The method of obtaining pinacoline

 

(57) Abstract:

The inventive methylbutan enter into interaction with the polymer of formaldehyde at a molar ratio of 1 : 0.4 to 1.1 in the environment of 20 - 40% aqueous solution of sulfuric acid at 20 to 40oC, separate the organic layer, process it at 70 - 180oC and the pressure methylbutanol when the mass ratio of the total amount of methylbutane and a polymer of formaldehyde is 1 : 0,9 - 1,1, aqueous solution of sulfuric or phosphoric acid or an aqueous solution of acidic alkali metal salt of one of these acids, or aqueous solution of one of these acids and acid salts, the concentration of the acid ranges from 0 to 60 wt.%, the salt concentration of 0 to 30 wt.%, as methylbutanol use isoamylenes fraction of intermediate isoprene production. 1 C.p. f-crystals, 1 table.

The invention relates to the chemistry of ketones, and in particular to methods of obtaining pinacoline (methyltretbutylether).

Pinacolin finds wide application in industry as a solvent for varnishes and paints, intermediate in the synthesis of medicinal and aromatic substances, pesticides group triazinones etc.

There are several ways of obtaining pinacoline, the quality of the catalyst;

2) the interaction of isoamylenes or derivatives thereof with formaldehyde or its derivatives in the presence of acids as catalysts (reaction Prince).

According to the first method pinacolin get in 2 stages:

1) electrochemical or chemical receiving enconcert from acetone to yield enconcert 50 - 60%;

2) pinacolada regrouping with the release of pinacoline up to 90 %.

Pinacolada rearrangement is an effective method of obtaining pinacoline. For example, a method of obtaining pinacoline from enconcert in the presence of sulfuric or phosphoric acid with simultaneous distillation of the desired product in the form of an azeotrope with water. The reaction temperature 90 - 115oC. the Yield of the target product is about 90%.

The main disadvantage of methods based on pinacolin rearrangement, is the accumulation of products resinification in the catalyst, which prevents its long-term use and high cost of enconcert due to the complexity of its production and low output. The total yield of pinacoline on the original acetone is 40 - 50%. More promising are the ways, the main reaction isoamylenes (methylbutanol) with formaldehyde. Eyrie. According to the method based on the reaction of the Prince, pinacolin get in two stages:

1) the interaction of 2-methylbutan-2 with an aqueous solution of formaldehyde using as catalyst sulfuric acid get 4,4,5-trimethyl-1,3-dioxane;

2) hydrolysis of 4,4,5-trimethyl-2,3-dioxane in the presence of acids get pinacolin and formaldehyde. The output pinacoline 2-methylbutane-2 is about 60%.

This method has not found industrial application, because it has major drawbacks:

1) high consumption of formaldehyde and difficulty of disposal;

2) insufficiently high output and a large amount of waste (resinous products and wastewater).

In subsequent years, this method has again attracted the attention of researchers in the patent literature there were various modifications with improved technical and economic performance, in one of which the second stage is carried out in the presence of 2-methylbutan-2, which can be disposed of formaldehyde to obtain the target product. The output pinacoline is 69%. Some modifications of this method include the use not only of isoamylenes and formaldehyde, but also their derivatives. These spoolbases and loses its activity, replacing it leads to the formation of large amounts of wastewater. Regeneration of its complex, energy intensive and also leads to the formation of wastewater. The use of polymers of formaldehyde excludes dilution of the catalyst, however, the yield of the target product while significantly below 60%. In addition, it is not possible continuous process, because the process is conducted at a pressure and dosage of solid reagents in these very difficult conditions.

Closest to the present invention is a method of obtaining pinacoline, in which the process is carried out in two stages: the interaction of methylbutanol at stage I with hydrochloric acid at 75 - 86oC and a molar ratio methylbutan : hydrogen chloride 1 : 3, then, after separation of the reaction mixture, the organic layer is distilled to isolate the intermediate product - chloride isoamylene that at stage II enter into interaction with aqueous formaldehyde solution in hydrochloric acid medium, after which the desired product is recovered from the reaction mass by distillation in the form of an azeotrope with water, followed by distillation.

The method allows to obtain a product with the output 78 of 89%.

Despite the high output, Hey hydrochloric acid, you need to either regenerate or to neutralize that leads to the formation of large amounts of wastewater;

2) the process can be complicated in hardware design, as required stage of selection of the intermediate product - chloride isoamylene and stage of regeneration of hydrochloric acid or its neutralization and wastewater treatment.

The aim of the invention is to reduce the education process wastewater and waste production and simplification of the apparatus registration process.

This goal is achieved by the fact that the interaction of 2-methylbutane-1, 2-methylbutane-2 or mixtures thereof, or isoamylenes fraction (intermediate isoprene production) with polymers of formaldehyde is carried out in 2 stages:

1) interaction of the polymer of formaldehyde with methylbutane when a molar ratio of 1 : 0.4 to 1.1, respectively, at a temperature of 20 - 40oC, atmospheric pressure in the environment of 20 - 40% aqueous solution of sulfuric acid, then the reaction mass is subjected to delamination, while the lower inorganic layer return in the cycle, and the upper organic layer is directed to the second stage;

2) the interaction of the organic layer with stage I additional kolichestvo 1:0,9-1,1, at a temperature of 70 -180oC and autogenous pressure (3 - 30 ATM) in aqueous solution of sulfuric, phosphoric, phosphonic, diphosphonic acids or their acid salts of alkali metals, or mixtures of these acids and their acid salts. After completion of the reaction the mixture rasclaat and the organic layer is directed to the selection of pinacoline known methods, and the aqueous layer was returned to the cycle. The concentration of acid in the aqueous phase, 0 to 60 wt.%, their salts 0 - 30 wt.%.

Both stages are conducted under vigorous stirring.

Example. In a reactor equipped with a stirrer, reflux condenser, addition funnel, load 20 to 40% solution of sulfuric acid in a quantity amounting to 0.5 volume of the reactor, and the polymer of formaldehyde. Then when mixing the metered isoamylenes fraction, the temperature in the reactor supports 20 - 40oC. After holding at this temperature and vigorous stirring for 2 to 5 h, the reaction mass rasclaat within 15 - 20 minutes Bottom aqueous solution of the catalyst return in the process, and the upper organic layer is passed to the second stage.

Getting pinacoline carried out in vials made of glass with a capacity of 15 ml Vial fitted with an airtight cover and device for Atara, the organic layer stage I and methylbutane that the total ratio of polymers of formaldehyde and methylbutanol was 1 : 0,9 - 1,1. After components are loaded ampoule is sealed and incubated with vigorous shaking at 70 - 180oC for a specified time. After cooling the contents of the ampoule is cooled, opened and the syringe being unloaded. The operation was performed 20 times, and then the organic layer are combined and subjected to fractional distillation. The results of the experiments are given in the table. The given examples show that the target product of the proposed method is obtained with the yield up to 89.9%. The temperature rise at the second stage above the upper limit leads to the reduction of the yield due to the formation of osmola, and when the temperature drops at stage I is below the lower limit reduces output. The total ratio of the polymer of formaldehyde : methylbutan 1 : 0,7 (i.e., outside the lower boundary) leads to lower output and 1 : 1,4 does not reduce output, but the excess methylbutanol reduces pickup of product per unit of reaction volume.

In laboratory and pilot plant tested that the catalysts I and II stages can be recycle for a long time (going to be replaced in khimpromstal. Thus, compared with the prototype of the proposed method, without reducing output, significantly reduce the amount of waste acids from 4.5 to 0.02 t/t, which leads to a drastic reduction of wastewater, and to simplify the hardware design process.

As a base case adopted a method of producing pinacoline electrochemical dimerization of acetone with subsequent rearrangement of enconcert in pinacolin. The output pinacoline on the acetone is 48%. On 1 t of the target product, playback method, is formed of 16 m3wastewater and 1.4 m3organic waste.

1. The method of obtaining pinacoline, including the interaction of methylbutane with formaldehyde, characterized in that, to simplify the way, methylbutan enter into interaction with the polymer of formaldehyde at a molar ratio of 1 : 0.4 to 1.1 in the environment of 20 - 40% aqueous solution of sulfuric acid at 20 to 40oTo separate the organic layer, process it at 70 - 180oC and autogenous pressure of methylbutanol when the mass ratio of the total amount of methylbutane and a polymer of formaldehyde of 1 : 0.9 to 1.1 in the aqueous solution of sulfuric, or phosphoric or phosphonic or diphosphonic acids or acid and its acid salts, the concentration of the acid ranges from 0 to 60 wt.%, the salt concentration of 0 to 30 wt.%.

2. The method according to p. 1, characterized in that as methylbutanol use isoamylenes fraction is an intermediate in the production of isoprene.

 

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