CN102093396B - Method for preparing Grignard reagent - Google Patents
Method for preparing Grignard reagent Download PDFInfo
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- CN102093396B CN102093396B CN2010106051329A CN201010605132A CN102093396B CN 102093396 B CN102093396 B CN 102093396B CN 2010106051329 A CN2010106051329 A CN 2010106051329A CN 201010605132 A CN201010605132 A CN 201010605132A CN 102093396 B CN102093396 B CN 102093396B
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Abstract
The invention discloses a method for preparing a Grignard reagent. In the conventional method for preparing the Grignard reagent by using magnesium powder, the magnesium content of the common magnesium ingot can reach over 99 percent; after the magnesium ingot forms the magnesium powder by cutting processing, the magnesium content of the magnesium powder is about 95 percent; 4 percent of metal magnesium is oxidized during the cutting processing; an oxidation film of the oxidized magnesium can delay the occurrence of a Grignard reaction to cause initiation difficulty; and if the dropping speed of halogenated hydrocarbon is increased, instant reaction is generated to release a great deal of reaction heat and a production accident occurs. The method for preparing the Grignard reagent is characterized in that: large-particle magnesium or magnesium ingot with nominal diameter of more than 1 mm serves a raw material; and the Grignard reaction is performed in a kettle reaction mode or an external circulation reaction mode. The large-particle magnesium or magnesium ingot serves the raw material, so the quantity of magnesium oxide in the magnesium is greatly reduced, proportion of byproducts formed by the magnesium oxide and an initiator is reduced, the quality of the Grignard regent is improved, and utilization ratio of the metal magnesium and utilization ratio of the halogenated hydrocarbon are increased.
Description
Technical field
The present invention relates to the reagent of chemical field, specifically a kind of preparation method of Grignard reagent.
Background technology
Grignard reagent is a kind of chemical reagent commonly used, and its common preparation method is: in reactor drum, drop into the magnesium powder, add reaction solvent ether, THF, methyltetrahydrofuran, toluene or its mixture, add initiator; Behind the nitrogen replacement, be warmed up to suitable reaction temperature, drip the mixed solution of halohydrocarbon or halohydrocarbon and solvent; Dropwise, insulation obtains qualified Grignard reagent after the cooling.This preparation method has a very big disadvantage: the utilization ratio of magnesium is low.The content of magnesium can reach more than 99% in the common magnesium ingot; And after magnesium ingot became the magnesium powder through cut, the content of magnesium had only about 95% in the magnesium powder, had 4% MAGNESIUM METAL 99 that oxidation has taken place in cut; And this part sull can be postponed the generation of grignard reaction; Cause and cause difficulty, be easy to cause the moment reaction to emit a large amount of reaction heat, industrial accident takes place if the rate of addition of halohydrocarbon is too fast.
Common Grignard reagent preparation method needs to add initiator and reacts (also can adopt batch Grignard reagent that obtains).All can cause the Grignard reagent ingress of air in metal magnesium powder and the discharging process and part takes place rotten each the throwing, have very big potential safety hazard.
One kettle way is all adopted in common Grignard reagent preparation; The halohydrocarbon charging capacity is more excessive more than 50% than theoretical amount usually; Part in this part excessive halohydrocarbon (about 1/4) is drained as waste gas; Another part (about 1/4) is dissolved in the Grignard reagent, and most of (about 1/2) and Grignard reagent generation side reaction are also brought in the subsequent reactions, and influence the quality of the finished product.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists; A kind of method that adopts macrobead magnesium or magnesium ingot to prepare Grignard reagent as raw material is provided; To reduce magnesian amount in the magnesium greatly; Improve the quality of Grignard reagent, improve the utilization ratio of MAGNESIUM METAL 99 and halohydrocarbon.
For this reason, the present invention adopts following technical scheme: a kind of preparation method of Grignard reagent, it is characterized in that adopting nominal diameter greater than the macrobead magnesium of 1mm or magnesium ingot as raw material magnesium, adopt still reaction mode or outer circulation reactive mode to carry out grignard reaction;
When adopting the still reaction mode, conversion unit is a reaction kettle, and the magnesium in the reaction kettle is in static or kinestate, and adding solvent and initiator carry out grignard reaction in reaction kettle, stir with stirring arm during grignard reaction; When adopting magnesium static, make the string bag and be fixed on the reaction kettle wall with Stainless Steel Cloth, magnesium places the string bag, the screen-aperture≤5mm of the string bag; When adopting the magnesium motion, make the string bag and be fixed on the stirring arm with Stainless Steel Cloth, magnesium places the string bag, the screen-aperture≤5mm of the string bag, and the overall dimension that makes the magnesium grain that from the string bag, spills is less than 5mm, damages in order to avoid stirring arm produced.
When adopting the outer circulation reactive mode; Conversion unit is the magnesium ingot tower of reaction kettle and series connection with it, and macrobead magnesium or magnesium ingot place the magnesium ingot tower, is provided with the back up pad and the filter core that is positioned at the back up pad below that are used to support macrobead magnesium or magnesium ingot in the magnesium ingot tower; The magnesium ingot tower has chuck outward; Adding solvent and initiator carry out grignard reaction in reaction kettle, and in the liquid inflow reaction kettle of filter element filtering, the liquid that comes out in the reaction kettle bottom is returned to the magnesium ingot tower with recycle pump; This liquid sprays to macrobead magnesium or magnesium ingot through the sparger that is positioned at magnesium ingot tower internal upper part, have on the magnesium ingot tower one be positioned at sparger below dog-house.
The string bag mainly functions as follows: 1, avoid MAGNESIUM METAL 99 and stirring arm to bump, cause the damage of stirring arm; 2, reduce MAGNESIUM METAL 99 and get into the quantity in the good Grignard reagent of reaction, thereby avoid MAGNESIUM METAL 99 the obstruction of pipeline and the danger of subsequent reactions; 3, be convenient to applying mechanically of MAGNESIUM METAL 99, when adopting macrobead magnesium to react, the charging capacity of MAGNESIUM METAL 99 is greater than theoretical charging capacity, and excessive magnesium will overlap to use in the next batch and react.The buffer action of the string bag is arranged, and grignard reaction finishes, and the Grignard reagent that reaction obtains can directly get into next step reaction, and MAGNESIUM METAL 99 can directly carry out the next batch grignard reaction because the effect of the string bag has been stayed in the reaction kettle.
In the used equipment of circulating reaction mode, the effect of sparger is that reaction solution was carried out uniform distribution before the contact magnesium ingot in the magnesium ingot tower, more helps the carrying out that reacts outside.Dog-house is to design for have high input particle magnesium or magnesium ingot specially.Because the charging capacity of the reaction magnesium of employing outer circulation form can be very big, so magnesium ingot need use bigger web plate of strength ratio silk screen or sieve plate (being back up pad) to support.The effect of filter core is to prevent that the big magnesium granules of diameter from getting in the reaction solution, and the filtration area of filter core is big, is convenient to clean.
The present invention adopts MAGNESIUM METAL 99 excessive, adopts macrobead magnesium to react and is convenient to recycle, has effectively reduced the unit consumption of halohydrocarbon, has improved the quality of Grignard reagent, direct or indirect reduction the discharging of the three wastes.
The preparation method of above-mentioned Grignard reagent; The charging capacity of macrobead magnesium or magnesium ingot is more than 3 times of theoretical charging capacity; When adopting the still reaction mode, take all factors into consideration the factor of applying mechanically number of times and output, macrobead magnesium or magnesium ingot charging capacity are preferably 5-7 times of theoretical charging capacity; When adopting the outer circulation reactive mode, take all factors into consideration the factor of applying mechanically number of times and output, the magnesium ingot charging capacity is preferably 15-35 times of theoretical charging capacity, and is too huge for preventing equipment, and macrobead magnesium charging capacity is preferably 5-15 times of theoretical charging capacity.
The used solvent of the present invention is selected ether solvent for use, or the mixture of ether solvent and aromatic solvent, like THF, methyltetrahydrofuran, ether, propyl ether etc.; Adopt initiator (like halogen etc.) to cause during first set reaction, the Grignard reagent that reaction for the second time adopts first set reaction to obtain causes.
In grignard reaction, temperature of reaction is controlled at-20～200 ℃, the atmospheric boiling point of preferred solvent; Reaction pressure is controlled at 0-2MPa, and reaction pressure need be taken all factors into consideration danger and equipment cost; The input speed of halohydrocarbon need be considered the activity of initiator and the rate of heat transfer of equipment, and general feed time was controlled at 1-10 hour, preferred 3-5 hour.
It is raw material that the present invention adopts macrobead magnesium or magnesium ingot; Because the specific surface area of macrobead magnesium is little more a lot of than normally used magnesium powder; Sull lacks than normally used magnesium powder, greatly reduces magnesian amount in the magnesium, has reduced the ratio that Natural manganese dioxide and initiator form by product; Thereby improved the quality of Grignard reagent, improved the utilization ratio of MAGNESIUM METAL 99 and halohydrocarbon; Adopt special reactor drum,, environmental protection more convenient than the reactor drum of routine; Owing to avoided the cutting process of magnesium, reduced production cost and eliminated the potential safety hazard of working angles.
Below in conjunction with Figure of description and embodiment the present invention is done further explain.
Description of drawings
Fig. 1 adopts the used equipment drawing of outer circulation reactive mode for the present invention.
Fig. 2 adopts the used equipment drawing of still reaction mode for the present invention.
Embodiment
embodiment 1.
In the outer circulation Grignard reagent preparation facilities of Fig. 1; Conversion unit is the magnesium ingot tower 1 of reaction kettle 9 and series connection with it, and macrobead magnesium or magnesium ingot 5 place magnesium ingot tower 1, is provided with the back up pad 6 and the filter core 7 that is positioned at the back up pad below that are used to support macrobead magnesium or magnesium ingot in the magnesium ingot tower 1; The magnesium ingot tower has chuck 4 outward; Adding solvent and initiator carry out grignard reaction in reaction kettle, and in the liquid inflow reaction kettle 9 of filter element filtering, the liquid that comes out in the reaction kettle bottom is returned to the magnesium ingot tower with recycle pump 10; This liquid sprays to macrobead magnesium or magnesium ingot through the sparger 2 that is positioned at magnesium ingot tower internal upper part, have on the magnesium ingot tower one be positioned at sparger 2 belows dog-house 3.
Concrete preparation method is following: in the magnesium ingot tower, drop into the magnesium ingot 500kg of 50*50*500 in advance, utilize vacuum in the 200L reaction kettle, to drop into THF 80L, add initiator elemental iodine 0.1Kg.Fill the nitrogen displacement in the reaction kettle, tail gas is discharged from the magnesium ingot cat head.Displacement finishes, and closes evacuation port.Drive the reaction kettle bottom valve, open cycle pump discharge valve, turn on pump is played circulation.Open reacting kettle jacketing heating steam and heat, the adjustment vapor pressure is 0.05MPa, slowly heats, and adjusts vapor pressure, with temperature control in the still at 80-90 ℃.Utilize nitrogen to be pressed into halohydrocarbon the mixed solution of 30Kg monochloro methane and 140L THF and drip in the groove, and in halohydrocarbon drips groove, charge into nitrogen make in pressure reach 0.5MPa.
When temperature in the still reaches about 80 ℃, the still internal pressure reaches 0.25-0.3MPa.Behind the temperature-stable, open halohydrocarbon and drip groove 8 bottom valves, begin to drip halohydrocarbon solution.Be controlled at and dropwised in 2 hours, the ratio that rises when the temperature in the kettle rate of addition that need slow down when very fast, reacting kettle jacketing feeds water coolant and cools off, and temperature is controlled in 90 ℃.After halohydrocarbon dropwises, continue under 80-90 ℃ of condition, to be incubated 2 hours.
Insulation reaction finishes, and reacting kettle jacketing is opened water coolant and cooled off.Be cooled in the still temperature below 50 ℃, in still, charge into nitrogen make in pressure reach 0.3MPa.Stop to play circulation, Grignard reagent in the still is got to use equipment with pump.After material had been beaten, related valve was closed in termination of pumping rapidly.
Open exhaust-valve on the magnesium ingot tower, let out 0.02MPa, need not add initiator and MAGNESIUM METAL 99, directly carry out next batch and feed intake pressing in the still.So reaction can be carried out between 32-35 criticizes altogether, near theoretical access times.
Can obtain methyl chloride Grignard reagent 245L, methyl chloride Ge Shi concentration 2.38mol/L, the methyl chloride yield is greater than 98%.
embodiment 2.
In the still reaction Grignard reagent preparation facilities of Fig. 2 (reactor volume is 500L).Magnesium adopts stationary state, makes the string bag 11 and is fixed on reaction kettle 12 walls with Stainless Steel Cloth, and magnesium places the string bag, the screen-aperture≤5mm of the string bag.
Concrete preparation method is following: utilize the magnesium of commissioning pipe around reaction kettle fixedly to drop into MAGNESIUM METAL 99 particle 200Kg (10*10*20) in the string bag in advance, utilize vacuum in reaction kettle, to drop into THF 95L, add initiator elemental iodine 0.12Kg.Fill the nitrogen displacement in the reaction kettle.Displacement finishes, and closes evacuation port.Open reacting kettle jacketing heating steam and heat, the adjustment vapor pressure is 0.05MPa, slowly heats, and adjusts vapor pressure, with temperature control in the still at 80-90 ℃.Utilize nitrogen to be pressed into halohydrocarbon the mixed solution of 40Kg monochloro methane and 215L THF and drip in the groove 12, and in halohydrocarbon drips groove, charge into nitrogen make in pressure reach 0.5MPa.
When temperature in the still reaches about 80 ℃, the still internal pressure can reach 0.25-0.3MPa.Behind the temperature-stable, open halohydrocarbon and drip the bottom land valve, begin to drip halohydrocarbon solution.Be controlled at and dropwised in 3 hours, the ratio that rises when the temperature in the kettle rate of addition that need slow down when very fast, reacting kettle jacketing feeds water coolant and cools off, and temperature is controlled in 90 ℃.After halohydrocarbon dropwises, continue under 80-90 ℃ of condition, to be incubated 2.5 hours.
Insulation reaction finishes, and reacting kettle jacketing is opened water coolant and cooled off.Be cooled in the still temperature below 50 ℃, in still, charge into nitrogen make in pressure reach 0.3MPa.Grignard reagent in the still is pressed onto use equipment with nitrogen.After material has been pressed, close related valve.
Can obtain methyl chloride Grignard reagent 341L, methyl chloride Ge Shi concentration 2.35mol/L, the methyl chloride yield is greater than 98%.So reaction can be carried out between 9-11 criticizes altogether, near theoretical access times.
Claims (7)
1. the preparation method of a Grignard reagent, it is characterized in that adopting nominal diameter greater than the macrobead magnesium of 1mm or magnesium ingot as raw material magnesium, adopt still reaction mode or outer circulation reactive mode to carry out grignard reaction;
When adopting the still reaction mode, conversion unit is a reaction kettle, and the magnesium in the reaction kettle is in static or kinestate, and adding solvent and initiator carry out grignard reaction in reaction kettle, stir with stirring arm during grignard reaction; When adopting magnesium static, make the string bag and be fixed on the reaction kettle wall with Stainless Steel Cloth, magnesium places the string bag, the screen-aperture≤5mm of the string bag; When adopting the magnesium motion, make the string bag and be fixed on the stirring arm with Stainless Steel Cloth, magnesium places the string bag, the screen-aperture≤5mm of the string bag;
When adopting the outer circulation reactive mode; Conversion unit is the magnesium ingot tower of reaction kettle and series connection with it; Magnesium places the magnesium ingot tower, is provided with the back up pad and the filter core that is positioned at the back up pad below that are used to support magnesium in the magnesium ingot tower, and adding solvent and initiator carry out grignard reaction in reaction kettle; Liquid through filter element filtering flows in the reaction kettle; The liquid that comes out in reaction kettle bottom is returned to the magnesium ingot tower with recycle pump, and this liquid sprays to magnesium through the sparger that is positioned at magnesium ingot tower internal upper part, have on the magnesium ingot tower one be positioned at the sparger below dog-house.
2. the preparation method of Grignard reagent according to claim 1, the consumption that it is characterized in that said macrobead magnesium or magnesium ingot is more than 3 times of theoretical charging capacity.
3. the preparation method of Grignard reagent according to claim 2 is characterized in that when adopting the still reaction mode, and macrobead magnesium or magnesium ingot charging capacity are 5-7 times of theoretical charging capacity.
4. the preparation method of Grignard reagent according to claim 2 is characterized in that when adopting the outer circulation reactive mode,
Macrobead magnesium charging capacity is 5-15 a times of theoretical charging capacity, and the magnesium ingot charging capacity is 15-35 a times of theoretical charging capacity.
5. the preparation method of Grignard reagent according to claim 1 and 2 is characterized in that solvent selects ether solvent for use, or the mixture of ether solvent and aromatic solvent.
6. the preparation method of Grignard reagent according to claim 5 is characterized in that described solvent is THF, methyltetrahydrofuran, ether or propyl ether.
7. the preparation method of Grignard reagent according to claim 1 adopts initiator to cause when it is characterized in that first set reaction, and the Grignard reagent that reaction for the second time adopts first set reaction to obtain causes.
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Families Citing this family (8)
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| CN102603775B (en) * | 2012-01-20 | 2015-08-05 | 上海海嘉诺医药发展股份有限公司 | A kind of device of continuous production Grignard reagent and use this device to carry out the method for Grignard reagent continuous production |
| CN103055788B (en) * | 2012-12-26 | 2014-04-16 | 淮安万邦香料工业有限公司 | Method for increasing metallic sodium reaction area |
| CN103539666B (en) * | 2013-09-27 | 2015-06-03 | 上虞新和成生物化工有限公司 | Preparation method of 2-methyl-3-butenoic acid ester |
| CN103936783B (en) * | 2014-04-14 | 2017-06-23 | 广东信翼科技有限公司 | A kind of continuous device prepared containing specific groups organic silicon monomer and the preparation method using the device |
| CN107556331A (en) * | 2017-09-04 | 2018-01-09 | 南京哈柏医药科技有限公司 | The production technology of RMgBr |
| KR20220132520A (en) * | 2020-01-27 | 2022-09-30 | 가부시키가이샤 도쿠야마 | Method for producing halogenated hydrocarbon magnesium compound, and method for producing tertiary alcohol compound and organosilicon compound |
| CN112047964A (en) * | 2020-09-07 | 2020-12-08 | 宋喂 | Preparation method and application of Grignard reagent |
| CN112574238A (en) * | 2020-12-11 | 2021-03-30 | 安徽金禾实业股份有限公司 | Method for preparing Grignard reagent in maltol Grignard section |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455718B1 (en) * | 1996-11-22 | 2002-09-24 | Albemarle Corporation | Halogen exchange reactions in preparing catalysts and their precursors |
| CN101129184A (en) * | 2007-09-12 | 2008-02-27 | 安徽金禾实业股份有限公司 | Grignard reaction method in production of maltol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ES473049A1 (en) * | 1976-11-09 | 1979-10-16 | Charbonnages Ste Chimique | Grignard reagents and processes for making them |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455718B1 (en) * | 1996-11-22 | 2002-09-24 | Albemarle Corporation | Halogen exchange reactions in preparing catalysts and their precursors |
| CN101129184A (en) * | 2007-09-12 | 2008-02-27 | 安徽金禾实业股份有限公司 | Grignard reaction method in production of maltol |
Non-Patent Citations (1)
| Title |
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| JP昭53-59628A 1978.05.29 |
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