WO2020252787A1 - 三甲基硅基乙炔的连续化合成系统及连续化合成方法 - Google Patents

三甲基硅基乙炔的连续化合成系统及连续化合成方法 Download PDF

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WO2020252787A1
WO2020252787A1 PCT/CN2019/092403 CN2019092403W WO2020252787A1 WO 2020252787 A1 WO2020252787 A1 WO 2020252787A1 CN 2019092403 W CN2019092403 W CN 2019092403W WO 2020252787 A1 WO2020252787 A1 WO 2020252787A1
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acetylene
grignard reagent
continuous
reaction
synthesis
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PCT/CN2019/092403
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English (en)
French (fr)
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洪浩
卢江平
丰惜春
孙兴芳
张峰
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辽宁凯莱英医药化学有限公司
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Publication of WO2020252787A1 publication Critical patent/WO2020252787A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages

Definitions

  • the invention relates to the field of organic intermediate synthesis, in particular to a continuous synthesis system and a continuous synthesis method of trimethylsilyl acetylene.
  • Trimethylsilylacetylene is a very important organic synthesis intermediate and one of the important silicon-based chemical raw materials; it is also an important alkynylation reagent, used in the preparation of various mono-alkynes and polyalkynes It is an essential synthesis unit.
  • trimethylsilylacetylene has a wide range of applications in heterocyclic chemistry, carbon-carbon coupling, drug synthesis, catalytic chemistry and materials industry. According to existing literature reports, the synthesis of trimethylsilylacetylene mostly adopts a batch synthesis process, which is mainly divided into the following stages:
  • a more effective method is to add acetylene gas while dripping Grignard reagent 2 to ensure the absolute excess of dissolved acetylene; (4) Preparation of trimethylsilyl acetylene 4: quickly drop trimethyl into the acetylene Grignard reagent Chlorosilane, otherwise there will be double-substituted impurities 5.
  • the synthesis route is as follows:
  • the Grignard reaction usually has a large amount of heat, and it is necessary to control the dropping rate of the halogenated hydrocarbon to control the reaction exotherm.
  • the preparation of the Grignard reagent by batch reaction has a long production cycle.
  • Grignard reagents are usually sensitive to air and water. If a large amount of Grignard reagents prepared by batch reaction cannot be used in time, it will increase storage risks and increase storage costs.
  • acetylene solution needs to be stored at a low temperature in the reactor, but when it encounters disturbance (such as stirring) or heating, a large amount of acetylene gas may be released, which increases the risk in the production process and increases the acetylene gas. Loss.
  • the trimethylchlorosilane needs to be added quickly when the trimethylchlorosilane is added dropwise.
  • the larger the reaction scale the longer the time required for feeding, which limits the scale of amplification.
  • the main purpose of the present invention is to provide a continuous synthesis system and continuous synthesis method of trimethylsilylacetylene to solve the problems in the prior art.
  • a continuous synthesis system of trimethylsilyl acetylene includes: a Grignard reagent continuous preparation unit, an acetylene Grignard reagent continuous synthesis unit, and three Continuous production equipment of methylsilyl acetylene.
  • the Grignard reagent continuous preparation unit is provided with a first feed port and a Grignard reagent outlet.
  • the first feed port is used to continuously input the halogenated hydrocarbon, the first organic solvent and the metal magnesium into the Grignard reagent continuous preparation unit, and the Grignard reagent It is continuously discharged through the Grignard reagent outlet;
  • the acetylene Grignard reagent continuous synthesis unit is provided with a Grignard reagent inlet, an acetylene solution inlet and an acetylene Grignard reagent outlet.
  • the Grignard reagent inlet and the Grignard reagent outlet are connected through a Grignard reagent transfer pipeline, It is used to continuously transport Grignard reagents to the continuous acetylene Grignard reagent synthesis unit; the continuous trimethylsilyl acetylene preparation device is equipped with a trimethyl halosilane inlet, an acetylene Grignard reagent inlet, and a trimethylsilyl acetylene outlet.
  • the Grignard reagent inlet and the acetylene Grignard reagent outlet are connected through the acetylene Grignard reagent transfer pipeline, which is used to continuously transport the acetylene Grignard reagent to the continuous trimethylsilyl acetylene preparation device, and pass the trimethylsilyl acetylene through the three The methylsilyl acetylene outlet is continuously discharged.
  • the Grignard reagent continuous preparation unit includes: a solid feeding device and a Grignard reagent reaction device, the Grignard reagent reaction device is provided with a first feeding port and a Grignard reagent outlet; and the solid feeding device is used to feed the Grignard reagent reaction device China supplies magnesium metal.
  • the Grignard reagent continuous preparation unit further includes a metal magnesium trap, which is arranged on the Grignard reagent transfer pipeline for removing residual metal magnesium in the Grignard reagent; preferably, the metal magnesium trap
  • the trap includes: a metal magnesium collecting part and a columnar reaction part connected in communication, and the columnar reaction part is provided with a first inlet, a first outlet and a second outlet, the first inlet is connected with the Grignard reagent outlet, and the first outlet is connected with the metal magnesium collecting The inlet end of the part is in communication, and the second outlet is in communication with the Grignard reagent inlet.
  • the continuous Grignard reagent preparation unit further includes a first temperature control device, and the first temperature control device is used to control the reaction temperature in the Grignard reagent reaction device.
  • the continuous acetylene Grignard reagent synthesis unit includes: an acetylene dissolution device and an acetylene Grignard reagent synthesis device, the acetylene dissolution device is provided with a second organic solvent inlet, an acetylene gas inlet, and an acetylene solution outlet; the acetylene Grignard reagent synthesis device is provided with The acetylene solution inlet, the Grignard reagent inlet and the acetylene Grignard reagent outlet, and the acetylene solution inlet and the acetylene solution outlet are connected through an overflow pipeline.
  • the outlet end of the overflow pipe extends to the bottom of the acetylene Grignard reagent synthesis device through the acetylene solution inlet.
  • the acetylene Grignard reagent synthesis device includes a shell, a stirring device, and a second temperature control device.
  • the shell is divided into a reaction section and a temperature recovery section.
  • the reaction section is provided with a Grignard reagent inlet, an acetylene solution inlet, and an acetylene tail gas outlet.
  • the temperature recovery section is provided with an acetylene Grignard reagent outlet;
  • the stirring device is arranged in the shell and extends along the length of the shell; the second temperature control device is used to control the temperature of the temperature recovery section.
  • the continuous synthesis system also includes a continuous quenching reaction device.
  • the continuous quenching reaction device is provided with a protective gas inlet, a quencher inlet, and an inlet for the product system to be quenched.
  • the inlet for the product system to be quenched and the trimethylsilyl group The acetylene continuous production device is connected through the delivery pipeline of the product system to be quenched.
  • the continuous synthesis system also includes an automatic feed control system, which is used to control the flow rate of the material in the Grignard reagent transfer pipeline, the flow rate of the second organic solvent, and the material in the acetylene Grignard reagent transfer pipeline. The flow rate and the flow rate of the material in the pipeline of the product system to be quenched.
  • the continuous synthesis method adopts the above-mentioned continuous synthesis system to prepare trimethylsilylacetylene.
  • the continuous synthesis method includes: The hydrocarbon, the first organic solvent and the metallic magnesium are continuously delivered to the Grignard reagent continuous preparation unit to perform the Grignard reagent continuous preparation reaction to obtain the Grignard reagent; the Grignard reagent and acetylene solution are continuously delivered to the acetylene Grignard reagent continuous synthesis unit Carry out the continuous synthesis reaction of the acetylene Grignard reagent to obtain the acetylene Grignard reagent.
  • the acetylene solution is formed by dissolving acetylene in the second organic solvent; and the acetylene Grignard reagent and trimethylhalosilane are continuously delivered to trimethylsilylacetylene.
  • the continuous preparation device performs continuous preparation reaction of trimethylsilyl acetylene to obtain trimethylsilyl acetylene.
  • the ratio of the number of moles of halogenated hydrocarbon, the number of moles of metal magnesium and the number of moles of the first organic solvent is 1:(1.0 ⁇ 1.5):(3.43 ⁇ 5.72), preferably 1:(1.05 ⁇ 1.15):(3.43 ⁇ 4.57).
  • the temperature of the continuous preparation reaction of Grignard reagent is 40-80°C, preferably 50-75°C, more preferably 65-75°C; the residence time of the materials in the continuous preparation reaction of Grignard reagent is 0.2-2h, preferably 0.5 ⁇ 1h.
  • the continuous synthesis method further includes: cooling the second organic solvent to a predetermined temperature, and then passing acetylene into the second organic solvent to obtain an acetylene solution; preferably, the predetermined temperature It is -50 to 0°C, more preferably -40 to -10°C, and even more preferably -35 to -20°C.
  • the ratio of the number of moles of acetylene, the number of moles of halogenated hydrocarbon to the number of moles of the second organic solvent is (1.2 ⁇ 3.5):1:(3.43 ⁇ 5.72), preferably (1.5 ⁇ 2.5):1:( 3.43 ⁇ 4.57).
  • reaction temperature of the continuous synthesis reaction of the acetylene Grignard reagent is -20 to 10°C, preferably -15 to 5°C, more preferably -10 to 0°C; the residence time of the material in the continuous synthesis reaction of the acetylene Grignard reagent is 0.5 to 2h, preferably 0.5 to 1h.
  • the continuous acetylene Grignard reagent synthesis unit includes an acetylene Grignard reagent synthesis device; the aforementioned continuous synthesis method further includes using an overflow pipeline to continuously deliver the acetylene solution to the acetylene Grignard reagent synthesis device, and the acetylene Grignard reagent is transferred
  • the outlet end of the pipeline extends to the bottom of the acetylene Grignard reagent synthesis device; preferably, the ratio of the number of moles of the acetylene Grignard reagent to trimethylhalosilane is 1:(0.7 ⁇ 1.0), more preferably 1:(0.8 ⁇ 0.9);
  • the trimethylhalosilane is selected from trimethylchlorosilane and/or trimethylbromosilane.
  • reaction temperature for the continuous preparation of trimethylsilyl acetylene is -10 to 30°C, preferably 0 to 20°C, more preferably 5 to 15°C; the retention of materials in the continuous preparation of trimethylsilyl acetylene The time is 0.5-2h, preferably 0.5-1h.
  • the continuous synthesis method further includes: under the atmosphere of a protective gas, the product system of the continuous preparation reaction of trimethylsilyl acetylene and the quencher are continuously delivered to the continuous quenching reaction device for quenching reaction to obtain three Methylsilyl acetylene; preferably, the volume ratio of the product system of the trimethylsilyl acetylene continuous preparation reaction to the quencher is 1: (0.2 ⁇ 0.5); preferably, the quencher is selected from water or 3 ⁇ 5wt % Aqueous hydrochloric acid.
  • the temperature of the quenching reaction is 10-30°C, preferably 15-25°C; the residence time of the materials in the quenching reaction is 0.1-1h, preferably 0.3-0.5h.
  • first organic solvent and the second organic solvent are independently selected from one or more of tetrahydrofuran, or 2-methyltetrahydrofuran, diethyl ether, and methyl tert-butyl ether.
  • the continuous synthesis system of trimethylsilyl acetylene can realize continuous preparation of Grignard reagent, continuous preparation of acetylene Grignard reagent and continuous preparation of trimethylsilyl acetylene.
  • the above-mentioned continuous synthesis system has a large specific surface area and strong heat exchange capacity, which can shorten the production cycle of Grignard reagents and acetylene Grignard reagents.
  • the preparation of Grignard reagents and acetylene Grignard reagents can be continuous, so that it can be done immediately.
  • the trimethylhalosilane reacts continuously with the acetylene Grignard reagent.
  • the equivalent ratio of the trimethylhalosilane to the acetylene Grignard reagent can be ensured to be relatively stable, thereby avoiding the risk of impurities in the batch reaction .
  • the use of the above-mentioned continuous synthesis system to prepare trimethylsilylacetylene can not only reduce the production cost, shorten the cycle, but also improve the safety of the entire process.
  • Figure 1 shows a schematic structural diagram of a continuous synthesis system for trimethylsilylacetylene according to a typical embodiment of the present invention.
  • Fig. 2 shows a schematic structural diagram of a metal magnesium trap according to a preferred embodiment of the present invention
  • Figure 3 shows a schematic structural diagram of a preferred columnar reactor according to the present invention.
  • Grignard reagent continuous preparation unit 11. Solid feeding device; 12. Grignard reagent reaction device; 13. Metal magnesium trap; 131. Metal magnesium collecting part; 132. Columnar reaction part; 14. First feed Pump; 15. The second feed pump;
  • this application provides a continuous synthesis system for trimethylsilyl acetylene, as shown in FIG. 1, the continuous synthesis system includes: Grignard reagent continuous preparation unit 10, acetylene Grignard reagent continuous The synthesis unit 20 and the continuous preparation device 30 of trimethylsilyl acetylene.
  • the Grignard reagent continuous preparation unit 10 is provided with a first feed port and a Grignard reagent outlet, and the first feed port is used to continuously input the halogenated hydrocarbon, the first organic solvent and the metal magnesium into the Grignard reagent continuous preparation unit 10, and The Grignard reagent is continuously discharged through the Grignard reagent outlet;
  • the acetylene Grignard reagent continuous synthesis unit 20 is provided with a Grignard reagent inlet, an acetylene solution inlet, and an acetylene Grignard reagent outlet.
  • the Grignard reagent inlet and the Grignard reagent outlet pass through the Grignard reagent
  • the transfer pipeline 201 is connected to continuously transport the Grignard reagent to the continuous acetylene Grignard reagent synthesis unit 20; the continuous trimethylsilyl acetylene preparation device 30 is provided with a trimethylhalosilane inlet, an acetylene Grignard reagent inlet, and three
  • the methylsilyl acetylene outlet, the acetylene Grignard reagent inlet and the acetylene Grignard reagent outlet are connected through the acetylene Grignard reagent transfer pipeline, and are used to continuously transport the acetylene Grignard reagent to the continuous trimethylsilyl acetylene preparation device 30, and
  • the trimethylsilyl acetylene is continuously discharged through the trimethylsilyl acetylene outlet.
  • the above-mentioned continuous synthesis system of trimethylsilyl acetylene can realize continuous preparation of Grignard reagent, continuous preparation of acetylene Grignard reagent, and continuous preparation of trimethylsilyl acetylene. It can realize automatic control and save Labor, save production time and effectively reduce production costs.
  • the above-mentioned continuous synthesis system has a large specific surface area and strong heat exchange capacity, which can shorten the production cycle of Grignard reagents and acetylene Grignard reagents.
  • the preparation of Grignard reagents and acetylene Grignard reagents can be continuous, so that it can be done immediately.
  • the trimethylhalosilane reacts continuously with the acetylene Grignard reagent.
  • the equivalent ratio of the trimethylhalosilane to the acetylene Grignard reagent can be ensured to be relatively stable, thereby avoiding the risk of impurities in the batch reaction .
  • the use of the above-mentioned continuous synthesis system to prepare trimethylsilylacetylene can not only reduce the production cost, shorten the cycle, but also improve the safety of the entire process.
  • the aforementioned Grignard reagent continuous preparation unit 10 includes a solid feeding device 11 and a Grignard reagent reaction device 12.
  • the Grignard reagent reaction device 12 is provided with a first feeding port and a Grignard reagent outlet; and the solid feeding device 11 is used to supply metal magnesium to the Grignard reagent reaction device 12.
  • the Grignard reagent continuous preparation unit 10 further includes a metal magnesium trap 13 ,
  • the metal magnesium trap 13 is arranged on the Grignard reagent transfer pipeline 201 for removing residual metal magnesium in the Grignard reagent.
  • the function of the magnesium trap is to settle the residual metallic magnesium particles in the Grignard reagent in the Grignard reagent transfer pipeline 201, and inhibit the metallic magnesium particles from entering the acetylene Grignard reagent continuous synthesis unit 20 with the Grignard reagent, thereby improving the process Security.
  • the magnesium metal trap 13 includes a magnesium metal collecting part 131 and a columnar reaction part 132 connected in communication, and the columnar reaction part 132 is provided with a first inlet and a first outlet.
  • the second outlet the first inlet communicates with the Grignard reagent outlet, the first outlet communicates with the inlet end of the magnesium metal collecting part, and the second outlet communicates with the Grignard reagent inlet.
  • the use of the above-mentioned structure of traps is beneficial to improve the removal rate of metal magnesium. More preferably, the level of the second outlet is higher than the level of the inlet end of the metallic magnesium collecting part, which is beneficial to further increase the sedimentation rate of metallic magnesium, thereby further reducing the residual amount of metallic magnesium in the Grignard reagent.
  • the aforementioned Grignard reagent continuous preparation unit 10 further includes a first temperature control device, The first temperature control device is used to control the reaction temperature in the Grignard reagent reaction device 12.
  • the acetylene used in the preparation process of the acetylene Grignard reagent needs to be stored under low temperature conditions, and the large amount of heat generated during the continuous preparation of the acetylene Grignard reagent will reduce the solubility of acetylene in the liquid reaction system, which will increase the safety risk of the production process.
  • the acetylene Grignard reagent continuous synthesis unit 20 includes: an acetylene dissolving device 21 and an acetylene Grignard reagent synthesizing device 22.
  • the acetylene dissolving device 21 is provided with a second organic solvent inlet, An acetylene gas inlet and an acetylene solution outlet;
  • the acetylene Grignard reagent synthesis device 22 is provided with an acetylene solution inlet, a Grignard reagent inlet and an acetylene Grignard reagent outlet, and the acetylene solution inlet and the acetylene solution outlet are connected through an overflow pipe 202.
  • the acetylene is continuously dissolved in the solvent to obtain the acetylene solution; then the acetylene solution is continuously transferred into the Grignard reagent continuous preparation unit 10 and combined with the grid Reagent reaction.
  • the setting of the acetylene dissolving device 21 greatly reduces the storage time of the acetylene solution, avoids the vaporization loss of the dissolved acetylene, and does not need to supplement the reaction system with acetylene.
  • the outlet end of the overflow pipe 202 extends to the bottom of the acetylene Grignard reagent synthesis device 22 through the acetylene solution inlet.
  • extending the outlet end of the overflow pipe 202 to the bottom of the acetylene Grignard reagent synthesis device 22 can reduce the temperature of the acetylene solution and reduce the volatilization of acetylene gas, thereby helping to improve the safety of the process.
  • the acetylene Grignard reagent synthesis device 22 includes a housing 221, a stirring device 222 and a second temperature control device.
  • the shell 221 is divided into a reaction section 221a and a temperature recovery section 221b.
  • the reaction section 221a is provided with a Grignard reagent inlet, an acetylene solution inlet, and an acetylene tail gas outlet, and the temperature recovery section 221b is provided with an acetylene Grignard reagent outlet;
  • a stirring device 222 is provided Inside the housing 221 and extending along the length of the housing 221; the second temperature control device is used to control the temperature of the temperature return section 221b.
  • the temperature of the temperature recovery section 221b is higher than the temperature of the reaction section 221a through the second temperature control device, which can increase The solubility of the acetylene Grignard reagent improves its outflow, reduces the risk of blockage in the columnar reactor, and shortens the production cycle.
  • first temperature control device and second temperature control device can be of conventional types in the field, such as temperature control jackets, water baths, oil baths, and the like.
  • the acetylene solution inlet is arranged at the junction of the reaction section 221a and the temperature recovery section 221b.
  • the continuous synthesis system further includes a continuous quenching reaction device 40, and the continuous quenching reaction device 40 is provided with protection
  • the gas inlet, the quencher inlet, and the product system inlet to be quenched, the product system inlet to be quenched, and the continuous trimethylsilylacetylene preparation device 30 are communicated with the product system to be quenched delivery pipeline.
  • the Grignard reagent reaction device 12 and the continuous quenching reaction device 40 can adopt continuous reaction devices commonly used in the art.
  • the Grignard reagent reaction device 12 and the continuous quenching reaction device 40 are independently selected from a columnar reactor and a continuous stirring reactor.
  • the aforementioned continuous synthesis system further includes an automatic feeding control system, which is used to control the Grignard reagent transfer pipeline 201
  • the flow rate of the material, the flow rate of the second organic solvent, the flow rate of the material in the acetylene Grignard reagent transfer pipeline, and the flow rate of the material in the delivery pipeline of the product system to be quenched.
  • this application also provides a continuous synthesis method of trimethylsilyl acetylene.
  • the continuous synthesis method adopts the above-mentioned continuous synthesis system to prepare trimethylsilyl acetylene.
  • the continuous synthesis method includes: The substituted hydrocarbon, the first organic solvent and the metal magnesium are continuously delivered to the Grignard reagent continuous preparation unit 10 for continuous Grignard reagent preparation reaction to obtain the Grignard reagent; the Grignard reagent and acetylene solution are continuously delivered to the acetylene Grignard reagent continuous
  • the synthesis unit 20 performs the continuous synthesis reaction of the acetylene Grignard reagent to obtain the acetylene Grignard reagent; and continuously transports the acetylene Grignard reagent and trimethylhalosilane to the continuous trimethylsilyl acetylene preparation device 30 for trimethylsilyl Acetylene is continuously prepared by reaction to obtain trimethylsilyl acetylene.
  • the above-mentioned continuous synthesis system of trimethylsilyl acetylene can realize continuous preparation of Grignard reagent, continuous preparation of acetylene Grignard reagent, and continuous preparation of trimethylsilyl acetylene. It can realize automatic control and save Labor, save production time and effectively reduce production costs.
  • the above-mentioned continuous synthesis method has strong heat exchange ability, and can shorten the production cycle of short Grignard reagent and acetylene Grignard reagent.
  • the preparation of Grignard reagent and acetylene Grignard reagent is continuous, so that it can be used immediately. Avoid long-term storage of Grignard reagent materials, thereby effectively reducing the probability of potential safety hazards.
  • trimethylhalosilane and acetylene Grignard reagent In the continuous reaction of trimethylhalosilane and acetylene Grignard reagent, continuous addition of trimethylhalosilane can ensure that the equivalent ratio of trimethylhalosilane to acetylene Grignard reagent is relatively stable, thereby avoiding the generation of impurities in batch reactions. risk.
  • the use of the above-mentioned continuous synthesis system to prepare trimethylsilylacetylene can not only reduce production costs, shorten production cycles, but also improve the safety of the entire process.
  • the number of moles of halogenated hydrocarbon and the number of moles of metal magnesium is 1:(1.0 ⁇ 1.5):(3.43 ⁇ 5.72), preferably 1:(1.05 ⁇ 1.15):(3.43 ⁇ 4.57)
  • the temperature of the continuous preparation reaction of the Grignard reagent is 40-80°C.
  • the reaction temperature during the continuous preparation reaction of the Grignard reagent includes but is not limited to the above range, and limiting it to the above range is beneficial to increase the conversion rate of the reaction raw materials and the sufficient degree of reaction.
  • the temperature of the continuous preparation reaction of the Grignard reagent is 50-75°C, more preferably 65-75°C.
  • the residence time of the materials in the continuous preparation reaction of the Grignard reagent is 0.2-2h.
  • the residence time of the materials during the continuous preparation reaction of the Grignard reagent includes but is not limited to the above range, and limiting it to the above range is beneficial to increase the yield of the Grignard reagent.
  • the residence time of the materials in the continuous preparation reaction of the Grignard reagent is 0.5 to 1 h.
  • the above-mentioned continuous synthesis method further includes adding an initiator to the reaction raw material for the continuous preparation reaction of the Grignard reagent.
  • the above-mentioned continuous synthesis method further includes: The solvent is cooled to a predetermined temperature, and then acetylene is passed into the second organic solvent to obtain an acetylene solution.
  • the predetermined temperature is -50 to 0°C, more preferably -40 to -10°C, and still more preferably -35 to -20°C.
  • the ratio of the number of moles of acetylene, the number of moles of halogenated hydrocarbon and the number of moles of the second organic solvent is (1.2 ⁇ 3.5):1:( 3.43 to 5.72), preferably (1.5 to 2.5):1:(3.43 to 4.57).
  • the reaction temperature of the continuous synthesis reaction of the acetylene Grignard reagent is -20-10°C.
  • the reaction temperature during the continuous synthesis reaction of the acetylene Grignard reagent includes but is not limited to the above range, and limiting it to the above range is beneficial to increase the conversion rate of the reaction raw materials and the full reaction degree. More preferably, the reaction temperature of the continuous synthesis reaction of the acetylene Grignard reagent is -15 to 5°C, further preferably -10 to 0°C.
  • the residence time of the materials in the continuous synthesis reaction of the acetylene Grignard reagent is 0.5-2h.
  • the residence time of the materials during the continuous synthesis reaction of the acetylene Grignard reagent includes but is not limited to the above range, and limiting it to the above range is beneficial to increase the yield of the Grignard reagent. More preferably, the residence time of the materials in the continuous synthesis reaction of the acetylene Grignard reagent is 0.5 to 1 h.
  • the aforementioned acetylene Grignard reagent continuous synthesis unit 20 includes an acetylene Grignard reagent synthesis device 22, and the aforementioned continuous synthesis method further includes using an overflow pipe 202 to remove the acetylene Grignard reagent from the acetylene Grignard reagent.
  • the synthesis device 22 is continuously delivered to the trimethylsilyl acetylene continuous preparation device 30, and the outlet end of the overflow pipe 202 extends to the bottom of the acetylene Grignard reagent synthesis device 22.
  • the setting of the overflow pipeline 202 enables the acetylene Grignard reagent to be continuously output in an overflow manner.
  • the overflow process can reduce the temperature of the acetylene Grignard reagent, which causes the acetylene dissolved in the acetylene Grignard reagent to escape;
  • the outlet end of the flow line 202 extends to the bottom of the acetylene Grignard reagent synthesis device 22 to enable the acetylene released from the solution due to the temperature difference to be reused in the reaction solution, thereby increasing the utilization of acetylene and reducing the cost of raw materials.
  • the ratio of the number of moles of the acetylene Grignard reagent to the trimethyl halosilane is 1: (0.7 to 1.0), and more preferably 1: (0.8 to 0.9) .
  • the reaction temperature of the continuous preparation reaction of trimethylsilylacetylene is -10 to 30°C.
  • the reaction temperature of the continuous preparation of trimethylsilyl acetylene includes but is not limited to the above range, and limiting it to the above range is beneficial to increase the conversion rate of the reaction raw materials and the sufficient degree of reaction. More preferably, the reaction temperature of the continuous preparation reaction of trimethylsilylacetylene is 0-20°C, more preferably 5-15°C.
  • the residence time of the materials in the continuous preparation reaction of trimethylsilylacetylene is 0.5-2h.
  • the residence time of the materials in the continuous preparation of trimethylsilyl acetylene includes but is not limited to the above range, and limiting it to the above range is beneficial to increase the yield of the Grignard reagent. More preferably, the residence time of the materials in the continuous preparation reaction of trimethylsilyl acetylene is 0.5 to 1 h.
  • the above-mentioned continuous synthesis method further includes: under a protective gas atmosphere, the continuous preparation of trimethylsilylacetylene
  • the product system and quenching agent are continuously delivered to the continuous quenching reaction device 40 for quenching reaction to obtain trimethylsilylacetylene.
  • the volume ratio of the product system of the trimethylsilyl acetylene continuous preparation reaction to the quencher is 1: (0.2-0.5). Limiting the volume ratio of the product system of the trimethylsilyl acetylene continuous preparation reaction to the quenching agent within the above range is beneficial to further improve the quenching effect.
  • the quencher includes but is not limited to water and/or 3 to 5 wt% aqueous hydrochloric acid.
  • the temperature of the quenching reaction is 10-30°C.
  • the temperature of the quenching reaction includes but is not limited to the above range, and limiting it to the above range is beneficial to increase the reaction rate of the quenching reaction and shorten the quenching time. More preferably, the temperature of the quenching reaction is 15-25°C.
  • the residence time of the materials in the quenching reaction is 0.1 to 1 h.
  • the residence time of the materials in the quenching reaction includes but is not limited to the above range, and limiting it to the above range is beneficial to increase the reaction degree of the quenching reaction, thereby increasing the purity of the product. More preferably, the residence time of the materials in the quenching reaction is 0.3-0.5h.
  • the first organic solvent and the second organic solvent are independently selected from one or more of tetrahydrofuran, or 2-methyltetrahydrofuran, diethyl ether, and methyl tert-butyl ether.
  • the use of the above-mentioned organic solvents is beneficial to further improve the compatibility of the components.
  • 2-methyltetrahydrofuran has a higher boiling point and is easier to separate from the product. In the industrial production process, the solvent recovery rate can be improved and the process cost can be saved.
  • the first organic solvent and the second organic solvent are a mixture of tetrahydrofuran and 2-methyltetrahydrofuran, and the volume ratio of 2-methyltetrahydrofuran and tetrahydrofuran is 9:1 to 1:9, and more preferably 8: 2 ⁇ 7:3.
  • the first temperature control device is used to control the temperature in the Grignard reagent reaction device 12, wherein an oil bath is provided in the first temperature control device. The oil bath was heated to 50°C and kept for 10 minutes. One drop of initiator (1,2-dibromoethane) is added dropwise to the Grignard reagent reaction device 12 to initiate the Grignard reagent preparation reaction.
  • the first temperature control device is used to keep the temperature of the Grignard reagent reaction device 12 at 70° C., and the residence time of the materials in the Grignard reagent reaction device 12 is 1 h.
  • the acetylene solution in the acetylene dissolving device 21 is fed into the acetylene Grignard reagent synthesis device 22 through an overflow pipe, and the outlet end of the overflow pipe 202 extends to the bottom of the acetylene Grignard reagent synthesis device 22.
  • the third feed pump 23 is turned on, and the Grignard reagent butylmagnesium chloride tetrahydrofuran solution prepared in the previous step is passed into the acetylene Grignard reagent synthesis device 22 at a rate of 4.29 g/min.
  • the fourth feed pump 24 is turned on to feed, and tetrahydrofuran is fed into the acetylene dissolving device 21 at a rate of 4.12 g/min.
  • the fifth feed pump 31 is turned on, and at a rate of 1.06 g/min, trimethylchlorosilane (from Samples were taken from the continuous trimethylsilyl acetylene preparation device 30, and gas chromatography was used to track the reaction effect), and the reaction time was 1 h.
  • the sixth feed pump 32 was turned on, and the product system of the continuous preparation reaction of trimethylsilyl acetylene was transferred to the continuous quenching reaction device 40 at a rate of 9.47 g/min, and the seventh feed pump 41 was turned on at the same time,
  • the quencher (water) was fed into the above-mentioned continuous quenching reaction device 40 at a rate of 4 g/min.
  • the reaction system undergoes batch operations such as liquid separation and rectification to obtain the product trimethylsilylacetylene.
  • a sample was taken from the preparation device 30 to track the reaction effect.
  • the purity of the trimethylsilylacetylene was 89.92%, the purity of the disubstituted impurity 5 was 1.18%, the purity of the product obtained after rectification was 98.65%, and the yield was 70%.
  • Embodiment 1 The difference from Embodiment 1 is that the acetylene solution overflow pipe is suspended and is not inserted into the bottom of the acetylene Grignard reagent synthesis device 22.
  • the first temperature control device is used to control the temperature in the Grignard reagent reaction device 12, wherein an oil bath is provided in the first temperature control device. The oil bath was heated to 50°C and kept for 10 minutes. One drop of initiator (1,2-dibromoethane) is added dropwise to the Grignard reagent reaction device 12 to initiate the Grignard reagent preparation reaction.
  • the first temperature control device is used to keep the temperature of the Grignard reagent reaction device 12 at 70° C., and the residence time of the materials in the Grignard reagent reaction device 12 is 1 h.
  • the acetylene solution in the acetylene dissolving device 21 is fed into the acetylene Grignard reagent synthesis device 22 through an overflow pipe, and the acetylene solution overflow pipe is suspended, and is not inserted into the bottom of the acetylene Grignard reagent synthesis device 22. Pass acetylene into the acetylene dissolving device 21 at a rate of 480 mL/min, and the ventilation time is 1 h.
  • the third feed pump 23 is turned on, and the Grignard reagent (butylmagnesium chloride tetrahydrofuran solution) prepared in the previous step is introduced into the acetylene Grignard reagent synthesis device 22 at a rate of 4.29 g/min.
  • the fourth feed pump 24 is turned on to feed, and tetrahydrofuran is fed into the acetylene dissolving device 21 at a rate of 4.12 g/min.
  • the fifth feed pump 31 is turned on, and at a rate of 1.06 g/min, trimethylchlorosilane (from Samples were taken from the continuous trimethylsilyl acetylene preparation device 30, and gas chromatography was used to track the reaction effect), and the reaction time was 1 h.
  • the sixth feed pump 32 was turned on, and the product system of the continuous preparation reaction of trimethylsilyl acetylene was transferred to the continuous quenching reaction device 40 at a rate of 9.47 g/min, and the seventh feed pump 41 was turned on at the same time,
  • the quencher (water) was fed into the above-mentioned continuous quenching reaction device 40 at a rate of 4 g/min.
  • the reaction system undergoes batch operations such as liquid separation and rectification to obtain the product trimethylsilylacetylene.
  • a sample was taken from the preparation device 30 to track the reaction effect.
  • the purity of trimethylsilylacetylene was 72.25%; the purity of the disubstituted impurity 5 was 17.77%, and the purity of the product obtained after rectification was 98.2%, and the yield was 54%.
  • Example 2 The difference from Example 1 is that the first organic solvent and the second organic solvent are both a mixed solution of 2-methyltetrahydrofuran and tetrahydrofuran, and the volume ratio of the two is 8:2.
  • the first temperature control device is used to control the temperature in the Grignard reagent reaction device 12, wherein an oil bath is provided in the first temperature control device. The oil bath was heated to 50°C and kept for 10 minutes. One drop of initiator (1,2-dibromoethane) is added dropwise to the Grignard reagent reaction device 12 to initiate the Grignard reagent preparation reaction.
  • the first temperature control device is used to keep the temperature of the Grignard reagent reaction device 12 at 70° C., and the residence time of the materials in the Grignard reagent reaction device 12 is 1 h.
  • the acetylene solution in the acetylene dissolving device 21 is fed into the acetylene Grignard reagent synthesis device 22 through an overflow pipe, and the outlet end of the overflow pipe 202 extends to the bottom of the acetylene Grignard reagent synthesis device 22.
  • the third feed pump 23 is turned on, and the Grignard reagent (butylmagnesium chloride tetrahydrofuran solution) prepared in the previous step is introduced into the acetylene Grignard reagent synthesis device 22 at a rate of 4.29 g/min.
  • the fourth feed pump 24 is turned on to feed, and the second organic solvent is introduced into the acetylene dissolving device 21 at a rate of 4.12 g/min.
  • the fifth feed pump 31 is turned on, and at a rate of 1.06 g/min, trimethylchlorosilane (from Samples were taken from the continuous trimethylsilyl acetylene preparation device 30, and gas chromatography was used to track the reaction effect), and the reaction time was 1 h.
  • the sixth feed pump 32 was turned on, and the product system of the continuous preparation reaction of trimethylsilyl acetylene was transferred to the continuous quenching reaction device 40 at a rate of 9.47 g/min, and the seventh feed pump 41 was turned on at the same time,
  • the quencher (water) was fed into the above-mentioned continuous quenching reaction device 40 at a rate of 4 g/min.
  • the reaction system undergoes batch operations such as liquid separation and rectification to obtain the product trimethylsilylacetylene.
  • a sample is taken from the preparation device 30 to track the reaction effect.
  • the purity of the trimethylsilylacetylene is 80.12%; the purity of the disubstituted impurity 5 is 10.15%, and the purity of the product obtained after rectification is 97.29%, and the yield is 62.2%.
  • Example 2 The difference from Example 1 is that the acetylene solution is prepared in a batch process.
  • the reaction temperature is 50°C, and the residence time of the materials is 2h;
  • the reaction temperature is -15°C, and the residence time of materials is 1h;
  • the reaction temperature is 20°C, and the residence time of the materials is 0.5h;
  • the reaction temperature is 10°C
  • the residence time of the material is 1h.
  • a sample is taken from the preparation device 30 to track the reaction effect.
  • the purity of trimethylsilylacetylene is 73.12%; the purity of the disubstituted impurity 5 is 1.26%, and the purity of the product obtained after rectification is 98.70%, and the yield is 62.5%.
  • the reaction temperature is 75°C, and the residence time of materials is 0.5h;
  • the reaction temperature is -5°C, and the residence time of materials is 0.5h;
  • the reaction temperature is 0°C, and the residence time of the materials is 1h;
  • the reaction temperature is 30°C
  • the residence time of the materials is 1 h.
  • a sample is taken from the preparation device 30 to track the reaction effect.
  • the purity of trimethylsilylacetylene is 82.12%; the purity of the disubstituted impurity 5 is 3.26%, and the purity of the product obtained after rectification is 98.30%, and the yield is 64.7%.
  • the reaction temperature is 40°C, and the residence time of the materials is 2h;
  • the reaction temperature is -20°C, and the residence time of the materials is 0.5h;
  • the reaction temperature is 30°C, and the residence time of materials is 0.5h;
  • the reaction temperature is 30°C, and the residence time of the materials is 0.1h.
  • Example 1 The difference from Example 1 is that the first organic solvent and the second organic solvent are both a mixed solution of 2-methyltetrahydrofuran and tetrahydrofuran, and the volume ratio of the two is 9:1.
  • a sample is taken from the preparation device 30 to track the reaction effect.
  • the purity of trimethylsilylacetylene is 70.12%; the purity of the disubstituted impurity 5 is 15.15%, and the purity of the product obtained after rectification is 96.69%, and the yield is 57.8%.
  • Example 1 The difference from Example 1 is that the first organic solvent and the second organic solvent are both mixed solutions of 2-methyltetrahydrofuran and tetrahydrofuran, and the volume ratio of the two is 5:5.
  • the temperature of the reaction system in the first reaction device was maintained at 70°C. After the dropwise addition of chlorobutane is completed, the reaction system in the first reaction device is continuously kept for 1 hour, and then it is lowered to room temperature to obtain the Grignard reagent, which is ready for use.
  • the temperature of the second reaction device was controlled at 10°C, and 105 g of trimethylhalosilane was quickly added dropwise to the second reaction device through a constant pressure dropping funnel for a total of 10 minutes. After the reaction was kept for 1 hour, trimethylsilyl was obtained. Acetylene product system. Then 400 g of purified water was added to the above trimethylsilyl acetylene product system to quench the reaction. After the quenching reaction is completed, the quenched product undergoes batch operations such as liquid separation and rectification to obtain trimethylsilyl acetylene. Following the reaction effect, the purity of trimethylsilylacetylene was 85.56%, and the purity of the disubstituted impurity 5 was 2.38%. After rectification, the purity of the pure product is 98.45%, and the yield is 63%.
  • the above-mentioned embodiments of the present invention achieve the following technical effects: the use of the above-mentioned continuous synthesis system to prepare trimethylsilylacetylene can not only reduce production costs, shorten the production cycle, but also improve the overall process The safety; at the same time, the use of the above-mentioned continuous synthesis process to prepare trimethylsilyl acetylene also has a higher yield and purity.

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Abstract

本发明提供了一种三甲基硅基乙炔的连续化合成系统及连续化合成方法。该连续化系统包括格氏试剂连续制备单元、乙炔格氏试剂连续合成单元和三甲基硅基乙炔连续制备装置。格氏试剂连续制备单元设置有第一加料口和格氏试剂出口；乙炔格氏试剂连续合成单元设置有格氏试剂入口、乙炔溶液入口和乙炔格氏试剂出口，格氏试剂入口与格氏试剂出口通过格氏试剂转移管路连通；三甲基硅基乙炔连续制备装置设置有三甲基卤硅烷入口、乙炔格氏试剂入口和三甲基硅基乙炔出口，乙炔格氏试剂入口与乙炔格氏试剂出口通过乙炔格氏试剂转移管路连通。采用上述连续化合成系统制备三甲基硅基乙炔不仅能够降低生产成本，缩短周期，还能够提高整个工艺的安全性。

Description

三甲基硅基乙炔的连续化合成系统及连续化合成方法 技术领域
本发明涉及有机中间体合成领域，具体而言，涉及一种三甲基硅基乙炔的连续化合成系统及连续化合成方法。
背景技术
三甲基硅基乙炔是一种非常重要的有机合成中间体，是重要的具硅基础化工原料之一；其也是重要的炔基化试剂，在各种单炔烃和多炔烃的制备中是必不可少的合成单元。此外三甲基硅基乙炔在杂环化学、碳-碳偶联、药物合成、催化化学和材料工业中有广泛应用。根据现有文献报道，三甲基硅基乙炔的合成大多采用批次性合成工艺，主要分为以下几个阶段：
(1)制备格氏试剂2：卤代烃1和金属镁制备；(2)制备乙炔溶液：用溶剂低温下吸收乙炔气体，制备乙炔溶液；(3)制备乙炔格氏试剂3：将格氏试剂2缓慢滴加到制备的乙炔溶液中，滴加过程中需要控温，否则温度回升会造成溶液中乙炔的溶解度降低，引起乙炔挥发。更加有效的办法是滴加格氏试剂2过程中，同时通乙炔气体，保证溶解乙炔的绝对过量；(4)制备三甲基硅基乙炔4：向乙炔格氏试剂中快速滴加三甲基氯硅烷，否则会出现双取代的杂质5，合成路线如下：
Figure PCTCN2019092403-appb-000001
上述合成路线的副反应为
Figure PCTCN2019092403-appb-000002
上述批次性合成工艺存在一些缺点：
1.格氏反应通常放热量大，需要控制卤代烃的滴加速度控制反应放热，用批次反应制备格氏试剂生产周期长。
2.反应釜中需提前加入大量易燃金属镁，反应结束后需要清理残余镁屑，增加了操作的潜在风险与反应放大风险。
3.格氏试剂通常对空气和水敏感，批次反应制备大量格氏试剂如无法及时使用，会增加存储风险，提高存储成本。
4.用批次方式溶解乙炔，乙炔溶液需要在反应釜中低温保存，但遇到扰动(比如搅拌)或者升温，可能会释放大量乙炔气体，增加了生产过程中的风险，同时增加了乙炔气体的损耗。
5.向乙炔溶液中滴加格氏试剂时，反应放热会引起溶解乙炔的释放，为保证反应效果，同时需要向反应体系中通乙炔，增加了乙炔气体的用量。
6.为控制杂质，滴加三甲基氯硅烷时需要快速滴加，反应规模越大，需要加料的时间会变长，限制了放大规模。
7.涉及到操作均需要独立的生产时间，因此三甲基硅基乙炔完整的批次生产时间较长。
发明内容
本发明的主要目的在于提供一种三甲基硅基乙炔的连续化合成系统及连续化合成方法，以解决现有技术中的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种三甲基硅基乙炔的连续化合成系统，连续化合成系统包括：格氏试剂连续制备单元、乙炔格氏试剂连续合成单元和三甲基硅基乙炔连续制备装置。格氏试剂连续制备单元设置有第一加料口和格氏试剂出口，第一加料口用于将卤代烃、第一有机溶剂和金属镁连续输入格氏试剂连续制备单元，并将格氏试剂经格氏试剂出口连续排出；乙炔格氏试剂连续合成单元设置有格氏试剂入口、乙炔溶液入口和乙炔格氏试剂出口，格氏试剂入口与格氏试剂出口通过格氏试剂转移管路连通，用于将格氏试剂连续输送至乙炔格氏试剂连续合成单元中；三甲基硅基乙炔连续制备装置设置有三甲基卤硅烷入口、乙炔格氏试剂入口和三甲基硅基乙炔出口，乙炔格氏试剂入口与乙炔格氏试剂出口通过乙炔格氏试剂转移管路连通，用于将乙炔格氏试剂连续输送至三甲基硅基乙炔连续制备装置，并将三甲基硅基乙炔经三甲基硅基乙炔出口连续排出。
进一步地，格氏试剂连续制备单元包括：固体加料装置和格氏试剂反应装置，格氏试剂反应装置设置有第一加料口和格氏试剂出口；及固体加料装置用于向格氏试剂反应装置中供应金属镁。
进一步地，格氏试剂连续制备单元还包括金属镁捕集阱，金属镁捕集阱设置在格氏试剂转移管路上，用于去除格氏试剂中残余的金属镁；优选地，金属镁捕集阱包括：连通设置的金属镁收集部和柱状反应部，且柱状反应部设置有第一入口、第一出口和第二出口，第一入口与格氏试剂出口连通，第一出口与金属镁收集部的入口端连通，第二出口与格氏试剂入口连通。
进一步地，格氏试剂连续制备单元还包括第一控温装置，第一控温装置用于控制格氏试剂反应装置中的反应温度。
进一步地，乙炔格氏试剂连续合成单元包括：乙炔溶解装置和乙炔格氏试剂合成装置，乙炔溶解装置设置有第二有机溶剂入口、乙炔气体入口和乙炔溶液出口；乙炔格氏试剂合成装置设置有乙炔溶液入口和格氏试剂入口和乙炔格氏试剂出口，乙炔溶液入口与乙炔溶液出口通过溢流管路连通。
进一步地，溢流管路的出口端经乙炔溶液入口延伸至乙炔格氏试剂合成装置的底部。
进一步地，乙炔格氏试剂合成装置包括：壳体和搅拌装置以及第二控温装置，壳体分为反应段和回温段，反应段设置有格氏试剂入口、乙炔溶液入口、乙炔尾气出口，回温段设置有乙炔格氏试剂出口；搅拌装置设置在壳体内，且沿壳体的长度方向延伸；第二控温装置用于控制回温段的温度。
进一步地，连续化合成系统还包括连续淬灭反应装置，连续淬灭反应装置设置有保护气入口、淬灭剂入口和待淬灭产物体系入口，待淬灭产物体系入口与三甲基硅基乙炔连续制备装置通过待淬灭产物体系输送管路连通。
进一步地，连续化合成系统还包括自动进料控制系统，自动进料控制系统用于控制格氏试剂转移管路中物料的流速、第二有机溶剂的流速、乙炔格氏试剂转移管路中物料的流速以及待淬灭产物体系输送管路中物料的流速。
本申请的另一方面还提供了一种三甲基硅基乙炔的连续化合成方法，连续化合成方法采用上述连续化合成系统制备三甲基硅基乙炔，连续化合成方法包括：使卤代烃、第一有机溶剂和金属镁连续地输送至格氏试剂连续制备单元进行格氏试剂连续制备反应，得到格氏试剂；将格氏试剂和乙炔溶液连续地输送至乙炔格氏试剂连续合成单元进行乙炔格氏试剂连续合成反应，得到乙炔格氏试剂，乙炔溶液由乙炔溶解在第二有机溶剂中形成；及使乙炔格氏试剂与三甲基卤硅烷连续地输送至三甲基硅基乙炔连续制备装置进行三甲基硅基乙炔连续制备反应，得到三甲基硅基乙炔。
进一步地，格氏试剂连续制备反应中，卤代烃的摩尔数、金属镁的摩尔数和第一有机溶剂的摩尔数之比为1:(1.0～1.5):(3.43～5.72)，优选为1:(1.05～1.15):(3.43～4.57)。
进一步地，格氏试剂连续制备反应的温度为40～80℃，优选为50～75℃，更优选为65～75℃；格氏试剂连续制备反应中物料的停留时间为0.2～2h，优选为0.5～1h。
进一步地，在进行乙炔格氏试剂连续合成反应之前，连续化合成方法还包括：将第二有机溶剂冷却至预定温度，然后向第二有机溶剂通入乙炔，得到乙炔溶液；优选地，预定温度为-50～0℃，更优选为-40～-10℃，进一步优选为-35～-20℃。
进一步地，乙炔的摩尔数、卤代烃的摩尔数与第二有机溶剂的摩尔数之比为(1.2～3.5):1:(3.43～5.72)，优选为(1.5～2.5):1:(3.43～4.57)。
进一步地，乙炔格氏试剂连续合成反应的反应温度为-20～10℃，优选为-15～5℃，更优选为-10～0℃；乙炔格氏试剂连续合成反应中物料的停留时间为0.5～2h，优选为0.5～1h。
进一步地，乙炔格氏试剂连续合成单元包括乙炔格氏试剂合成装置；上述连续化合成方法还包括采用溢流管路将乙炔溶液连续输送至乙炔格氏试剂合成装置中，且乙炔格氏试剂转移管路的出口端延伸至乙炔格氏试剂合成装置的底部；优选地，乙炔格氏试剂与三甲基卤硅烷的摩尔数之比为1:(0.7～1.0)，更优选为1:(0.8～0.9)；
优选地，三甲基卤硅烷选自三甲基氯硅烷和/或三甲基溴硅烷。
进一步地，三甲基硅基乙炔连续制备反应的反应温度为-10～30℃，优选为0～20℃，更优选为5～15℃；三甲基硅基乙炔连续制备反应中物料的停留时间为0.5～2h，优选0.5～1h。
进一步地，连续化合成方法还包括：在保护气的氛围下，将三甲基硅基乙炔连续制备反应的产物体系和淬灭剂连续输送至连续淬灭反应装置中进行淬灭反应，得到三甲基硅基乙炔；优选地，三甲基硅基乙炔连续制备反应的产物体系与淬灭剂的体积比为1:(0.2～0.5)；优选地，淬灭剂选自水或3～5wt％的盐酸水溶液。
进一步地，淬灭反应的温度为10～30℃，优选为15～25℃；淬灭反应中物料的停留时间为0.1～1h，优选为0.3～0.5h。
进一步地，第一有机溶剂和第二有机溶剂分别独立地选自四氢呋喃、或2-甲基四氢呋喃、乙醚和甲基叔丁基醚中的一种或多种。
应用本发明的技术方案，采用上述三甲基硅基乙炔的连续化合成系统能够实现格氏试剂连续制备、乙炔格氏试剂连续制备和三甲基硅基乙炔的连续制备等操作的连续化工艺，可以实现自动化控制，节省人工，节省生产时间，有效降低生产成本。上述连续化合成系统比表面积大，设备换热能力强，能够缩短格氏试剂和乙炔格氏试剂的生产周期，同时将格氏试剂和乙炔格氏试剂的制备实现连续化，做到即做即用，避免格氏试剂物料长时间存储，从而有效较低安全隐患发生几率。三甲基卤硅烷与乙炔格氏试剂连续反应，通过连续加入三甲基卤硅烷，可以保证三甲基卤硅烷与乙炔格氏试剂的当量比相对稳定，从而避免批次反应中杂质产生的风险。综上所述，采用上述连续化合成系统制备三甲基硅基乙炔不仅能够降低生产成本，缩短周期，还能够提高整个工艺的安全性。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1示出了根据本发明的一种典型的实施方式提供的三甲基硅基乙炔的连续化合成系统的结构示意图；以及
图2示出了根据本发明的一种优选的实施方式提供的金属镁捕集阱的结构示意图；
图3示出了根据本发明的一种优选的柱状反应器的结构示意图。
其中，上述附图包括以下附图标记：
10、格氏试剂连续制备单元；11、固体加料装置；12、格氏试剂反应装置；13、金属镁捕集阱；131、金属镁收集部；132、柱状反应部；14、第一进料泵；15、第二进料泵；
20、乙炔格氏试剂连续合成单元；201、转移管路；202、溢流管路；21、乙炔溶解装置；22、乙炔格氏试剂合成装置；221、壳体；221a、反应段；221b、回温段；222、搅拌装置；23、第三进料泵；24、第四进料泵；
30、三甲基硅基乙炔连续制备装置；31、第五进料泵；32、第六进料泵；
40、连续淬灭反应装置；41、第七进料泵。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术所描述的，现有的制备三甲基硅基乙炔均采用批次性工艺，这类工艺存在安全隐患、工艺成本高和工艺周期长的问题。为了解决上述技术问题，本申请提供了一种三甲基硅基乙炔的连续化合成系统，如图1所示，该连续化合成系统包括：格氏试剂连续制备单元10、乙炔格氏试剂连续合成单元20和三甲基硅基乙炔连续制备装置30。其中，格氏试剂连续制备单元10设置有第一加料口和格氏试剂出口，第一加料口用于将卤代烃、第一有机溶剂和金属镁连续输入格氏试剂连续制备单元10，并将格氏试剂经格氏试剂出口连续排出；乙炔格氏试剂连续合成单元20设置有格氏试剂入口、乙炔溶液入口和乙炔格氏试剂出口，格氏试剂入口与格氏试剂出口通过格氏试剂转移管路201连通，用于将格氏试剂连续输送至乙炔格氏试剂连续合成单元20中；三甲基硅基乙炔连续制备装置30设置有三甲基卤硅烷入口、乙炔格氏试剂入口和三甲基硅基乙炔出口，乙炔格氏试剂入口与乙炔格氏试剂出口通过乙炔格氏试剂转移管路连通，用于将乙炔格氏试剂连续输送至三甲基硅基乙炔连续制备装置30，并将三甲基硅基乙炔经三甲基硅基乙炔出口连续排出。
采用上述三甲基硅基乙炔的连续化合成系统能够实现格氏试剂连续制备、乙炔格氏试剂连续制备和三甲基硅基乙炔的连续制备等操作的连续化工艺，可以实现自动化控制，节省人工，节省生产时间，有效降低生产成本。上述连续化合成系统比表面积大，设备换热能力强，能够缩短格氏试剂和乙炔格氏试剂的生产周期，同时将格氏试剂和乙炔格氏试剂的制备实现连续化，做到即做即用，避免格氏试剂物料长时间存储，从而有效较低安全隐患发生几率。三甲基卤硅烷与乙炔格氏试剂连续反应，通过连续加入三甲基卤硅烷，可以保证三甲基卤硅烷与乙炔格氏试剂的当量比相对稳定，从而避免批次反应中杂质产生的风险。综上所述，采用上述连续化合成系统制备三甲基硅基乙炔不仅能够降低生产成本，缩短周期，还能够提高整个工艺的安全性。
在一种优选的实施例中，如图1所示，上述格氏试剂连续制备单元10包括固体加料装置11和格氏试剂反应装置12。其中格氏试剂反应装置12设置有第一加料口和格氏试剂出口；及固体加料装置11用于向格氏试剂反应装置12中供应金属镁。通过设置固体加料装置11能够实现连续控制金属镁的加入量，使反应器内的镁屑残留始终控制在一个较少的水平，从而能够进一步降低控操作风险。
金属镁具有易燃属性，为了降低格氏试剂中残留的金属镁的含量，在一种优选的实施例中，如图1所示，格氏试剂连续制备单元10还包括金属镁捕集阱13，金属镁捕集阱13设置在格氏试剂转移管路201上，用于去除格氏试剂中残余的金属镁。镁捕集阱的作用是将格氏试剂转移管路201中的格氏试剂中残余的金属镁颗粒进行沉降，抑制金属镁颗粒随格氏试剂进入乙炔格氏试剂连续合成单元20，进而提高工艺的安全性。
在一种优选的实施例中，如图2所示，金属镁捕集阱13包括连通设置的金属镁收集部131和柱状反应部132，且柱状反应部132设置有第一入口、第一出口和第二出口，第一入口与格氏试剂出口连通，第一出口与金属镁收集部的入口端连通，第二出口与格氏试剂入口连通。相比于其它结构的金属镁捕集阱，采用上述结构的捕集阱有利于提高金属镁的去除率。更优选地，第二出口的水平高度高于金属镁收集部的入口端的水平高度，这有利于进一步提高金属镁的沉降速度，进而进一步降低格氏试剂中金属镁的残余量。
由于格氏反应过程会释放大量的热，为了更好地控制格氏试剂连续制备反应的温度，在一种优选的实施例中，上述格氏试剂连续制备单元10还包括第一控温装置，第一控温装置用于控制格氏试剂反应装置12中的反应温度。
乙炔格氏试剂制备过程中使用的乙炔需要在低温条件下储存，而乙炔格氏试剂连续制备过程中产生的大量热会降低乙炔在液体反应体系中的溶解度，这会增加生产过程的安全风险。在一种优选的实施例中，如图1所示，乙炔格氏试剂连续合成单元20包括：乙炔溶解装置21和乙炔格氏试剂合成装置22，乙炔溶解装置21设置有第二有机溶剂入口、乙炔气体入口和乙炔溶液出口；乙炔格氏试剂合成装置22设置有乙炔溶液入口和格氏试剂入口和乙炔格氏试剂出口，乙炔溶液入口与乙炔溶液出口通过溢流管路202连通。
在乙炔格氏试剂连续合成单元20中，通过设置乙炔溶解装置21，先将乙炔连续溶解在溶剂中，得到乙炔溶液；然后将乙炔溶液连续转移入格氏试剂连续制备单元10中，并与格氏试剂反应。通过乙炔溶解装置21的设置大幅度减少了乙炔溶液的保存时间，避免了溶解乙炔的气化损失，而且不用再额外向反应体系中补充乙炔。
在一种优选的实施例中，溢流管路202的出口端经乙炔溶液入口延伸至乙炔格氏试剂合成装置22的底部。相比于其它设置方式，将溢流管路202的出口端延伸至乙炔格氏试剂合成装置22的底部可以降低乙炔溶液的温度，减少乙炔气体挥发，从而有利于提高工艺的安全性。
在一种优选的实施例中，如图3所示，乙炔格氏试剂合成装置22包括：壳体221、搅拌装置222和第二控温装置。其中，壳体221分为反应段221a和回温段221b，反应段221a设置有格氏试剂入口、乙炔溶液入口、乙炔尾气出口，回温段221b设置有乙炔格氏试剂出口； 搅拌装置222设置在壳体221内，且沿壳体221的长度方向延伸；第二控温装置用于控制回温段221b的温度。
由于乙炔格氏试剂合成过程中的反应温度较低，乙炔格氏试剂容易以固体的形式析出，因而通过第二控温装置将回温段221b的温度高于反应段221a的温度，这能够提高乙炔格氏试剂的溶解度，提高其流出性，降低柱状反应器发生堵塞的风险，同时缩短生产周期。
上述第一控温装置和第二控温装置可以采用本领域常规的种类，如控温夹套、水浴、油浴等。
为了进一步提高乙炔的利用率，优选地，乙炔溶液入口设置在反应段221a和回温段221b的交界处。
为了进一步提高反应的连续化程度，缩短生产周期，在一种优选的实施例中，如图1所示，连续化合成系统还包括连续淬灭反应装置40，连续淬灭反应装置40设置有保护气入口、淬灭剂入口和待淬灭产物体系入口，待淬灭产物体系入口与三甲基硅基乙炔连续制备装置30通过待淬灭产物体系输送管路连通。
上述连续化合成系统中，格氏试剂反应装置12和连续淬灭反应装置40可以采用本领域常用的连续化反应装置。为了提高原料的转化率，优选地，格氏试剂反应装置12和连续淬灭反应装置40分别独立地选自柱状反应器和连续搅拌反应器。
为了进一步提高连续化合成反应系统的自动化程度，在一种优选的实施例中，上述连续化合成系统还包括自动进料控制系统，自动进料控制系统用于控制格氏试剂转移管路201中物料的流速、第二有机溶剂的流速、乙炔格氏试剂转移管路中物料的流速以及待淬灭产物体系输送管路中物料的流速。
本申请另一方面还提供了一种三甲基硅基乙炔的连续化合成方法，该连续化合成方法采用上述连续化合成系统制备三甲基硅基乙炔，该连续化合成方法包括：使卤代烃、第一有机溶剂和金属镁连续地输送至格氏试剂连续制备单元10进行格氏试剂连续制备反应，得到格氏试剂；将格氏试剂和乙炔溶液连续地输送至乙炔格氏试剂连续合成单元20进行乙炔格氏试剂连续合成反应，得到乙炔格氏试剂；及使乙炔格氏试剂和三甲基卤硅烷连续地输送至三甲基硅基乙炔连续制备装置30进行三甲基硅基乙炔连续制备反应，得到三甲基硅基乙炔。
采用上述三甲基硅基乙炔的连续化合成系统能够实现格氏试剂连续制备、乙炔格氏试剂连续制备和三甲基硅基乙炔的连续制备等操作的连续化工艺，可以实现自动化控制，节省人工，节省生产时间，有效降低生产成本。上述连续化合成方法具有换热能力强，且能够缩短短格氏试剂和乙炔格氏试剂的生产周期，同时将格氏试剂和乙炔格氏试剂的制备实现连续化，做到即做即用，避免格氏试剂物料长时间存储，从而有效较低安全隐患发生几率。三甲基卤硅烷与乙炔格氏试剂连续反应中，通过连续加入三甲基卤硅烷，可以保证三甲基卤硅烷与乙炔格氏试剂的当量比相对稳定，从而避免批次反应中杂质产生的风险。综上所述，采用上述 连续化合成系统制备三甲基硅基乙炔不仅能够降低生产成本，缩短生产周期，还能够提高整个工艺的安全性。
为了提高格氏试剂的转化率，同时降低格氏试剂中金属镁的残余量，在一种优选的实施例中，格氏试剂连续制备反应中，卤代烃的摩尔数、金属镁的摩尔数和第一有机溶剂的摩尔数比为1:(1.0～1.5):(3.43～5.72)，优选为1:(1.05～1.15):(3.43～4.57)
在一种优选的实施例中，格氏试剂连续制备反应的温度为40～80℃。格氏试剂连续制备反应过程中的反应温度包括但不限于上述范围，而将其限定在上述范围内有利于提高反应原料的转化率和充分反应程度。优选地，格氏试剂连续制备反应的温度为50～75℃，更优选为65～75℃。
在一种优选的实施例中，格氏试剂连续制备反应中物料的停留时间为0.2～2h。格氏试剂连续制备反应过程中物料的停留时间包括但不限于上述范围，而将其限定在上述范围内有利于提高格氏试剂的收率。优选格氏试剂连续制备反应中物料的停留时间为0.5～1h。
为了提高格氏试剂的反应速率，在一种优选的实施例中，上述连续化合成方法还包括向格氏试剂连续制备反应的反应原料中加入引发剂。
为了提高乙炔在液相反应体系中的溶解度和反应原料的利用率，在一种优选的实施例中，在进行乙炔格氏试剂连续合成反应之前，上述连续化合成方法还包括：将第二有机溶剂冷却至预定温度，然后向第二有机溶剂通入乙炔，得到乙炔溶液。优选地，预定温度为-50～0℃，更优选为-40～-10℃，进一步优选为-35～-20℃。
为了提高乙炔格氏试剂的收率，在一种优选的实施例中，乙炔的摩尔数、卤代烃的摩尔数与第二有机溶剂的摩尔数之比为(1.2～3.5):1:(3.43～5.72)，优选为(1.5～2.5):1:(3.43～4.57)。
在一种优选的实施例中，乙炔格氏试剂连续合成反应的反应温度为-20～10℃。乙炔格氏试剂连续合成反应过程中的反应温度包括但不限于上述范围，而将其限定在上述范围内有利于提高反应原料的转化率和充分反应程度。更优选地，乙炔格氏试剂连续合成反应的反应温度为-15～5℃，进一步优选为-10～0℃。
在一种优选的实施例中，乙炔格氏试剂连续合成反应中物料的停留时间为0.5～2h。乙炔格氏试剂连续合成反应过程中物料的停留时间包括但不限于上述范围，而将其限定在上述范围内有利于提高格氏试剂的收率。更优选地，乙炔格氏试剂连续合成反应中物料的停留时间为0.5～1h。
在一种优选的实施例中，上述乙炔格氏试剂连续合成单元20包括乙炔格氏试剂合成装置22，上述连续化合成方法还包括采用溢流管路202将乙炔格氏试剂从乙炔格氏试剂合成装置22连续输送至三甲基硅基乙炔连续制备装置30中，且溢流管路202的出口端延伸至乙炔格氏试剂合成装置22的底部。
溢流管路202的设置能够使乙炔格氏试剂以溢流的方式连续输出，溢流过程能够使乙炔格氏试剂的温度降低，这导致溶解在乙炔格氏试剂中的乙炔逸出；同时溢流管路202的出口端延伸至乙炔格氏试剂合成装置22的底部能够使从溶液中因为温差释放出来的乙炔在反应溶液中再次被利用，进而提高乙炔的利用，降低原料成本。为了提高三甲基硅基乙炔的收率，更优选地，乙炔格氏试剂与三甲基卤硅烷的摩尔数之比为1:(0.7～1.0)，进一步优选为1:(0.8～0.9)。
在一种优选的实施例中，三甲基硅基乙炔连续制备反应的反应温度为-10～30℃。三甲基硅基乙炔连续制备反应的反应温度包括但不限于上述范围，而将其限定在上述范围内有利于提高反应原料的转化率和充分反应程度。更优选地，三甲基硅基乙炔连续制备反应的反应温度为0～20℃，更优选为5～15℃。
在一种优选的实施例中，三甲基硅基乙炔连续制备反应中物料的停留时间为0.5～2h。三甲基硅基乙炔连续制备反应中物料的停留时间包括但不限于上述范围，而将其限定在上述范围内有利于提高格氏试剂的收率。更优选地，三甲基硅基乙炔连续制备反应中物料的停留时间为0.5～1h。
为了进一步提高连续化合成方法的自动化程度，缩短工艺周期，在一种优选的实施例中，上述连续化合成方法还包括：在保护气的氛围下，将三甲基硅基乙炔连续制备反应的产物体系和淬灭剂连续输送至连续淬灭反应装置40中进行淬灭反应，得到三甲基硅基乙炔。优选地，三甲基硅基乙炔连续制备反应的产物体系与淬灭剂的体积比为1:(0.2～0.5)。三甲基硅基乙炔连续制备反应的产物体系与淬灭剂的体积比限定在上述范围内有利于进一步提高淬灭效果。优选地，淬灭剂包括但不限于水和/或3～5wt％的盐酸水溶液。
在一种优选的实施例中，淬灭反应的温度为10～30℃。淬灭反应的温度包括但不限于上述范围，而将其限定在上述范围内有利于提高淬灭反应的反应速率，缩短淬灭时间。更优选地，淬灭反应的温度为15～25℃。
在一种优选的实施例中，淬灭反应中物料的停留时间为0.1～1h。淬灭反应中物料的停留时间包括但不限于上述范围，而将其限定在上述范围内有利于提高淬灭反应的反应程度，进而提高产物的纯度。更优选地，淬灭反应中物料的停留时间为0.3～0.5h。
在一种优选的实施方式中，第一有机溶剂和第二有机溶剂分别独立地选自四氢呋喃、或2-甲基四氢呋喃、乙醚和甲基叔丁基醚中的一种或多种。相比于其它有机溶剂，采用上述几种有机溶剂有利于进一步提高各组分的相容性，同时相比于其它溶剂，2-甲基四氢呋喃的沸点较高，更容易与产物分离。在工业化生产过程中，可以提高溶剂回收率，节省工艺成本。更优选地，第一有机溶剂和第二有机溶剂为四氢呋喃和2-甲基四氢呋喃的混合液中，2-甲基四氢呋喃和四氢呋喃的体积比为9:1～1:9，进一步优选为8:2～7:3。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
实施例1
向500ml格氏试剂反应装置12中提前加入5g氯丁烷，15g第一有机溶剂(四氢呋喃)，1.5g金属镁中。采用第一控温装置控制格氏试剂反应装置12中的温度，其中第一控温装置中设置有油浴。将油浴升温至50℃，保温10min。向格氏试剂反应装置12中滴加一滴引发剂(1，2-二溴乙烷)，以引发格氏试剂制备反应。当观察到格氏试剂反应装置12中的温度有明显提升后，开启第一进料泵14，以1g/min的速率加入氯丁烷；开启第二进料泵15，以3g/min的速率加入四氢呋喃；开启固体加料器，以0.29g/min的速率加入属镁。同时采用第一控温装置使格氏试剂反应装置12的温度保持在70℃，格氏试剂反应装置12中物料的停留时间为1h。
提前向乙炔溶解装置21中加入180mL第二有机溶剂(四氢呋喃)，并将乙炔溶解装置21的温度降至-30℃，将乙炔格氏试剂合成装置22的温度降至-5℃，三甲基硅基乙炔连续制备装置30的温度降至10℃，连续淬灭反应装置40的温度降至20℃。将乙炔溶解装置21中的乙炔溶液经溢流管输入乙炔格氏试剂合成装置22中，且溢流管路202的出口端延伸至乙炔格氏试剂合成装置22的底部。以480mL/min的速率向乙炔溶解装置21中通入乙炔，通气时间为1h。开启第三进料泵23，以4.29g/min的速率向乙炔格氏试剂合成装置22中通入上一步骤中制得的格氏试剂丁基氯化镁四氢呋喃溶液。开启第四进料泵24进料，以4.12g/min的速率向乙炔溶解装置21中通入四氢呋喃。待有乙炔格氏试剂反应的产物体系溢流到三甲基硅基乙炔连续制备装置30中，开启第五进料泵31，以1.06g/min的速率，向加入三甲基氯硅烷(从三甲基硅基乙炔连续制备装置30中取样，利用气相色谱跟踪反应效果)，反应时间为1h。
1h后，开启第六进料泵32，以9.47g/min的速率将三甲基硅基乙炔连续制备反应的产物体系输送至连续淬灭反应装置40中，同时开启第七进料泵41，以4g/min的速率向上述连续淬灭反应装置40中输入淬灭剂(水)。经淬灭后，反应体系经过分液，精馏等批次操作，得到产物三甲基硅基乙炔。从制备装置30中取样跟踪反应效果，三甲基硅基乙炔的纯度为89.92％，双取代杂质5的纯度为1.18％，精馏后得到产品纯度为98.65％，收率为70％。
实施例2
与实施例1的区别为：乙炔溶液溢流管悬空，未插入乙炔格氏试剂合成装置22的底部。
向500ml格氏试剂反应装置12中提前加入5g氯丁烷，15g第一有机溶剂(四氢呋喃)，1.5g金属镁中。采用第一控温装置控制格氏试剂反应装置12中的温度，其中第一控温装置中设置有油浴。将油浴升温至50℃，保温10min。向格氏试剂反应装置12中滴加一滴引发剂(1，2-二溴乙烷)，以引发格氏试剂制备反应。当观察到格氏试剂反应装置12中的温度有明显提升后，开启第一进料泵14，以1g/min的速率加入氯丁烷；开启第二进料泵15，以3g/min的速率加入四氢呋喃；开启固体加料器，以0.29g/min的速率加入属镁。同时采用第一控温装置使格氏试剂反应装置12的温度保持在70℃，格氏试剂反应装置12中物料的停留时间为1h。
提前向乙炔溶解装置21中加入180mL第二有机溶剂(四氢呋喃)，并将乙炔溶解装置21的温度降至-30℃，将乙炔格氏试剂合成装置22的温度降至-5℃，三甲基硅基乙炔连续制备装置30的温度降至10℃，连续淬灭反应装置40的温度降至20℃。将乙炔溶解装置21中的乙 炔溶液经溢流管输入乙炔格氏试剂合成装置22中，且乙炔溶液溢流管悬空，未插入乙炔格氏试剂合成装置22的底部。以480mL/min的速率向乙炔溶解装置21中通入乙炔，通气时间为1h。开启第三进料泵23，以4.29g/min的速率向乙炔格氏试剂合成装置22中通入上一步骤中制得的格氏试剂(丁基氯化镁四氢呋喃溶液)。开启第四进料泵24进料，以4.12g/min的速率向乙炔溶解装置21中通入四氢呋喃。待有乙炔格氏试剂反应的产物体系溢流到三甲基硅基乙炔连续制备装置30中，开启第五进料泵31，以1.06g/min的速率，向加入三甲基氯硅烷(从三甲基硅基乙炔连续制备装置30中取样，利用气相色谱跟踪反应效果)，反应时间为1h。
1h后，开启第六进料泵32，以9.47g/min的速率将三甲基硅基乙炔连续制备反应的产物体系输送至连续淬灭反应装置40中，同时开启第七进料泵41，以4g/min的速率向上述连续淬灭反应装置40中输入淬灭剂(水)。经淬灭后，反应体系经过分液，精馏等批次操作，得到产物三甲基硅基乙炔。从制备装置30中取样跟踪反应效果，三甲基硅基乙炔的纯度为72.25％；双取代杂质5的纯度为17.77％，精馏后得到产品纯度为98.2％，收率为54％。
实施例3(混合溶剂)
与实施例1的区别为：第一有机溶剂和第二有机溶剂均为2-甲基四氢呋喃与四氢呋喃的混合溶液，且二者的体积比为8:2。
向500ml格氏试剂反应装置12中提前加入5g氯丁烷，15g第一有机溶剂(2-甲基四氢呋喃与四氢呋喃的混合溶液，且二者的体积比为8:2)，1.5g金属镁中。采用第一控温装置控制格氏试剂反应装置12中的温度，其中第一控温装置中设置有油浴。将油浴升温至50℃，保温10min。向格氏试剂反应装置12中滴加一滴引发剂(1，2-二溴乙烷)，以引发格氏试剂制备反应。当观察到格氏试剂反应装置12中的温度有明显提升后，开启第一进料泵14，以1g/min的速率加入氯丁烷；开启第二进料泵15，以3g/min的速率加入第一有机溶剂；开启固体加料器，以0.29g/min的速率加入属镁。同时采用第一控温装置使格氏试剂反应装置12的温度保持在70℃，格氏试剂反应装置12中物料的停留时间为1h。
提前向乙炔溶解装置21中加入180mL第二有机溶剂(2-甲基四氢呋喃与四氢呋喃的混合溶液，且二者的体积比为8:2)，并将乙炔溶解装置21的温度降至-30℃，将乙炔格氏试剂合成装置22的温度降至-5℃，三甲基硅基乙炔连续制备装置30的温度降至10℃，连续淬灭反应装置40的温度降至20℃。将乙炔溶解装置21中的乙炔溶液经溢流管输入乙炔格氏试剂合成装置22中，且溢流管路202的出口端延伸至乙炔格氏试剂合成装置22的底部。以480mL/min的速率向乙炔溶解装置21中通入乙炔，通气时间为1h。开启第三进料泵23，以4.29g/min的速率向乙炔格氏试剂合成装置22中通入上一步骤中制得的格氏试剂(丁基氯化镁四氢呋喃溶液)。开启第四进料泵24进料，以4.12g/min的速率向乙炔溶解装置21中通入第二有机溶剂。待有乙炔格氏试剂反应的产物体系溢流到三甲基硅基乙炔连续制备装置30中，开启第五进料泵31，以1.06g/min的速率，向加入三甲基氯硅烷(从三甲基硅基乙炔连续制备装置30中取样，利用气相色谱跟踪反应效果)，反应时间为1h。
1h后，开启第六进料泵32，以9.47g/min的速率将三甲基硅基乙炔连续制备反应的产物体系输送至连续淬灭反应装置40中，同时开启第七进料泵41，以4g/min的速率向上述连续淬灭反应装置40中输入淬灭剂(水)。经淬灭后，反应体系经过分液，精馏等批次操作，得到产物三甲基硅基乙炔。从制备装置30中取样跟踪反应效果，三甲基硅基乙炔的纯度为80.12％；双取代杂质5的纯度为10.15％，精馏后得到产品纯度为97.29％，收率为62.2％。
实施例4
与实施例1的区别为：乙炔溶液采用批次化过程配制。
从制备装置30中取样跟踪反应效果，三甲基硅基乙炔的纯度为67.12％；双取代杂质5的纯度为22.15％，精馏后得到产品纯度为95.2％，收率为50.5％。
实施例5
与实施例1的区别为：
格氏试剂制备反应中，反应温度为50℃，物料的停留时间为2h；
乙炔格氏试剂合成反应中，反应温度为-15℃，物料的停留时间为1h；
三甲基硅基乙炔制备反应中，反应温度为20℃，物料的停留时间为0.5h；
连续化淬灭反应中，反应温度为10℃，物料的停留时间为1h。
从制备装置30中取样跟踪反应效果，三甲基硅基乙炔的纯度为73.12％；双取代杂质5的纯度为1.26％，精馏后得到产品纯度为98.70％，收率为62.5％。
实施例6
与实施例1的区别为：
格氏试剂制备反应中，反应温度为75℃，物料的停留时间为0.5h；
乙炔格氏试剂合成反应中，反应温度为-5℃，物料的停留时间为0.5h；
三甲基硅基乙炔制备反应中，反应温度为0℃，物料的停留时间为1h；
连续化淬灭反应中，反应温度为30℃，物料的停留时间为1h。
从制备装置30中取样跟踪反应效果，三甲基硅基乙炔的纯度为82.12％；双取代杂质5的纯度为3.26％，精馏后得到产品纯度为98.30％，收率为64.7％。
实施例7
与实施例1的区别为：
格氏试剂制备反应中，反应温度为40℃，物料的停留时间为2h；
乙炔格氏试剂合成反应中，反应温度为-20℃，物料的停留时间为0.5h；
三甲基硅基乙炔制备反应中，反应温度为30℃，物料的停留时间为0.5h；
连续化淬灭反应中，反应温度为30℃，物料的停留时间为0.1h。
从制备装置30中取样跟踪反应效果，三甲基硅基乙炔的纯度为52.12％；双取代杂质5的纯度为2.12％，精馏后得到产品纯度为96.50％，收率为42.7％。
实施例8
与实施例1的区别为：第一有机溶剂和第二有机溶剂均为2-甲基四氢呋喃与四氢呋喃的混合溶液，且二者的体积比为9:1。
从制备装置30中取样跟踪反应效果，三甲基硅基乙炔的纯度为70.12％；双取代杂质5的纯度为15.15％，精馏后得到产品纯度为96.69％，收率为57.8％。
实施例9
与实施例1的区别为：第一有机溶剂和第二有机溶剂均为2-甲基四氢呋喃与四氢呋喃的混合溶液，且二者的体积比为5:5。
从制备装置30中取样跟踪反应效果，三甲基硅基乙炔的纯度为84.20％；双取代杂质5的纯度为6.15％，精馏后得到产品纯度为98.38％，收率为66.2％。
对比例1(批次反应)
在氮气的保护下，向装有冷凝器的1L第一反应装置(四口瓶)中提前加入10g氯丁烷，300g四氢呋喃，28.9g金属镁。采用油浴将上述四口瓶的温度升至50℃，保温10min后。然后向上述第一反应装置中滴加一滴1，2-二溴乙烷引发反应，当观察到第一反应装置中有明显温升后，向其中缓慢滴加剩余90g氯丁烷。在氯丁烷的滴加过程中，使第一反应装置中反应体系的温度保持在70℃。氯丁烷的滴加完成后，将第一反应装置中反应体系继续保温1h，然后将其降至室温，得到格氏试剂，待用。
向2L第二反应装置(四口瓶)中加入410g四氢呋喃，并将第二反应装置的温度降至-30℃，向四氢呋喃中通乙炔，直至增重56g(四氢呋喃吸收的乙炔的量为卤代烃摩尔数的2倍)。然后通过恒压滴液漏斗向第二反应装置中滴加制备好的格氏试剂，滴加过程中，反应体系缓慢回温。回温过程中，反应体系中有气泡冒出，通过控制格氏试剂的滴加速度将反应体系的温度控制在-5℃。同时向上述反应体系中继续通乙炔气体，并维持乙炔气体过量。整个滴加过程共消耗2.5h。滴加完毕后，使第二反应装置在-5℃下反应1h，得到乙炔格氏试剂。
将第二反应装置的温度控制在10℃，通过恒压滴液漏斗向第二反应装置中快速滴加三甲基卤硅烷105g，共滴加10min，保温反应1h后，得到三甲基硅基乙炔产物体系。然后向上述三甲基硅基乙炔产物体系中加入400g纯化水进行淬灭反应。淬灭反应完毕后，淬灭产物经过 分液、精馏等批次操作，得到三甲基硅基乙炔。跟踪反应效果，三甲基硅基乙炔的纯度为85.56％，双取代杂质5的纯度为2.38％。精馏后得到纯品纯度为98.45％，收率63％，
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：采用上述连续化合成系统制备三甲基硅基乙炔不仅能够降低生产成本，缩短生产周期，还能够提高整个工艺的安全性；同时采用上述连续化合成工艺制备三甲基硅基乙炔还具有较高的收率和纯度。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (20)

  1. 一种三甲基硅基乙炔的连续化合成系统，其特征在于，所述连续化合成系统包括：
    格氏试剂连续制备单元(10)，所述格氏试剂连续制备单元(10)设置有第一加料口和格氏试剂出口，所述第一加料口用于将卤代烃、第一有机溶剂和金属镁连续输入所述格氏试剂连续制备单元(10)，并将格氏试剂经所述格氏试剂出口连续排出；
    乙炔格氏试剂连续合成单元(20)，所述乙炔格氏试剂连续合成单元(20)设置有格氏试剂入口、乙炔溶液入口和乙炔格氏试剂出口，所述格氏试剂入口与所述格氏试剂出口通过格氏试剂转移管路(201)连通，用于将所述格氏试剂连续输送至所述乙炔格氏试剂连续合成单元(20)中；
    三甲基硅基乙炔连续制备装置(30)，所述三甲基硅基乙炔连续制备装置(30)设置有三甲基卤硅烷入口、乙炔格氏试剂入口和三甲基硅基乙炔出口，所述乙炔格氏试剂入口与所述乙炔格氏试剂出口通过乙炔格氏试剂转移管路连通，用于将乙炔格氏试剂连续输送至所述三甲基硅基乙炔连续制备装置(30)，并将所述三甲基硅基乙炔经所述三甲基硅基乙炔出口连续排出。
  2. 根据权利要求1所述的连续化合成系统，其特征在于，所述格氏试剂连续制备单元(10)包括：
    固体加料装置(11)，用于向所述格氏试剂反应装置(12)中供应金属镁；及
    格氏试剂反应装置(12)，所述格氏试剂反应装置(12)设置有所述第一加料口和所述格氏试剂出口。
  3. 根据权利要求1或2所述的连续化合成系统，其特征在于，所述格氏试剂连续制备单元(10)还包括金属镁捕集阱(13)，所述金属镁捕集阱(13)设置在所述格氏试剂转移管路(201)上，用于去除格氏试剂中残余的所述金属镁；
    优选地，所述金属镁捕集阱(13)包括：连通设置的金属镁收集部(131)和柱状反应部(132)，且柱状反应部(132)设置有第一入口、第一出口和第二出口，第一入口与格氏试剂出口连通，第一出口与金属镁收集部(131)的入口端连通，第二出口与格氏试剂入口连通。
  4. 根据权利要求2或3所述的连续化合成系统，其特征在于，所述格氏试剂连续制备单元(10)还包括第一控温装置，所述第一控温装置用于控制所述格氏试剂反应装置(12)中的反应温度。
  5. 根据权利要求1至4中任一项所述的连续化合成系统，其特征在于，所述乙炔格氏试剂连续合成单元(20)包括：
    乙炔溶解装置(21)，所述乙炔溶解装置(21)设置有第二有机溶剂入口、乙炔气体入口和乙炔溶液出口；
    乙炔格氏试剂合成装置(22)，所述乙炔格氏试剂合成装置(22)设置有所述乙炔溶液入口和所述格氏试剂入口和所述乙炔格氏试剂出口，所述乙炔溶液入口与所述乙炔溶液出口通过溢流管路(202)连通。
  6. 根据权利要求5所述的连续化合成系统，其特征在于，所述溢流管路(202)的出口端经所述乙炔溶液入口延伸至所述乙炔格氏试剂合成装置(22)的底部。
  7. 根据权利要求5或6所述的连续化合成系统，其特征在于，所述乙炔格氏试剂合成装置(22)包括：
    壳体(221)，所述壳体(221)分为反应段(221a)和回温段(221b)，所述反应段(221a)设置有格氏试剂入口、乙炔溶液入口和乙炔尾气出口，所述回温段(221b)设置有乙炔格氏试剂出口；
    搅拌装置(222)，所述搅拌装置(222)设置在所述壳体(221)内，且沿所述壳体(221)的长度方向延伸；
    第二控温装置，所述第二控温装置用于控制所述回温段(221b)的温度。
  8. 根据权利要求1至7中任一项所述的连续化合成系统，其特征在于，所述连续化合成系统还包括连续淬灭反应装置(40)，所述连续淬灭反应装置(40)设置有保护气入口、淬灭剂入口和待淬灭产物体系入口，所述待淬灭产物体系入口与所述三甲基硅基乙炔连续制备装置(30)通过待淬灭产物体系输送管路连通。
  9. 根据权利要求7或8所述的连续化合成系统，其特征在于，所述连续化合成系统还包括自动进料控制系统，所述自动进料控制系统用于控制所述格氏试剂转移管路(201)中物料的流速、所述第二有机溶剂的流速、所述乙炔格氏试剂转移管路中物料的流速以及所述待淬灭产物体系输送管路中物料的流速。
  10. 一种三甲基硅基乙炔的连续化合成方法，其特征在于，所述连续化合成方法采用权利要求1至9中任一项所述的连续化合成系统制备三甲基硅基乙炔，所述连续化合成方法包括：
    使卤代烃、第一有机溶剂和金属镁连续地输送至格氏试剂连续制备单元(10)进行格氏试剂连续制备反应，得到格氏试剂；
    将所述格氏试剂和乙炔溶液连续地输送至乙炔格氏试剂连续合成单元(20)进行乙炔格氏试剂连续合成反应，得到乙炔格氏试剂，乙炔溶液由乙炔溶解在第二有机溶剂中形成；及
    使所述乙炔格氏试剂与三甲基卤硅烷连续地输送至三甲基硅基乙炔连续制备装置(30)进行三甲基硅基乙炔连续制备反应，得到所述三甲基硅基乙炔。
  11. 根据权利要求10所述的连续化合成方法，其特征在于，所述格氏试剂连续制备反应中，所述卤代烃的摩尔数、所述金属镁的摩尔数和所述第一有机溶剂的摩尔数之比为1:(1.0～1.5):(3.43～5.72)，优选为1:(1.05～1.15):(3.43～4.57)。
  12. 根据权利要求10或11所述的连续化合成方法，其特征在于，所述格氏试剂连续制备反应的温度为40～80℃，优选为50～75℃，更优选为65～75℃；
    所述格氏试剂连续制备反应中物料的停留时间为0.2～2h，优选为0.5～1h。
  13. 根据权利要求10所述的连续化合成方法，其特征在于，在进行所述乙炔格氏试剂连续合成反应之前，所述连续化合成方法还包括：将所述第二有机溶剂冷却至预定温度，然后向所述第二有机溶剂通入乙炔，得到所述乙炔溶液；
    优选地，所述预定温度为-50～0℃，更优选为-40～-10℃，进一步优选为-35～-20℃。
  14. 根据权利要求11所述的连续化合成方法，其特征在于，所述乙炔的摩尔数、所述卤代烃的摩尔数与所述第二有机溶剂的摩尔数之比为(1.2～3.5):1:(3.43～5.72)，优选为(1.5～2.5):1:(3.43～4.57)。
  15. 根据权利要求11所述的连续化合成方法，其特征在于，所述乙炔格氏试剂连续合成反应的反应温度为-20～10℃，优选为-15～5℃，更优选为-10～0℃；
    所述乙炔格氏试剂连续合成反应中物料的停留时间为0.5～2h，优选为0.5～1h。
  16. 根据权利要求11所述的连续化合成方法，其特征在于，所述乙炔格氏试剂连续合成单元(20)包括乙炔格氏试剂合成装置(22)；
    所述制备方法还包括采用溢流管路(202)将所述乙炔溶液连续输送至所述乙炔格氏试剂合成装置(22)中，且所述乙炔格氏试剂转移管路的出口端延伸至所述乙炔格氏试剂合成装置(22)的底部；
    优选地，所述乙炔格氏试剂与所述三甲基卤硅烷的摩尔数之比为1:(0.7～1.0)，更优选为1:(0.8～0.9)；
    优选地，所述三甲基卤硅烷选自三甲基氯硅烷和/或三甲基溴硅烷。
  17. 根据权利要求11所述的连续化合成方法，其特征在于，所述三甲基硅基乙炔连续制备反应的反应温度为-10～30℃，优选为0～20℃，更优选为5～15℃；所述三甲基硅基乙炔连续制备反应中物料的停留时间为0.5～2h，优选0.5～1h。
  18. 根据权利要求11所述的连续化合成方法，其特征在于，所述连续化合成方法还包括：在保护气的氛围下，将所述三甲基硅基乙炔连续制备反应的产物体系和淬灭剂连续输送至连续淬灭反应装置(40)中进行淬灭反应，得到所述三甲基硅基乙炔；
    优选地，所述三甲基硅基乙炔连续制备反应的产物体系与所述淬灭剂的体积比为1: (0.2～0.5)；
    优选地，所述淬灭剂选自水或3～5wt％的盐酸水溶液。
  19. 根据权利要求18所述的连续化合成方法，其特征在于，所述淬灭反应的温度为10～30℃，优选为15～25℃；
    所述淬灭反应中物料的停留时间为0.1～1h，优选为0.3～0.5h。
  20. 根据权利要求11至19中任一项所述的连续化合成方法，其特征在于，所述第一有机溶剂和所述第二有机溶剂分别独立地选自四氢呋喃、或2-甲基四氢呋喃、乙醚和甲基叔丁基醚中的一种或多种。
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