阅读说明：本技术 3-氯甲基-3-乙基氧杂环丁烷的制备方法 (Preparation method of 3-chloromethyl-3-ethyl oxetane ) 是由 钱晓春 翁云峰 马丽君 胡春青 衡京 于 2019-10-31 设计创作，主要内容包括：本发明提供了一种3-氯甲基-3-乙基氧杂环丁烷的制备方法。该制备方法包括：向熔融的三羟甲基丙烷中通入氯化氢气体进行氯代反应,得到含有一氯代物和二氯代物的混合物体系,氯化氢气体每小时的通入重量为三羟甲基丙烷投入总重量的2‰～13‰；精馏分离上述混合物体系分别得到二氯代物中间体和含一氯代物的母液；上述二氯代物中间体进行环合反应,得到3-氯甲基-3-乙基氧杂环丁烷产物；含一氯代物的母液直接套用至下一批反应的氯代反应。通过限定氯化氢的通气量,提高了氯化氢的利用率；反应生成的二氯代物可以继续反应制备成产品,残余母液再次作为氯代反应的原料,从而实现氯化氢和三羟甲基丙烷的高效利用,降低制备成本。(The invention provides a preparation method of 3-chloromethyl-3-ethyl oxetane. The preparation method comprises the following steps: introducing hydrogen chloride gas into the molten trimethylolpropane to perform chlorination reaction to obtain a mixture system containing monochloride and dichlorinate, wherein the introduction weight of the hydrogen chloride gas per hour is 2-13 per mill of the total weight of the trimethylolpropane; rectifying and separating the mixture system to respectively obtain a dichlorinated intermediate and a mother liquor containing monochloride; performing cyclization reaction on the dichloro compound intermediate to obtain a 3-chloromethyl-3-ethyl oxetane product; the mother liquor containing monochloride is directly applied to the chlorination reaction of the next batch of reaction. The utilization rate of the hydrogen chloride is improved by limiting the ventilation quantity of the hydrogen chloride; the dichlorinated product generated by the reaction can be continuously reacted to prepare a product, and the residual mother liquor is used as the raw material of the chlorination reaction again, so that the high-efficiency utilization of the hydrogen chloride and the trimethylolpropane is realized, and the preparation cost is reduced.)

1. A method for preparing 3-chloromethyl-3-ethyl oxetane, which comprises the following steps:

introducing hydrogen chloride gas into the molten trimethylolpropane to perform chlorination reaction to obtain a mixture system containing monochloride and dichlorine, wherein the introduction weight of the hydrogen chloride gas per hour is controlled to be 2-13 per thousand of the total weight of the trimethylolpropane;

rectifying and separating the mixture system to respectively obtain a dichlorinated intermediate and a mother liquor containing monochloride;

performing cyclization reaction on the dichloro compound intermediate to obtain the 3-chloromethyl-3-ethyl oxetane product;

directly applying mother liquor containing monochloride to next reaction to replace trimethylolpropane in equal amount, and continuously introducing hydrogen chloride gas to make chlorination reaction.

2. The preparation method according to claim 1, wherein the chlorination reaction is carried out in a closed reactor under a pressure of 1.01-1.50 MPa.

3. The method according to claim 1, wherein the reaction is terminated when the conversion of the dichloro compound is 45 to 80%.

4. The method of claim 2, wherein the closed reactor is a multistage tandem falling film reactor.

5. The method of manufacturing according to claim 1, further comprising: carrying out the chlorination reaction under the action of an organic acid catalyst; the dosage of the organic acid catalyst is 5-15% of the charging amount of the trimethylolpropane.

6. The method according to claim 5, wherein the organic acid catalyst is one or more selected from the group consisting of acetic acid, propionic acid, malonic acid, succinic acid, and adipic acid.

7. The method according to claim 1, wherein the temperature of the chlorination reaction is 120 to 140 ℃.

8. The method according to claim 2, wherein when the chlorination reaction is carried out under a pressurized condition, the pressure of the reaction system is 1.2 to 1.5MPa, and the weight of the introduced hydrogen chloride per hour is 6 to 13% o of the charged amount of the trimethylolpropane.

Technical Field

The invention relates to the field of organic synthesis, and in particular relates to a preparation method of 3-chloromethyl-3-ethyl oxetane.

Background

The oxetane monomer is one of the key components in the formula of the existing cationic system, and has excellent application performance and huge market prospect. 3-chloromethyl-3-ethyloxetane in the preparation of oxetane monomersIs the most important intermediate and is the irreparable factor for solving the problem of cost of the oxetane monomer. The conventional production method of 3-chloromethyl-3-ethyl oxetane needs to use highly toxic sulfonate, and along with the increasingly strict requirement on environmental protection, the original production method is difficult to ensure normal production, and the operation cost is sharply increased, so that the productivity is increasingly reduced. At present, a hydrogen chloride process is used for preparing 3-chloromethyl-3-ethyl oxetane instead of the original sulfonic acid ester process, for example, a hydrogen chloride preparation process is used in a patent JPB0003367549, although toxic substances are avoided, the utilization rate of hydrogen chloride gas and the conversion rate of dichlorides are not considered, the overall cost is too high, and the requirement of industrialization on low cost cannot be met; the JPB0004760827 patent adopts tower equipment to improve the process and improve the utilization rate of hydrogen chloride, but the conversion rate of dichlorinated products and the recovery of hydrogen chloride gas are not controlled, the cost is still high, and the purposes of low cost and large industrialization cannot be achieved. Therefore, the production cost of the conventional 3-chloromethyl-3-ethyloxetane is too high to realize industrialization.

Disclosure of Invention

The invention mainly aims to provide a preparation method of 3-chloromethyl-3-ethyl oxetane, which solves the problem of high preparation cost of the existing preparation method of oxetane monomers.

In order to achieve the above object, the present invention provides a method for preparing 3-chloromethyl-3-ethyloxetane, comprising: introducing hydrogen chloride gas into the molten trimethylolpropane to perform chlorination reaction to obtain a mixture system containing monochloride and dichlorinate, wherein the introduction weight of the hydrogen chloride gas per hour is 2-13 per mill of the total weight of the trimethylolpropane; rectifying and separating the mixture system to respectively obtain a dichlorinated intermediate and a mother liquor containing monochloride; performing cyclization reaction on the dichloro compound intermediate to obtain the 3-chloromethyl-3-ethyl oxetane product; directly applying mother liquor containing monochloride to next reaction to replace trimethylolpropane in equal amount, and continuously introducing hydrogen chloride gas to make chlorination reaction.

Furthermore, a closed reactor is adopted for chlorination reaction, and the reaction pressure is controlled to be 1.01-1.50 MPa.

Further, the reaction is terminated when the conversion rate of dichlorinated products is 45-80%.

Further, the chlorination reaction is carried out in a multistage falling film reactor arranged in series.

Further, the preparation method also comprises the following steps: carrying out chlorination reaction under the action of an organic acid catalyst; the dosage of the organic acid catalyst is 5-15% of the charging amount of the trimethylolpropane.

Further, the organic acid catalyst is one or more selected from the group consisting of acetic acid, propionic acid, malonic acid, succinic acid, and adipic acid.

Further, the temperature of the chlorination reaction is 120-140 ℃.

Further, when the chlorination reaction is carried out under a pressurized condition, the pressure of the reaction system is 1.2-1.5 MPa, and the weight of the introduced hydrogen chloride per hour is 6-13 per thousand of the input weight of the trimethylolpropane.

By applying the technical scheme of the invention, the utilization rate of the hydrogen chloride is improved by limiting the ventilation quantity of the hydrogen chloride; the occurrence of side reactions is reduced by controlling the conversion rate; the dichlorinated product generated by the reaction can be continuously reacted to prepare a product, the residual mother liquor is used as the raw material of the chlorination reaction again, the high-efficiency utilization of the hydrogen chloride and the trimethylolpropane is realized, the preparation cost of the 3-chloromethyl-3-ethyl oxetane can be effectively reduced, and the industrial popularization is facilitated.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As described in the background art, the existing methods for preparing oxetane monomers have the problem of high preparation cost. In order to solve the above technical problems, the present application provides an industrial preparation method of a 3-chloromethyl-3-ethyloxetane compound, comprising: introducing hydrogen chloride gas into the molten trimethylolpropane to perform chlorination reaction to obtain a mixture system containing monochloride and dichlorinate, wherein the introduction weight of the hydrogen chloride gas per hour is 2-13 per mill of the total weight of the trimethylolpropane; rectifying and separating the mixture system to respectively obtain a dichlorinated intermediate and a mother liquor containing monochloride; performing cyclization reaction on the dichloro compound intermediate to obtain the 3-chloromethyl-3-ethyl oxetane product; directly applying mother liquor containing monochloride to next reaction to replace trimethylolpropane in equal amount, and continuously introducing hydrogen chloride gas to make chlorination reaction.

In the preparation method, the utilization rate of the hydrogen chloride is improved by limiting the ventilation quantity of the hydrogen chloride; the dichlorinated product generated by the reaction can be continuously reacted to prepare a product, the residual mother liquor is used as the raw material of the chlorination reaction again, the high-efficiency utilization of the hydrogen chloride and the trimethylolpropane is realized, the preparation cost of the 3-chloromethyl-3-ethyl oxetane can be effectively reduced, and the industrial popularization is facilitated.

It should be noted that the cyclization of the dichlorides can be carried out by a technique known in the art. Preferably, the above-mentioned ring-closing process comprises: reacting dichlorinated products, a catalyst and alkali, when the content of the dichlorinated products in the raw materials is less than or equal to 2%, finishing the reaction, filtering, wherein a filter cake is solid salt, and carrying out reduced pressure rectification on the filtrate to obtain the product 3- (chloromethyl) -3-ethyl oxetane. Preferably, the catalyst may be tetrabutylammonium bromide, a crown ether, or a combination thereof.

Before the unreacted hydrogen chloride is reused, it is preferably subjected to compression and drying.

The process can effectively reduce the amount of the recovered hydrogen chloride and reduce the production and treatment cost; for cost reasons, the hydrochloric acid solution can also be prepared by absorbing unreacted hydrogen chloride gas with water.

The above reaction can be carried out under normal pressure or pressurized environment. In order to further improve the utilization rate of the hydrogen chloride, in a preferred embodiment, the chlorination reaction adopts a closed reactor, and the reaction pressure is controlled to be 1.01-1.50 MPa.

In another preferred embodiment, the reaction is terminated when the conversion of dichlorine is 45-80%. By controlling the conversion, the production of by-products is reduced. In order to further improve the recycling rate of the reaction materials and further reduce the cost, the chlorination reaction is preferably stopped when the conversion rate of dichlorinated products is 55-70%. When the conversion rate of dichlorinated products exceeds the range, impurities of trichloro-compounds and etherified high boiling point products are increased, so that the utilization rate of trimethylolpropane is reduced; when the conversion of the dichloro compound is less than the above range, the productivity of the product batch becomes low, which is not favorable for industrial demand.

In a preferred embodiment, the closed reactor used in the chlorination reaction is a multistage tandem falling film reactor. The chlorination reaction is carried out in a multistage tandem falling film reactor, which is favorable for further improving the conversion rate of the hydrogen chloride. More preferably, in the chlorination reaction process, hydrogen chloride gas is introduced from the bottom of the falling film reactor, and then unreacted hydrogen chloride escapes from the upper part of the falling film reactor and is introduced into the bottom of the next-stage reaction kettle.

In a preferred embodiment, the above preparation method further comprises: carrying out chlorination reaction under the action of an organic acid catalyst. The chlorination reaction is carried out in the presence of an organic acid catalyst, which is beneficial to improving the reaction rate of the chlorination reaction and reducing the generation of byproducts. More preferably, the amount of the organic acid catalyst is 5-15% of the charged amount of the trimethylolpropane, and the organic acid catalyst includes, but is not limited to, one or more of the group consisting of acetic acid, propionic acid, malonic acid, succinic acid and adipic acid. Compared with other organic acid catalysts, the organic acid catalyst is beneficial to further improving the reaction rate of the chlorination reaction and shortening the preparation period.

In a preferred embodiment, the temperature of the chlorination reaction is 120 to 140 ℃. Limiting the temperature range of the chlorination reaction to the above range is advantageous in reducing the reaction time and increasing the yield of the dichloride, compared to other temperature ranges.

In a preferred embodiment, when the chlorination reaction is carried out under pressurized conditions, the pressure of the reaction system is 1.2-1.5 MPa, and the hydrogen chloride is introduced in an amount of 6-13% per hour of the charged amount of trimethylolpropane. The yield of dichlorohydrins can be advantageously further improved in the above-mentioned pressure range and raw material ratio as compared with other pressurizing conditions.

The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.

Example 1

1340Kg of trimethylolpropane and 100Kg of adipic acid are put into a reaction kettle, the temperature is raised to 80 ℃, stirring is started after the trimethylolpropane is melted, the temperature is raised, the internal temperature in the reaction kettle is controlled at 130 ℃, hydrogen chloride gas starts to be introduced, the ventilation quantity of the hydrogen chloride gas is controlled at 13Kg/h (9.7 per thousand), the reaction is carried out for 58h under normal pressure, the Gas Chromatography (GC) is controlled, the monochloride conversion rate is 35 percent, the dichlorine conversion rate is 61 percent, and the reaction is finished.

Rectifying the dichlorinated product by a rectifying tower, wherein the vacuum degree is controlled to be 8mmHg, the temperature is controlled to be 140 ℃, and fractions below 95 ℃ are collected to obtain 940Kg of dichlorinated product, the purity is 97 percent, and the yield is 92 percent; the residual mother liquor 725Kg is directly applied to the next production, and the utilization rate of the hydrogen chloride in the process is 77%.

1740Kg of dichlorine and 2.2Kg of crown ether are added into a reaction kettle, the internal temperature is controlled to be 60 ℃, the flake caustic soda is added in batches, 410Kg of flake caustic soda is added, the use time is 3h, the reaction is kept for 2h, the sampling is controlled in the middle, the dichlorine of the raw material is less than or equal to 2%, the reaction is finished, the filter cake is filtered, the filter cake is solid salt, and the mother liquor is rectified under reduced pressure to obtain 1180Kg of the product 3- (chloromethyl) -3-ethyl oxetane, the purity is 97.5%, and the yield is 89%.

Example 2

725Kg of the mother liquor obtained by the rectification in the example 1 is put into the reaction kettle, 615Kg of trimethylolpropane is put into the reaction kettle, the temperature is raised to 80 ℃, stirring is started after the trimethylolpropane is melted, the temperature is raised to control the internal temperature to be 130 ℃, hydrogen chloride gas starts to be introduced, the ventilation quantity of the hydrogen chloride gas is controlled to be 13Kg/h (9.7 per thousand), the reaction is carried out under normal pressure for 58h, GC (gas chromatography) is controlled, the monochloride conversion rate is 34%, and the dichlorinate conversion rate is 60%, and the reaction is ended.

Rectifying dichlorides by a rectifying tower, controlling the vacuum to be 8mmHg and the temperature to be 140 ℃, and collecting distillate below 95 ℃ to obtain 925Kg of dichlorides with the purity of 97 percent and the yield of 91 percent; 745Kg of residual mother liquor is directly applied to the next batch production, and the utilization rate of the hydrogen chloride in the process is 77 percent.

Example 3

745Kg of the residual mother liquor obtained by rectification in the example 2 is put into a reaction kettle, 595Kg of trimethylolpropane is put into the reaction kettle, the temperature is raised to 80 ℃, stirring is started after the trimethylolpropane is melted, the temperature is raised to control the internal temperature to be 130 ℃, hydrogen chloride gas starts to be introduced, the ventilation quantity of the hydrogen chloride gas is controlled to be 13Kg/h (9.7 per thousand), the reaction is carried out under normal pressure for 58h, the GC control is carried out, the monochloride conversion rate is 34 percent, and the dichlorinate conversion rate is 60 percent, and the reaction is finished.

Rectifying dichlorides by a rectifying tower, controlling the vacuum to be 8mmHg and the temperature to be 140 ℃, and collecting fractions below 95 ℃ to obtain 910Kg of dichlorides, wherein the purity is 97 percent, and the yield is 90 percent; 763Kg of residual mother liquor is directly used in the next production, and the utilization rate of hydrogen chloride in the process is 77%.

Example 4

The difference from example 1 is that:

the aeration rate of hydrogen chloride gas is controlled at 10Kg/h (7.5 thousandths), the reaction is carried out under normal pressure for 72h to obtain 938Kg of dichloride with the purity of 97 percent, and the utilization rate of the hydrogen chloride in the process is 81 percent.

Example 5

The difference from example 1 is that:

the reaction time is 46h, the monochloride conversion rate is 53 percent, the dichloride conversion rate is 45 percent, and the utilization rate of the hydrogen chloride in the process is 87 percent.

Example 6

The difference from example 1 is that:

the reaction time is 66 hours, the monochloride conversion rate is 17 percent, the dichlorine conversion rate is 78 percent, and the utilization rate of the hydrogen chloride in the process is 73 percent.

Example 7

The difference from example 1 is that:

the aeration rate of hydrogen chloride gas is controlled at 17Kg/h (12.7 per mill), the reaction is carried out under the micro-positive pressure, the pressure in the kettle is controlled at 1.25MPa, the reaction is carried out for 40 hours, and 920Kg of dichlorinated products with the purity of 97 percent are obtained, and the utilization rate of the hydrogen chloride in the process is 86 percent.

Example 8

The difference from example 1 is that:

the aeration quantity of hydrogen chloride gas is controlled at 15Kg/h (11.1 per thousand), the reaction is carried out under the micro-positive pressure, the pressure in the kettle is controlled at 1.35MPa, the reaction is carried out for 45h, 925Kg of dichlorinated products are obtained, the purity is 97 percent, and the utilization rate of the hydrogen chloride is 87 percent.

Example 9

The difference from example 1 is that: and carrying out chlorination reaction in a three-stage falling film reactor arranged in series. The method comprises the following steps of (1) transferring a monochloride conversion rate of 35% and a dichloride conversion rate of 61% in a first reactor, transferring materials in the first reactor out for distillation, transferring materials in a second reactor into the first reactor, transferring materials in a third reactor into the second reactor, feeding materials in the third reactor again, and continuing introducing hydrogen chloride gas for reaction, wherein the utilization rate of hydrogen chloride in the process is 88%.

Example 10

The difference from example 1 is that: when the chlorination reaction is carried out under normal pressure, the weight of the introduced hydrogen chloride per hour is 5.4Kg/h (4.0 per thousand) of the input amount of the trimethylolpropane, and the reaction time is 70 h.

The monochloride conversion is 24%, the dichloride conversion is 69%, and the utilization rate of the hydrogen chloride in the process is 85%.

Comparative example 1

The difference from example 1 is that: when the conversion of dichloro product was 85%, the reaction was stopped.

The monochloride conversion is 6%, the dichlorine conversion is 85%, and the hydrogen chloride utilization rate of the process is 71%.

Comparative example 2

In a four-necked flask, 134g of trimethylolpropane, 100ml of m-xylene, and 6.4g of glacial acetic acid were charged while raising the temperature to about 140 ℃ by reflux stirring with a magnetic stirrer under atmospheric pressure, and hydrogen chloride gas was supplied at a feed rate of 9.1g/h to initiate the reaction. Then, while stirring, the temperature was gradually raised while maintaining the reflux state, and after liquid-liquid separation with distilled water and m-xylene, only the xylene layer was returned to the reactor, and reacted for 21 hours with a monochloride conversion of 14%, a dichloride conversion of 77%, and a hydrogen chloride utilization rate of 19% in the process.

From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:

compared with the existing preparation method, the preparation method provided by the application can effectively improve the utilization rate of the hydrogen chloride, so that the preparation cost of the 3-chloromethyl-3-ethyl oxetane can be greatly reduced, and the industrial popularization is facilitated.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.