ratio of the carrier gas to the liquid phase introduced (200-350): 1 and the residence time of the reaction mixture is adjusted to at least 20 minutes and the alcohol released from the fluidization reactor with the carrier gas separating, condensing the alcohol from the mixture of carrier gas and alcohol, draining the condensed alcohol and returning the carrier gas to the beginning of the process, passing the reaction mixture from the fluidization reactor to a stabilizing reactor, heating to 140-180 ° C and releasing the traces of alcohol followed by removal of the solvent-diluted cyclic alumina carboxylate trimer. 2. Azl. The process according to claim 1, wherein the molar ratios of the reaction components introduced into the fluidization reactor are maintained at H ₂ O: Al (OR) ₃ = 0.8-0.95 and R'COOH: A 1 (OR) ₃ = 0.80.95. . Process according to claim 1 or 2, characterized in that the residence time of the reaction mixture in the fluidization reactor is adjusted to 20-40 minutes. 4. The process according to any one of claims 1 to 3, wherein the temperature of the fluidization reactor is maintained at 120-130 ° C. 5. Process according to any one of claims 1 to 3, characterized in that the solvent is a hydrocarbon having a boiling point above 140 'C or a mixture of hydrocarbons. 6. A process according to any one of claims 1 to 3, wherein the carrier gas is nitrogen or a nitrogen / air mixture.