RO110490B1 - Alkylglycidilethers preparation process - Google Patents

Abstract

The process of obtaining a alkylglycidyl ethers used in the preparation of stabilizers for photo emulsions are the reaction to 2 moles of alcohol (n-butyl, n-pentyl or n-hexyl) with 1 mol of epichlorohydrin, in the presence of the catalyst BF3: Et2 O and ZnCl2 or BF3: AcOH and ZnCl2 at T = 90-95 ° C for 4-6 hours, the epichlorohydrin being introduced dropwise into T = 80 ° C, in the 2nd step recycling takes place of the intermediate obtained in the presence of 20% NaOH to yield the alkylpolyethers are purified by distillation.

Description

The present invention relates to a process for obtaining alkylglycidyl ethers.

It is known that epoxeters are chemical compounds used as intermediates in many organic syntheses, such as, for example, obtaining acrylic epoxy monomers or stabilizers for photo emulsions.

The alkylpoxieters are obtained by the reaction of 2 moles of alcohol with 1 mol of epichlorohydrin in acid catalysis, at temperatures between

-10 ° C and 100 ° C.

The reaction consists of two steps, the first being α-monohydroxy hydrochloride, according to the reaction:

ROH + CI -CH ₂ -CH-CH ₂ --------> RO-CH, -CH-CH ₂ -Ci \ / Ί

An OH in the second step taking place 15 forming alkylglycidyl ethers: recycling the obtained intermediate product,

RO-CH ₂ -CH-CH, -C1 —-.......> RO-CH ₂ -CH-CH ₂ + NaCl + H ₂ O

I \ /

OH NaOH O

Obtaining α-monohydroxy-α'-20 alkyl ether in the first step occurs in acid catalysis, as catalyst using BF ₃ : Ft ₂ O or SnCl ₄ , in the amount of 0.0060.02 mol to 1 mol epichlorohydrin.

Although, in the specialized literature there are 25 yields up to 85-90% in the case of using as a catalyst the complex BF ₃ : Et ₂ O, in practice these yields do not exceed 50%.

The process according to the invention removes this disadvantage by using as a catalyst a mixture of 0.005-0.02 mol BF ₃ : Et ₂ O and 0.003-0.01 mol ZnCl ₂ for 1 mol epilchlorhydrine, yielding alkylglycidyl ethers. , wherein the alkyl groups are 35 "-butyl, π-pentyl and" -hexyl, with yields between 90 and 95% relative to epichlorohydrin.

The advantages of applying the invention are the following: 40

- the technology for obtaining the alkylglycidyl ether is easy to achieve;

- the raw materials used are accessible;

- the reaction yields are between 45 and 95% compared to epichlorohydrin;

- the alkylglycidyl ethers obtained have a purity of 90-95%.

The following are four examples of the invention:

Example 1. In a 2 1 flask, fitted with a stirrer, thermometer, drip funnel and heating source, 5 moles of «-butanol (370 g), 0.015 mol (2 ml) BF ₃ : Et ₂ O are introduced. and 0.007 mol (1 g) ZnCl ₂ .

The mixture was heated to 80-85 ° C, when slowly, 2.5 moles of epichlorohydrin (231.2 g) were introduced dropwise for 0.5 h, the temperature then rising to 90-95 ° C, where is maintained for 4 h, after which the reaction mixture is cooled.

At 25-30 ° C add 500 g 20% NaOH solution and the mixture is heated to 40-45 ° C for 4 hours.

The reaction mixture is separated into a separating funnel, the upper organic layer being collected, which is then distilled at atmospheric pressure, and the distillation fraction between 165 and 170 ° C is collected as a clear liquid butylglycidyl ether. .

292 g butylglycidyl ether is obtained in a yield of 91% over epichlorohydrin. The product was analyzed by infrared spectrometry and gas chromatography, its purity being 93.25%.

Example 2. In the same installation, described in Example 1, at an addition of 5 moles «-butanol (370 g), 0.01 mol (ί, 5 ml) BF ₃ : AcOH and 0.007 mol (1 g) ZnCL, dropwise, at 80-85 ° C, 231 g epichlorohydrin (2.5 5 moles) for 0.5 h, the temperature had risen to 100 ° C, where it is maintained for 4 h, after which the reaction mixture is cooled.

At 25-30 ° C, add 500 ml of 20% NaOH solution and heat for 10 hours at 40-45 ° C.

The reaction mixture was distilled at atmospheric pressure, yielding the distillation fraction between 165 and 170 ° C, butylglycidyl ether. 15

280 g butylglycidyl ether is obtained in a yield of 90.5% over epichlorohydrin. The product was analyzed by spectrometry, infrared and gas chromatography, its purity being 94.3%. 2 0

Example 3. In the installation, described in Examples 1 and 2, at an addition of 5 moles «pentanol (440 g), 1.5 ml BF ₃ : Et ₂ O (0.01 mol) and 0.007 mol ZnCl ₂ (1 g ), add dropwise at 80-85 ° C, 231 g 25 epichlorohydrin (2.5 moles) for 0.5 h, the temperature rising to 100 ° C, where it is maintained for 6 h, after which the mixture of reaction cools.

At 25-30 ° C, 500 ml of 20% NaOH solution is added and heated for 40 hours at 40-45 ° C.

The reaction mixture is separated into a separating funnel, the upper organic layer being collected. 3 5

The product is distilled at atmospheric pressure, collecting the fraction 190-200 ° C, as a pentylglycidyl ether, with a clear liquid appearance. 330 g of product are obtained, with a yield of 93%, the purity of the product being 93.88%.

Example 4. In the laboratory installation, described in the previous examples, with an addition of 150 g «-hexanol (5 moles), 2.5 ml BF ₃ : Et, O (0.02 mol) and 0.007 mol ZnCl ₂ (1 g), dropwise added at 85 ° C, 231 g epichlorohydrin (2.5 moles) for 0.5 h, the temperature rising to 100 ° C, where it is kept for 5 h, after which the mixture is cooled to temperature at 25-30 ° C, add 500 ml NaOH solution and heat for 4 hours at 40-45 ° C.

The two layers, aqueous and organic, are separated, and the organic layer is distilled, yielding ter hexylglycides, as a distillation fraction, between 210 and 220 ° C. 368 g of product are obtained, with a yield of 92%. The product was analyzed by infrared spectrometry and gas chromatography, the purity being 91.38%.

Claims (1)

Claim Process for obtaining alkylglycidyl ethers by reacting alcohols having 4 to 6 carbon atoms with epichlorohydrin in acid catalysis, followed by recycling the resulting intermediates, characterized in that a mixture of 0.005-0.02 mol is used as catalyst in the reaction medium. BF ₃ : Et ₂ O and 0.003-0.01 mol ZnCl ₂ or 0.005-0.02 mol BF ₃ : AcOH and 0.003-0.01 mol ZnCl ₂ for 1 mol epichlorohydrin, yielding alkylglycidyl ethers, wherein the alkyl groups are «-Butyl, n-pentyl and« hexyl with yields between 90 and 95%, the purity of the products being 90-95%.