CN114920621A - Preparation method of high-selectivity 3-chloro-2-chloromethyl propylene - Google Patents
Preparation method of high-selectivity 3-chloro-2-chloromethyl propylene Download PDFInfo
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Abstract
The invention provides a preparation method of high-selectivity 3-chloro-2-chloromethyl propylene, which is characterized by comprising the following steps: directly carrying out liquid phase substitution reaction on liquid isobutene and liquid chlorine in a tubular microreactor under high pressure to obtain 3-chlorine-2-chloromethylpropene, wherein the reaction formula is as follows:
according to the embodiment of the invention, liquid isobutene and liquid chlorine are used as raw materials, and liquid phase substitution reaction is directly carried out in a tubular microreactor to obtain a product 3-chloro-2-chloromethyl propylene, and the method has the advantages of easily obtained raw materials, simple steps and no need of a catalyst; by utilizing the high-efficiency mixing and rapid heat transfer performance of the microreactor, the occurrence of side reactions can be effectively reduced, and the selectivity of a target product is high and can reach 70-80 percent; book (notebook)The method can realize continuous production and improve production efficiency.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 3-chloro-2-chloromethyl propylene.
Background
The 3-chloro-2-chloromethyl propylene (CCMP) contains olefinic bond and two active chlorine atoms, can be used for synthesizing various organic synthesis reactions such as reverse transcriptase virus protease inhibitor, muscone and the like, relates to the fields of medicine, pesticide and the like, and has long-term application research on the synthesis.
The main synthesis method of 3-chloro-2-chloromethylpropene reported at present is that 1, 3-dichloroacetone is subjected to carbonization reaction under the action of a catalyst, as described in patent CN 113024348A, but the preparation of the reaction catalyst is complicated.
Li Hui Nu et al reported in the article that the synthesis of 3-chloro-2-chloromethylpropene by gas-phase continuous chlorination of isobutylene in a tubular reactor with a cooling jacket, but the exothermic reaction is not easy to control, more side reactions still exist, and the selectivity of 3-chloro-2-chloromethylpropene is 45%.
The microchannel in the microreactor has the performance of efficient mixing and rapid heat transfer, can strengthen the mass transfer and heat transfer processes in the chemical reaction process, avoids local hot spots and uneven concentration distribution, effectively inhibits the generation of adverse reactions, and improves the product yield.
Disclosure of Invention
In view of the background art, the invention aims to provide a preparation method of high-selectivity 3-chloro-2-chloromethylpropene, which has the advantages of easily available raw materials, simple steps, no need of a catalyst and high selectivity of a target product.
In order to achieve the purpose, the invention adopts the following technical scheme:
the purpose of the invention is realized by the following technical scheme:
a preparation method of high-selectivity 3-chloro-2-chloromethyl propene comprises the following steps:
directly carrying out liquid phase substitution reaction on liquid isobutene and liquid chlorine in a tubular microreactor under high pressure to obtain 3-chloro-2-chloromethylpropene, wherein the reaction formula is as follows:
preferably, the tubular microreactor is a T-shaped or Y-shaped microchannel, the diameter of the microchannel is 0.5-1 mm, and the length of the microchannel is 120-150 mm.
Preferably, the tubular microreactor has a volume (8000 to 15000) m in terms of actual reaction volume 2 /m 3 The heat exchange area of (2).
Preferably, the molar ratio of isobutene and liquid chlorine entering the tubular microreactor is 1: (1.8-2.2). More preferably, the molar ratio of isobutylene to liquid chlorine entering the tubular microreactor is 1: (1.95-2.05).
Preferably, the flow rate of the isobutene is 0.5-0.6 g/min, and the flow rate of the liquid chlorine is 1.3-1.5 g/min.
In the technical scheme, the temperature of the substitution reaction is controlled to be 20-50 ℃, the pressure is controlled to be 1-2 Mpa, and the retention time is 1-5 min. Preferably, the substitution reaction temperature is controlled to be 30-40 ℃, and the pressure is controlled to be 1.5-1.7 MPa.
In the above technical scheme, the reaction product is collected by a normal pressure tank, the residual gas is collected by a hydrogen chloride absorption tank, and the absorbent in the absorption tank is preferably water.
Compared with the prior art, the invention has the beneficial effects that:
according to the embodiment of the invention, liquid isobutene and liquid chlorine are used as raw materials, and liquid phase substitution reaction is directly carried out in a tubular microreactor to obtain a product 3-chloro-2-chloromethylpropene, so that the method has the advantages of easily available raw materials, simple steps and no need of a catalyst; by utilizing the high-efficiency mixing and quick heat transfer performance of the microreactor, the occurrence of side reactions can be effectively reduced, and the selectivity of a target product is high and can reach 70-80 percent; the method can realize continuous production and improve the production efficiency.
Drawings
FIG. 1 is a flow chart of a continuous preparation method of 3-chloro-2-chloromethylpropene using a tubular microreactor according to an embodiment of the present invention.
FIG. 2 is a schematic cross-sectional view of a T-shaped microchannel reactor.
FIG. 3 is a schematic cross-sectional view of a Y-type microchannel reactor.
FIG. 4 is a schematic view of the internal structure of a conventional tubular reactor.
Detailed Description
In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The technical solutions provided by the present invention will be clearly and completely described below with reference to specific embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The following examples all adopt a tubular microreactor, also called a microchannel reactor, as shown in fig. 2 and fig. 3, wherein fig. 2 is a schematic sectional structure of a T-type microchannel reactor, and fig. 3 is a schematic sectional structure of a Y-type microchannel reactor. Taking fig. 2 as an example, the microchannel reactor comprises two input channels 1 and a reaction channel 2, wherein the two input channels 1 are both communicated with the reaction channel 2, the reaction channel 2 is linear, the two input channels 1 and the reaction channel 2 are T-shaped, liquid isobutene and liquid chlorine are respectively injected from the two input channels 1, and then liquid phase reaction is carried out in the straight reaction channel 2. The Y-shaped microchannel reactor has the same principle.
The tubular microreactor used in the embodiment of the present invention is different from a conventional ordinary tubular reactor (as shown in fig. 4) in that: the reaction channels differ in both diameter and length. The reaction channels of the tubular microreactors used in examples 1 to 4 all had a diameter of 0.7mm, whereas the reaction channel 20 of comparative example 2 had a size Φ 12mm x 500 mm.
Example 1:
preparing a tubular micro-reactor with a tube diameter of 0.7mm and a length of 150mm (the heat exchange area calculated according to the actual reaction volume is 12000m 2 /m 3 ) And continuously injecting the mixture into two input ports of the tubular micro-reactor according to a molar ratio of 1: 2.05 of liquid isobutene and liquid chlorine, wherein the flow of the liquid isobutene is 0.5g/min, the flow of the liquid chlorine is 1.3g/min, the pressure of the micro-reactor is controlled to be 1.5Mpa, the temperature is 30 ℃, the internal liquid phase reaction is ensured, and the retention time is 3 min.
The reaction product is collected in a normal pressure tank, the residual gas is absorbed by a hydrogen chloride absorption tank, and the absorption liquid is water.
After stable operation for 30min, taking the liquid in the normal pressure tank for analysis and composition, wherein the mass content is as follows: 75.5 percent of 2-chloro-3-chloromethylpropene, 20.3 percent of 3, 3-dichloroisobutylene, 1.3 percent of 2-methylallyl chloride, 1.8 percent of chlorinated tert-butane, 0.7 percent of dichloroisobutane and 0.4 percent of trichloroisobutane. Based on this, the selectivity of 2-chloro-3-chloromethylpropene was calculated to be 76.0%.
Example 2:
preparing a tubular micro-reactor with a tube diameter of 0.7mm and a length of 150mm (the heat exchange area calculated according to the actual reaction volume is 12000m 2 /m 3 ) And continuously injecting the mixture into two input ports of the tubular micro-reactor according to a molar ratio of 1: 1.95 of liquid isobutene and liquid chlorine, wherein the flow rate of the isobutene is 0.6g/min, the flow rate of the liquid chlorine is 1.5g/min, the pressure of the microreactor is controlled to be 1.5Mpa, the temperature is 30 ℃, the internal liquid phase reaction is ensured, and the liquid phase reaction is keptThe time period is 3 min.
The reaction product is collected in a normal pressure tank, the residual gas is absorbed by a hydrogen chloride absorption tank, and the absorption liquid is water.
After stable operation for 30min, taking the liquid in the normal pressure tank for analysis and composition, wherein the mass content is as follows: 70.6 percent of 2-chloro-3-chloromethylpropene, 15.8 percent of 3, 3-dichloroisobutylene, 9.9 percent of 2-methylallyl chloride, 2.4 percent of chlorinated tert-butane, 0.6 percent of dichloroisobutane and 0.7 percent of trichloroisobutane. Based on this, the selectivity of 2-chloro-3-chloromethylpropene was calculated to be 72.9%.
Example 3:
preparing a tubular micro-reactor with a tube diameter of 0.7mm and a length of 150mm (the heat exchange area calculated according to the actual reaction volume is 12000m 2 /m 3 ) And continuously injecting the mixture into two input ports of the tubular micro-reactor according to a molar ratio of 1: 2.05 liquid isobutene and liquid chlorine, wherein the flow rate of the isobutene is 0.5g/min, the flow rate of the liquid chlorine is 1.3g/min, the pressure of the microreactor is controlled to be 1.5Mpa, the temperature is 40 ℃, the internal liquid phase reaction is ensured, and the retention time is 3 min.
The reaction product is collected in a normal pressure tank, the residual gas is absorbed by a hydrogen chloride absorption tank, and the absorption liquid is water.
After stable operation for 30min, taking the liquid in the normal pressure tank for analysis and composition, wherein the mass content is as follows: 77.9 percent of 2-chloro-3-chloromethylpropene, 19.3 percent of 3, 3-dichloroisobutylene, 1.0 percent of 2-methylallyl chloride, 0.8 percent of chlorinated tert-butane, 0.6 percent of dichloroisobutane and 0.4 percent of trichloroisobutane. The selectivity of 2-chloro-3-chloromethylpropene was calculated to be 78.2%.
Example 4:
a tubular microreactor having a tube diameter of 0.7mm and a length of 150mm (a heat exchange area calculated from an actual reaction volume of 12000m2/m3) was prepared, and a solution having a molar ratio of 1: 2.05 liquid isobutene and liquid chlorine, wherein the flow rate of the isobutene is 0.5g/min, the flow rate of the liquid chlorine is 1.3g/min, the pressure of the microreactor is controlled to be 1.7Mpa, the temperature is controlled to be 40 ℃, the internal liquid phase reaction is ensured, and the retention time is 3 min.
The reaction product is collected in a normal pressure tank, the residual gas is absorbed by a hydrogen chloride absorption tank, and the absorption liquid is water.
After stable operation for 30min, taking the liquid in the normal pressure tank for analysis and composition, wherein the mass content is as follows: 79.3 percent of 2-chloro-3-chloromethylpropene, 18.8 percent of 3, 3-dichloroisobutylene, 0.7 percent of 2-methylallyl chloride, 0.4 percent of chlorinated tert-butane, 0.3 percent of dichloroisobutane and 0.5 percent of trichloroisobutane. Based on this, the selectivity of 2-chloro-3-chloromethylpropene was calculated to be 79.4%.
Comparative example 1:
preparing a tubular micro-reactor with a tube diameter of 0.7mm and a length of 150mm (the heat exchange area calculated according to the actual reaction volume is 12000m 2 /m 3 ) And continuously injecting the mixture into two input ports of the tubular micro-reactor according to a molar ratio of 1: 2.05 of isobutene and chlorine, wherein the flow of the isobutene is 0.5g/min, the flow of the liquid chlorine is 1.3g/min, the temperature of the microreactor is controlled to be 40 ℃, the reaction is carried out at normal pressure, the reaction is carried out in a gas phase manner inside, and the retention time is 3 min.
The reaction product is collected in a normal pressure tank, the residual gas is absorbed by a hydrogen chloride absorption tank, and the absorption liquid is water. After stable operation for 30min, taking the liquid in the normal pressure tank for analysis and composition, wherein the mass content is as follows: 60.5 percent of 2-chloro-3-chloromethylpropene, 13.7 percent of 3, 3-dichloroisobutylene, 22.9 percent of 2-methylallyl chloride, 1.2 percent of chlorinated tert-butane, 1.3 percent of dichloroisobutane and 0.4 percent of trichloroisobutane. Based on this, the selectivity of 2-chloro-3-chloromethylpropene was calculated to be 64.7%.
Comparative example 2:
continuously feeding into a common tubular reactor (phi 12mm x 500mm) a mixture of: 2.05 reaction of isobutene and chlorine under normal pressure, temperature controlled at 40 deg.C and total gas flow at 0.3L/min.
The reaction product is collected in a normal pressure tank, the residual gas is absorbed by a hydrogen chloride absorption tank, and the absorption liquid is water.
After stable operation for 30min, taking the liquid in the normal pressure tank for analysis and composition, wherein the mass content is as follows: 40.2 percent of 2-chloro-3-chloromethylpropene, 12.3 percent of 3, 3-dichloroisobutylene, 41.9 percent of 2-methylallyl chloride, 3.1 percent of chlorinated tert-butane, 1.7 percent of dichloroisobutane and 0.8 percent of trichloroisobutane. Based on this, the selectivity of 2-chloro-3-chloromethylpropene was 45.7%.
From examples 1 to 4, it can be seen that the preparation method of 3-chloro-2-chloromethylpropene provided by the present invention has a high yield, which can reach 70% to 80%, and the generation of 3-chloro-2-chloromethylpropene is facilitated by the high temperature, high pressure and slight excess of liquid chlorine, so as to finally improve the selectivity of the target product.
Comparing examples 3 to 4 with comparative example 1, it is understood that the reason why the high-pressure condition in the tubular microreactor can improve the selectivity of 3-chloro-2-chloromethylpropene is that the increase in pressure changes the gas-phase reaction at normal pressure to a liquid-phase reaction, and the formation of 3-chloro-2-chloromethylpropene by the gas-phase chlorination reaction requires two-step chlorination, wherein the second chlorination is a gas-liquid reaction, the reaction contact area becomes small, and the reaction is hindered. The high-pressure liquid phase reaction can theoretically reduce the mass transfer difference of two-step chlorination reaction, thereby improving the generation efficiency of the 3-chloro-2-chloromethyl propylene and further improving the selectivity of a target product.
Comparing examples 1 to 4 and comparative example 2, it can be seen that the method for synthesizing 3-chloro-2-chloromethylpropene by using a microreactor in a high-pressure liquid phase has the advantage of high selectivity compared with the reported gas phase synthesis method in a common tubular reactor.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A preparation method of high-selectivity 3-chloro-2-chloromethyl propene is characterized by comprising the following steps: directly carrying out liquid phase substitution reaction on liquid isobutene and liquid chlorine in a tubular microreactor under high pressure to obtain 3-chlorine-2-chloromethylpropene, wherein the reaction formula is as follows:
2. the preparation method according to claim 1, wherein the tubular microreactor is a T-shaped or Y-shaped microchannel, the diameter of the microchannel is 0.5-1 mm, and the length of the microchannel is 120-150 mm.
3. The method for preparing 3-chloro-2-chloromethylpropene according to claim 2, wherein the tubular microreactor has an actual reaction volume of 8000 to 15000m 2 /m 3 The heat exchange area of (2).
4. The method for preparing 3-chloro-2-chloromethylpropene according to claim 1, wherein the molar ratio of liquid isobutylene to liquid chlorine entering the tubular microreactor is 1: (1.80-2.20).
5. The method for preparing 3-chloro-2-chloromethylpropene according to claim 1, wherein the liquid isobutylene has a flow rate of 0.5 to 0.6g/min and the liquid chlorine has a flow rate of 1.3 to 1.5 g/min.
6. The method for preparing 3-chloro-2-chloromethylpropene according to claim 1 to 5, wherein the liquid phase substitution reaction is carried out at a temperature of 20 to 50 ℃ and a pressure of 1.0 to 2.0MPa for a residence time of 1 to 5 min.
7. The method for preparing 3-chloro-2-chloromethylpropene according to claim 6, wherein the liquid phase substitution reaction is carried out at 30 to 40 ℃ and 1.5 to 1.7 MPa.
8. The method for preparing 3-chloro-2-chloromethylpropene according to claim 1, wherein the reaction product is collected in a normal temperature and pressure storage tank, and the residual hydrogen chloride gas is absorbed in a hydrogen chloride absorption tank.
9. The method for preparing 3-chloro-2-chloromethylpropene according to claim 8, wherein the hydrogen chloride gas absorbing solution is water.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164389A (en) * | 2018-01-29 | 2018-06-15 | 浙江大学 | A kind of synthetic method and synthesis reactor of highly selective 2- methallyl chlorides |
| CN110642667A (en) * | 2019-10-19 | 2020-01-03 | 湘潭大学 | Method for co-production of methyl chloropropene and chloro tert-butane by chlorination of isobutene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164389A (en) * | 2018-01-29 | 2018-06-15 | 浙江大学 | A kind of synthetic method and synthesis reactor of highly selective 2- methallyl chlorides |
| CN110642667A (en) * | 2019-10-19 | 2020-01-03 | 湘潭大学 | Method for co-production of methyl chloropropene and chloro tert-butane by chlorination of isobutene |
Non-Patent Citations (1)
| Title |
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| 李惠萍: "管式反应器中3-氯-2-氯甲基丙烯的合成研究" * |
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