JPS58203927A - Production of chloromethyl alkyl ether - Google Patents

Abstract

PURPOSE:The mixture resulting from reaction between an aliphatic alcohol, formaldehyde and hydrogen chloride is separated into the oil phase and aqueous phase and the titled substance is obtained from the oil phase, further the aqueous phase is distilled to recover the titled compound dissolved in the phase. CONSTITUTION:A hydrogen chloride gas is blown into the alkylated formalin formed by introducing formaldehyde into an aliphatic alcohol under normal pressure at 10-25 deg.C for 2-4hr, then the reaction mixture is stood to effect separation and the titled substance is obtained from the oil phase. The aqueous phase is heated over 90 deg.C, preferably at 100 deg.C to distill off more than 70wt% of organic compounds in the aqueous phase and 8-40wt%, preferably 10-30wt%, of the total aqueous phase, thus recovering the titled substance more than double the amount dissolved in the aqueous phase. EFFECT:Since the organic components in the aqueous phase is markedly reduced, the load on the active sludge is decreased in waste water disposition. USE:An agent for introducing anion-exchange groups in the production of anion- exchange resins.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to chloromethyl alkyl ether (hereinafter referred to as CAE).
(abbreviated as )).

Chloromethyl alkyl ethers such as chloromethyl ether (hereinafter abbreviated as CMR) are useful as processing agents for introducing exchange groups into polymer particles when producing anion exchange resins. Typically, for example, OMB
A known method for producing is to react methanol, formaldehyde and hydrogen chloride as shown in the reaction formula below.

OH, OH+ HOHO+ HOj□aa, oaH, c
t + H,0 In this method, the mixture FicMK after the reaction
Since the oil phase is a mixture of water and oil, the oil phase and water phase are separated and CMIC is recovered from the oil phase, but unreacted methanol and hydrogen chloride are left in the water phase after separation. In addition, a small amount of 0Mll1 and, for example, methyl (OH
, 0OII, OCR, ). However, since the amount of OMII contained in the aqueous phase of 0rIC is extremely small, conventionally, the 0rIC in the aqueous phase is not recovered, but is usually disposed of after neutralizing the aqueous phase with an alkali and then treated with activated sludge. was.

The present inventors have conducted various studies on methods for recovering Om2 contained in the aqueous phase obtained by the above reaction, etc., and have found that by depositing the aqueous phase at a certain temperature, OA of one or more times the amount of 0mX dissolved in the aqueous phase in advance
The present invention was completed by demonstrating that K can be distilled and recovered in a high yield.

That is, the gist of the present invention is a method for producing OAK by reacting aliphatic alcohol, formaldehyde, and hydrogen chloride, which comprises separating the reaction mixture into an oil phase and an aqueous phase,
Chloromethylalkyl ether, characterized in that dichloromethylalkyl-kl-thyl is produced by heating the aqueous phase under distillation conditions, and chloromethylalkyl ether is recovered in an amount greater than the amount of chloromethylalkyl ether dissolved in the aqueous phase. It lies in the method of manufacturing ether.

The present invention will be explained in detail below.

The present invention is directed to a reaction in which an aliphatic alcohol, formaldehyde, and hydrogen chloride are reacted to produce OAR. Aliphatic alcohol-h,! Examples of the alcohol include alcohols having carbon number/-4, such as methanol, ethanol, n-propanol, and n-butanol. The product is determined depending on the type of alcohol; for example, in the case of methanol, CMIC is synthesized. This reaction is an equilibrium reaction, and the desired product OAK
Since an equimolar amount of water is generated along with the reaction, it is desirable that the water concentration in the reaction raw material be low. Therefore, although the raw material formaldehyde may be used as an aqueous solution, it is usually used as so-called alkylated formalin, which is obtained by absorbing formaldehyde in an aliphatic alcohol in advance. In addition, when formaldehyde is used as an aqueous solution,
For example, a high concentration of 3 oiltt11 or more is preferable. On the other hand, as hydrogen chloride, gaseous hydrogen chloride is usually used.

Further, in this reaction, a small amount of methitool or the like may be present.

The amount of formaldehyde used is usually O, S to 1 mole, preferably o, g to 8 moles, relative to the aliphatic alcohol. Although it varies somewhat depending on the water content, it is usually 7 to 1 mole times, preferably 8 to 1 J mole times, relative to the aliphatic alcohol.

If the amount of hydrogen chloride used is too small atb, the reaction will not proceed well, and conversely, even if it is too large, there will be no difference in the effect, which is not economical.

The reaction temperature is usually 1. t-QOC1 preferably 10
The reaction time is usually about 1 to 10 hours. This reaction can be carried out, for example, by keeping a solution of formaldehyde absorbed in a predetermined amount of aliphatic alcohol at a predetermined temperature under stirring, and then blowing hydrogen chloride gas into the solution.

Since the mixture after the reaction is a mixture of an oil phase containing OAK as a main component and an aqueous phase, this is usually left to stand and then separated into an oil phase and an aqueous phase. This liquid separation produces the desired product, CAE.
is recovered as an oil phase. On the other hand, in the aqueous phase there are usually 3 to 3
! The aqueous phase is further processed to recover the ahx, which contains a weight of CA1, a t-70 weight of aliphatic alcohol, and a J-3 weight of methictool.

In the present invention, the organic compounds in the aqueous phase are distilled out and the distillate is recovered by heat-treating the aqueous phase, but the heat treatment is usually performed at a temperature of tOC1, preferably 1OOCK, at a temperature of the aqueous phase under normal pressure.
is carried out until it is reached. In this treatment, a distillate fraction of at least 10% by weight, preferably at least /θ weight, is distilled out from the total aqueous phase. Preferably, the reaction is carried out until almost all of the organic compound in the aqueous phase has been distilled off. With this heat treatment, 0A
Organic components such as In, aliphatic alcohols, and metetool are distilled out, but in this process, the O contained in the aqueous phase is initially removed.
It is faster to collect 0AIC, which is approximately twice as much as AK. Although the cause of this is not clear, it is thought that some of the methictool, aliphatic alcohol, hydrogen chloride, etc. present in the aqueous phase react during distillation, and OAK is synthesized.

What is the recovery rate of chloromethyl alkyl ether?

When the distillate exceeds qo weight relative to the original aqueous phase, it is effectively saturated. Therefore, the distillate is t-diO to the aqueous phase.
It is effective to select from a range of high weight, preferably Fi 70 to 30 weight, from the viewpoint of recovery rate and heat source cost.

It contains an organic component mainly consisting of distillate 1jOAllf recovered by the above-mentioned distillation, and water distilled together with the organic component. Therefore, this distillate is, for example, CAII! By sending the manufactured reaction product to the liquid separation step, it can be separated and recovered together with CAB in the reaction mixture. For example, this distillate is further separated into an oil phase and an aqueous phase, and the oil phase is circulated to the CAI manufacturing plant.
, it can also be collected.

In the present invention, OAK can be efficiently recovered from the aqueous phase after one liquid separation by the above-described treatment. It is surprising that the present invention can recover a larger amount of CAB than expected, which is about twice as much as the amount of CAB contained in the aqueous phase. Historically, organic components in the aqueous phase are significantly reduced, so even when the aqueous phase is used for wastewater treatment, it also has the effect of reducing the load on activated sludge.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example Equipped with a stirrer, temperature controller, and hydrogen chloride gas blowing pipe.

, r in a reactor, methylated formalincoSt, *t, in which 1 mol of formaldehyde was absorbed in 1 mol of methanol.
The reaction was carried out by blowing hydrogen chloride gas into the reactor at a rate of 3 t/hr for a period of time while stirring and maintaining the temperature at 150°C.

After the reaction, the mixture was allowed to stand, and then the oil phase was separated.
r, jf and aqueous phase/! 411 were recovered. When the oil phase was analyzed by gas chromatography, the content of CMIC was 1113.3% by weight, and when the aqueous phase was analyzed in the same way, it was found that CM! ,? , j% by weight, methanol t,
4 by weight and Metetool J, 1 by weight.

The paddy rice obtained above was transferred to a 300 ml flask equipped with a distillation apparatus, and heat-treated by increasing the temperature from 2 IC to s hours to obtain distillate-4, rif.

In addition, the hydrochloric acid concentration f in the pot residue after heat treatment was 41% by weight.

Almost no organic compounds remained. The composition of the distillate recovered by this method was analyzed and the results are shown in Table WE1.
The recovered 90MIIi contents are shown in Table 1.

Table 1 Table J, Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - (1 other person)

Claims (4)

[Claims] (1) In a method for producing chloromethyl alkyl ether by reacting aliphatic alcohol, formaldehyde, and hydrogen arsenide, the mixture after one reaction is separated into an oil phase and an aqueous phase, and the aqueous phase is heat-treated under distillation conditions. A method for producing chloromethyl alkyl ether, which comprises producing chloromethyl alkyl ether by doing so, and recovering chloromethyl alkyl ether in an amount greater than the amount dissolved in the aqueous phase of the chloromethyl alkyl ether. (2) A method for producing chloromethyl alkyl ether according to claim (1), characterized in that 0% by weight or more of organic compounds in the extract phase is distilled out by heat-treating the aqueous phase. . (3) The heat treatment is performed until t-+0mt* of the total weight of the aqueous phase is distilled out.
) A method for producing the glue tetraalkyl ether described in section 2. (4) The method for producing chloromethyl alkyl ether according to claim (1), characterized in that the aqueous phase is heat-treated at a temperature of 90C or higher under normal pressure.