JPS58144328A - Production of alkyl chloride - Google Patents

Abstract

PURPOSE:The reaction between hydrochloric acid and an alkyl alcohol under pressure gives an alkyl halide easily in very low costs, which is used as a starting material for cationic surface active agents and as an esterification agent for carboxylic and phosphoric acids. CONSTITUTION:The reaction between an alkyl alcohol such as n-butyl alcohol or 2-ethylhexyl alcohol and hydrochloric acid is carried out under pressure of 0.5- 50kg/cm<2>, preferably 1-30kg/cm<2> to give an alkyl chloride such as n-butyl chloride or n-ethylhexyl chloride. The present process does not employ zinc chloride, which makes the process complicated, and thionyl chloride, which is expensive, both of which have been used in conventional methods.

Description

[Detailed description of the invention] The present invention relates to a method for producing alkyl chlorides.

Conventionally, the main methods for producing alkyl chloride from alkyl alcohol are (1) heating a mixture of alcohol containing zinc chloride and hydrochloric acid at normal pressure, or (2) heating the alcohol with water-free hydrogen chloride. Either by mixing and heating to cause a direct reaction, or (6) by reacting the alcohol with thionyl chloride.

However, in method (1), zinc chloride must be used in an amount equivalent to or more than the mole of alcohol, and furthermore, when zinc chloride that has been used once is to be reused, it must be ignited to 250°C or higher. Therefore, if this method is used industrially, a large amount of zinc monide is used, making the operation complicated, and furthermore, the regeneration of zinc chloride is carried out at a high temperature, which is difficult due to the material of the equipment. In addition, the method (χ) is industrially unfavorable because hydrogen chloride, which does not contain water, is more expensive than hydrochloric acid. Furthermore, in method (3), not only is thionyl chloride more expensive than hydrochloric acid, but hydrogen chloride and sulfur dioxide gas are produced as by-products, which require treatment.

Therefore, this method is not only industrially expensive but also complicated to operate, making C.S.

Therefore, the present inventors conducted intensive research on a method for producing alkyl octachloride from only hydrochloric acid and alkyl alcohol at an extremely low cost, and as a result, completed the present invention.

That is, the present invention is a method for producing alkyl chloride, which is characterized by reacting an alkyl alcohol and hydrochloric acid under pressure.

The alcohol used as a raw material in method 9 of the present invention is:
Straight chain or branched, cyclic, having 6 to 20 carbon atoms;
Furthermore, these hydrogen atoms are substituted with phenyl groups. These alcohols are primary or secondary.

For example, Eva? L-furobyl alcohol, n-7”
f alcohol, 2-ethylhexyl alcohol, 9-nonyl alcohol, 9-dodecyl alcohol, n-pentatecanyl alcohol, n-ophtathecyl alcohol, inpropyl alcohol, sec-7' tyl alcohol, 2-octyl alcohol, 6 - Benzyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, 2-ethylcyclohexyl alcohol, benzyl alcohol, 2-phenylethyl alcohol, etc. 6° Hydrochloric acid may be 10 or more, and the reaction will proceed even if it is less than this, but the reaction will proceed. It takes a long time and is not practical.

In other words, 66% or more must be produced under pressure using hydrogen chloride gas, which is industrially disadvantageous as it is more expensive than when only hydrochloric acid is used. Therefore, the concentration of hydrochloric acid is preferably in the range of 10 to 66%.

The amount of hydrochloric acid used should be at least equivalent to the alcohol.
It is usually in the range of 1 to 5 equivalents. Within this range, alkyl chloride can be obtained with a sufficiently good yield. More than 5 equivalents may be used, but it is not necessary.

In the method of the invention, the reaction is carried out under pressure. The pressure is 0.5-5゜hg/at at the reaction temperature,
Preferably it is 1 to 50 kq/cl. 0.5 kq
/d or less, the reaction requires a long time and is not practical;
If it exceeds s o ka/cr/I, the reaction equipment becomes expensive, which is industrially disadvantageous. Normally, alcohol and hydrochloric acid are added to a reactor at room temperature and pressure, the reactor is sealed as is, the reaction temperature is set to a specified temperature, and the reaction is continued for a certain period of time under the increased internal pressure, or alcohol and hydrochloric acid are reacted first. After that, the inside of the container is raised to a predetermined pressure with an inert gas such as nitrogen, and then the reaction is carried out.

The reaction temperature is from 110 to 180'O, and if it is lower than this, the reaction will take a long time, while if it is higher than 1800C, it is not preferable because it will result in the formation of abrasives such as olefins and ethers.

The reaction time varies depending on the concentration of hydrochloric acid used, but is 1 to 20
Time is enough. A short reaction time of 1 hour or less will not yield a sufficient yield, while a long reaction time of over 20 hours will not have the effect of further improving the already sufficiently achieved yield. I can't wait.

After the reaction is carried out as described above, it is cooled and returned to normal pressure. At this time, if the product is liquid at room temperature, the reaction solution is separated into two layers, so by liquid separation operation,
If the product is solid at room temperature, it can be removed by filtration. Alkyl chloride of sufficient purity can be obtained only by such isolation operations. However, if higher purity is required depending on the purpose of use, the purpose can be achieved by ordinary methods such as distillation and recrystallization.Also, if the raw material alcohol is soluble in water or hydrochloric acid, By washing the unreacted starting alcohol mixed in the isolated product with water or hydrochloric acid, alkyl chloride can be obtained with a purity comparable to that obtained by distillation.

According to the method of the present invention, alkyl chloride can be easily and extremely inexpensively produced in a high yield, without using zinc fumedide, which requires complicated post-treatment, or using expensive thionyl chloride, as in conventional methods. be able to.

The obtained alkyl chloride can be used as a raw material for a cationic surfactant or as an esterifying agent for carboxylic acid or phosphoric acid.

The present invention will be explained below with reference to Examples.

Example 1 n-butyl alcohol 22.2.9 (0.5 mol) and 1
365 g (1.2 mol) of 21% hydrochloric acid was added to a 5 [] Oml glass autoclave equipped with a pressure gauge, the autoclave was sealed, and the autoclave was placed in an oil bath at 120°C (7). Pressure gauge is O
kq /crl became to &9 /crl.

This was left as it was without stirring for 18 hours. After the reaction was completed, it was cooled, the reaction solution was added to a separatory funnel, and the upper layer of spore-butyl chloride was taken out. The yield was 243 g, and the purity was 97% according to gas chromatography analysis, and the third component was 9-butyl alcohol, the raw material. The yield was 85 fO. This was washed twice with 30 g of 12% hydrochloric acid to remove n-butyl alcohol. Yield 26°05. lit, purity is 9
The yield was 85%.

The boiling point was 78.5°C.

Elemental analysis 0. CH04 as H2O2 Theoretical value (451,919,8038,30 Actual value ((a) (1.5 mol) was placed in a stainless steel autoclave equipped with a pressure gauge and a stirring bar containing a 500ml glass reaction tube, and the autoclave was sealed, and then pressurized with nitrogen until the pressure gauge read 1ohq/c-++1. This product was heated to an internal temperature of 150°C in an oil bath.

The pressure gauge at this time read 13 #/d. 10 as is
Stir for hours.

After the reaction is completed, it is cooled and returned to normal pressure, and the chloride 2-
The ethylhexyl layer was separated. The yield was 71.3 g, and the purity was 97% according to gas chromatography analysis.

Yield: 93 cm. This was purified by vacuum distillation.

Yield 66.99 (63°c/18try44g),
Yield 90%.

Elemental analysis 08H1701 0H (J Theoretical value (□□□ 64.63 11.53 23
．． 84 actual value (@ 64.51 11.60
23.71 Example 3 2-phenylethyl alcohol 122 g (1.0 mol)
and 152.1 g (1.5 mol) of 36% hydrochloric acid at 500 m/
! The mixture was placed in a glass autoclave equipped with a pressure gauge, sealed, and placed in an oil bath at 160°C.

The pressure gauge is 3. from ohg/cri. Oko became /7. This was left as it was for 2 hours without stirring. After the reaction was completed, the mixture was cooled and the 2-phenylethyl chloride layer was separated by a liquid separation operation. The yield was 1264I, and the purity was 98% as determined by gas chromatography. Yield: 86 cm.

This was purified by vacuum distillation. Yield 115.3.9 (
92°C/16NfnHfI) Yield: 82cm.

Elemental analysis 0, HC1 theoretical value (qQ 6B filter 4 6.45 25.2
1 Actual value (%) 68,21 6.51 2
5.23 Example 4 9-octadecyl alcohol B i g (0.5 mol) and 164.6 g (1 g 5 mol) of 30% hydrochloric acid in 500 m
The glass reactor No. 1 was placed in a stainless steel autoclave equipped with a pressure gauge and a stirring bar, and the autoclave was sealed, and then pressurized with nitrogen until the pressure gauge read 2 okq/d. This material was heated to an internal temperature of 17,000 ℃ by soaking it in oil gas.

At this time, the pressure gauge read 25 kg/crd. The mixture was stirred as it was for 10 hours. After the reaction was completed, the mixture was cooled and returned to normal pressure, and the n-octadecyl chloride layer was separated by a liquid separation operation at 3,000 or more. The yield was 867 g, and the purity was 97% according to gas chromatography analysis. Yield: 97. This was purified by vacuum distillation.

Accommodation 4482.4.9 (185-190'C/15mmH
y), yield 95%.

Elemental analysis 018H3tO (1 0HC1 Theoretical value (@ 74.82 12.91 12
．． 27 actual measurement value ((6) 74.91 12.82
12. Filter 1 Example 5 Cyclohexyl alcohol 50. (Sooml: 1g (0.5 mol) and 165.9g (10 mol) of 22nd hydrochloric acid
Place in a glass autoclave fitted with a pressure gauge and close.
, and placed in an oil bath at 12o°C. The pressure gauge is Okg/
crt! From 2. It became OKG/CRI.

The mixture was left as it was for 5 hours without stirring. After the reaction was completed, the mixture was cooled and the cyclohexyl chloride layer was separated by a liquid separation operation. The yield was 562 g, and the purity was 95% as determined by gas chromatography. Yield: 90 cm. This was purified by vacuum distillation. Yield 516 g (68°C/62 Ht), Yield 87 Elemental analysis OHOl as 06H, □01 Theoretical value (Long 60.76 9.55 29.89
Actual value ((6) 60,81 9.51 29.
99 Patent Applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) A method for producing alkyl chloride, which comprises reacting an alkyl alcohol and hydrochloric acid under pressure.