CN117024452B - Preparation process of phenyl magnesium chloride - Google Patents
Preparation process of phenyl magnesium chloride Download PDFInfo
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- CN117024452B CN117024452B CN202310987013.1A CN202310987013A CN117024452B CN 117024452 B CN117024452 B CN 117024452B CN 202310987013 A CN202310987013 A CN 202310987013A CN 117024452 B CN117024452 B CN 117024452B
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- chlorobenzene
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- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 149
- 239000011550 stock solution Substances 0.000 claims abstract description 143
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 138
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 41
- 239000011777 magnesium Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000004321 preservation Methods 0.000 claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 82
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 54
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 29
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 27
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical group CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 28
- 235000010290 biphenyl Nutrition 0.000 abstract description 14
- 239000004305 biphenyl Substances 0.000 abstract description 14
- 238000007086 side reaction Methods 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- 238000005070 sampling Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- 125000003944 tolyl group Chemical group 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000003747 Grignard reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a preparation process of phenyl magnesium chloride. In the preparation process, chlorobenzene or a mixed solution of chlorobenzene, a solvent A and a solvent B is used as a first stock solution, a mixed solution of the solvent A and the solvent B is used as a second stock solution, and magnesium chips and an initiator are mixed as a third stock solution; firstly, part of the first stock solution is put into a reaction kettle to be mixed with the third stock solution, the reaction is initiated at a certain temperature, part of the first stock solution and the second stock solution are simultaneously dripped at 90-110 ℃, then the rest of the first stock solution and the second stock solution are simultaneously dripped at 85-95 ℃ for 2-3 hours, and the heat preservation reaction is carried out to obtain the product phenylmagnesium chloride solution with high yield. The invention is beneficial to control the side reaction for generating biphenyl by adopting limited feed liquid and reaction, thereby improving the yield of the phenylmagnesium chloride, being more energy-saving, and the conversion rate of the chlorobenzene reaches more than 99.5 percent, and the yield of the phenylmagnesium chloride reaches more than 98.8 percent.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation process of high-yield phenyl magnesium chloride.
Background
The phenyl magnesium chloride is an intermediate for preparing triphenylphosphine, and the triphenylphosphine is a basic raw material of a rhodium-phosphine complex catalyst and has wide application in petrochemical industry. Triphenylphosphine is also used in the fields of pharmaceutical industry, organic synthesis, analysis and the like, can be used for preparing Wittig reagent, can also be used as a brightening agent for dye technology, an antioxidant for high molecular polymerization and color film development, and a stabilizer for poly epoxidation, and can be used as an analysis reagent.
Phenyl magnesium chloride is generally synthesized by grignard reaction of chlorobenzene and magnesium in a mixed solvent of toluene (or benzene) and tetrahydrofuran (or 2-methyltetrahydrofuran), and the reaction equation is as follows:
the main side reaction is that phenyl magnesium chloride reacts with chlorobenzene to generate biphenyl, and the reaction equation is as follows:
，
and the reaction temperature is generally increased, which is more beneficial to the side reaction for producing biphenyl.
Chinese patent CN102887919B refers to a method for synthesizing phenyl magnesium chloride by using chlorobenzene and magnesium in a mixed solvent of toluene and tetrahydrofuran, wherein toluene (80-120 parts), tetrahydrofuran (26-35 parts) and magnesium (6-8.5 parts) are all put into a reaction kettle, chlorobenzene (220-260 parts) is dropwise added in stages, 1/4-1/2 chlorobenzene is dropwise added at 80+/-5 ℃ in the first stage, then the temperature is raised to 100-105 ℃ for 30min, then the temperature is lowered to 80+/-5 ℃ for dropwise adding residual chlorobenzene, and then the temperature is raised to 100-105 ℃ for dropwise adding residual chlorobenzene. The process has great excess chlorobenzene relative to magnesium, and the temperature is raised to 100-105 ℃ twice, which is unfavorable for controlling the occurrence of biphenyl side reaction, and the yield of the product phenylmagnesium chloride is low.
Chinese patent CN108084225A refers to a method for synthesizing phenyl magnesium chloride by chlorobenzene and magnesium in mixed solvent of toluene and tetrahydrofuran, after chlorobenzene, toluene and tetrahydrofuran are mixed, about 10% of mixed solution is firstly added into a reaction kettle to be mixed with magnesium scraps, reaction is initiated at 50-60 ℃, then the mixed solution of residual chlorobenzene and solvent is slowly dripped at 100-110 ℃ for 4.5-5.5h, and the reaction is finished after heat preservation at 100-110 ℃ for 4.5-5.5 h. The process also controls the excessive amount of chlorobenzene relative to magnesium, does not control the generation amount of biphenyl, and extracts biphenyl as a byproduct in the separation stage of triphenylphosphine as a final product. The biphenyl product has low economic value, two molecules of chlorobenzene and one molecule of magnesium are consumed for obtaining one molecule of biphenyl, the raw material value is greatly over the product value, the yield of phenyl magnesium chloride is sacrificed, and the practicability is poor.
Chinese patent CN111454292a mentions a method for synthesizing phenylmagnesium chloride from chlorobenzene and magnesium in a mixed solvent of benzene and 2-methyltetrahydrofuran, which comprises mixing chlorobenzene, benzene and 2-methyltetrahydrofuran in a mass ratio of 1:2: (1.3-2) mixing to obtain a first reaction stock solution, mixing magnesium and a catalyst to obtain a second reaction stock solution, wherein the mass ratio of chlorobenzene to magnesium is (4-7): 1, heating the second reaction stock solution to 50-100 ℃, then dripping the first reaction stock solution for reaction, and keeping the temperature for 2 hours after dripping to obtain the phenyl magnesium chloride. The process has large excess of chlorobenzene relative to magnesium, is unfavorable for inhibiting side reaction of biphenyl, and has low yield of phenyl magnesium chloride.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a process for preparing phenyl magnesium chloride with high yield, which can effectively inhibit biphenyl side reaction, improve chlorobenzene conversion rate and main reaction selectivity.
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation process of phenyl magnesium chloride specifically comprises the following steps:
1) The method comprises the steps of taking chlorobenzene or a mixed solution of chlorobenzene, a solvent A and a solvent B as a first stock solution, taking a mixed solution of the solvent A and the solvent B as a second stock solution, taking magnesium chips and an initiator as a third stock solution after mixing, wherein the solvent A is toluene or benzene, and the solvent B is tetrahydrofuran or 2-methyltetrahydrofuran;
2) Heating the third stock solution to 65-90 ℃ in a reaction kettle, adding 2-20wt% of the first stock solution into the reaction kettle to initiate reaction, simultaneously dropwise adding 40-60wt% of the rest first stock solution and 60-100deg.C of the second stock solution within 3-6h at 90-110 ℃, continuously dropwise adding the rest first stock solution and the rest second stock solution within 2-3h at 85-95 ℃, and carrying out heat preservation reaction for 2-5h at 80-90 ℃ after the dropwise adding is completed, thus obtaining the high-yield product phenylmagnesium chloride solution.
Further, the invention defines that the total mass ratio of the solvent A to the total mass of the solvent B in the first stock solution and the second stock solution is 4-6.5:6-3.5; the sum of the mass of the solvent A and the solvent B in the first stock solution is 0-30% of the total mass of the solvent A and the solvent B in the first stock solution and the second stock solution; the mole ratio of chlorobenzene to the total amount of solvent B in the first stock solution and the second stock solution is 1:1.9-3.0; the mol ratio of chlorobenzene to magnesium chip is 1:1.0-1.4.
Furthermore, the invention limits the mixed solution of the solvent A and the solvent B, wherein the initiator is phenylmagnesium chloride, and the mixed solution used as the initiator can be externally added into a kettle or can be a partial product of the residue of the previous batch reaction.
Further, the present invention defines that the initiation reaction stage may be charged with 2 to 15wt% of the second stock solution in addition to 2 to 20wt% of the first stock solution.
Further, the invention limits the dripping of the rest first stock solution and the second stock solution and the heat preservation reaction stage after dripping, and the stirring speed of the reaction kettle is 125rpm-250rpm; and in the heat preservation reaction stage, the feed liquid in the reaction kettle is pumped by an external circulating pump to circulate and strengthen the mixing of the feed liquid in the reaction kettle.
Further, the invention defines a thermal insulation reaction stage, the feed liquid in the reaction kettle is pumped and circulated by the external circulating pump to strengthen the mixing of the feed liquid in the reaction kettle, and the pipe orifice pumped and circulated by the external circulating pump into the reaction kettle is positioned below the liquid level in the reaction kettle.
Further, the invention is limited in that the reaction kettle is internally provided with a jet mixer for a tank, a pipe orifice which is circulated into the reaction kettle is inserted into the reaction kettle to be connected with the jet mixer for the tank, and the feed liquid is circulated through the jet mixer for the tank.
In order to better control the reaction, the invention can also be provided with baffle plates in the reaction kettle, wherein the number of the baffle plates is 3-8, and the baffle plates are uniformly distributed along the wall of the reaction kettle.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1) According to the invention, chlorobenzene and a mixed solvent are separately and bi-dropwise added into a reaction kettle in a separated mode, flexible inhibition of biphenyl side reaction according to reaction progress is realized, high concentration of magnesium chips and low concentration of chlorobenzene in a reaction system are ensured in the early stage of reaction, and higher reaction temperature is ensured, so that main reaction for generating phenyl magnesium chloride is rapidly carried out, and side reaction of chlorobenzene and phenyl magnesium chloride is inhibited; as the reaction proceeds, the concentration of the phenylmagnesium chloride in the system is increased, the concentration of magnesium chips is reduced, more solvent is added to dilute the concentration of the phenylmagnesium chloride, the reaction temperature is reduced, the inhibition of the side reaction of biphenyl is realized, and the yield of the main reaction is ensured;
2) According to the invention, the baffle is arranged in the reaction kettle, and in the later reaction period, through enhanced stirring, increased external circulation and an internal jet mixer, the contact between residual magnesium chips in the system and chlorobenzene is enhanced, the main reaction is continuously promoted, and the main reaction yield is ensured;
3) The invention controls the excessive magnesium compared with chlorobenzene, is favorable for controlling the side reaction for generating biphenyl, and unreacted magnesium can be reserved in a kettle for the production of next batch of phenylmagnesium chloride by a standing separation means; compared with magnesium, the method has the advantages that the method is unfavorable for controlling the side reaction of biphenyl because of excessive chlorobenzene, the conversion rate of chlorobenzene is low, and more energy is consumed for recycling unreacted chlorobenzene in the subsequent process through distillation or rectification. The invention not only can improve the yield of the phenyl magnesium chloride, but also can save more energy.
4) The process provided by the invention can achieve high conversion rate of chlorobenzene and high yield of phenyl magnesium chloride, the conversion rate of chlorobenzene reaches more than 99.5%, and the yield of phenyl magnesium chloride reaches more than 98.8%.
Drawings
FIG. 1 is a schematic structural view of a reaction apparatus according to the present invention.
In the figure: 1-a reaction kettle; 2-magnesium chip feeding hopper; 3-a first stock solution metering tank; 4-a second stock solution metering tank; 5-an external circulating pump; 6, a baffle; 7-tank jet mixer.
Detailed Description
The present invention is further defined by the following examples, although the scope of the present invention is not limited thereto.
The invention relates to a device for preparing phenyl magnesium chloride with high yield, which has the structure shown in figure 1, and comprises a reaction kettle 1, a magnesium chip feeding hopper 2, an external circulating pump 5, a first stock solution metering tank 3 and a second stock solution metering tank 4; the reaction kettle 1 is provided with a plurality of inlets; the outlet of the magnesium chip feeding hopper 2 is connected with a magnesium chip inlet arranged on the reaction kettle 1, the bottom and the side wall of the reaction kettle 1 are provided with circulating liquid outlets, the side wall of the reaction kettle is provided with a circulating liquid inlet, the inlet end in the reaction kettle is provided with a tank jet mixer 7, the circulating liquid outlet is connected with the inlet of an external circulating pump 5, and the outlet of the external circulating pump 5 is connected with the inlet of an internal tank jet mixer 7; the outlet of the first stock solution metering tank 3 is connected with a first stock solution inlet arranged on the reaction kettle 1 and used for feeding the first stock solution, and the outlet of the second stock solution metering tank 4 is connected with a second stock solution inlet arranged on the reaction kettle 1 and used for feeding the second stock solution.
In order to improve the material liquid circulation effect, the bottom and the side wall of the reaction kettle are respectively provided with a circulating liquid outlet, and the circulating liquid outlet is connected with an inlet of an external circulating pump 5 through a pipeline.
The circulating liquid inlet on the side wall of the reaction kettle 1 is positioned at any position below the side wall of the reaction kettle 1 or the lower end socket except the bottom outlet.
In order to further control the reaction, the invention is also provided with baffle plates 6 in the reaction kettle 1, the number of the baffle plates is 3-8, and the baffle plates are uniformly distributed along the wall of the reaction kettle 1.
In order to facilitate the feeding of the initiator, the invention is provided with an initiator inlet on the reaction kettle 1.
Example 1
1) Chlorobenzene is used as a first stock solution, a mixed solution of toluene and tetrahydrofuran with a mass ratio of 5:5 is used as a second stock solution, and the mol ratio of the chlorobenzene in the first stock solution to the tetrahydrofuran in the second stock solution is 1:2.1; mixing magnesium chips and an initiator as a third stock solution, wherein the molar ratio of the magnesium chips to chlorobenzene in the first stock solution is 1.05:1, the initiator is toluene and tetrahydrofuran solution of phenylmagnesium chloride, the dosage is 20% of the volume of the first stock solution, the mass concentration of the phenylmagnesium chloride is 25%, and the mass ratio of toluene to tetrahydrofuran is 5:5;
2) Heating the third stock solution to 75 ℃ in a reaction kettle, adding 10wt% of the first stock solution into the reaction kettle to initiate reaction, dropwise adding 50wt% of the rest first stock solution and 60wt% of the second stock solution into the reaction kettle at the rotating speed of 100rpm and the kettle temperature of 100 ℃ for 5 hours, stirring and rotating the reaction kettle to 125rpm, continuously dropwise adding the rest first stock solution and the rest second stock solution at the temperature of 95 ℃ for 2 hours, starting an external circulating pump to pump and circulate after the dropwise adding is finished, enabling a pipe orifice of the circulating pipe to enter below the liquid level in the reaction kettle, arranging a tank jet mixer at the pipe orifice, carrying out heat preservation reaction at the temperature of 85 ℃ for 2 hours to obtain a high-yield phenyl magnesium chloride solution, sampling and inspecting, and calculating the chlorobenzene conversion rate of 99.89% and the phenyl magnesium chloride yield of 99.26% according to detection results.
Example 2
1) Benzene and tetrahydrofuran are mixed according to a mass ratio of 5:5, wherein 20% of the benzene and the chlorobenzene are mixed to form a first stock solution, the remaining 80% of the benzene and the tetrahydrofuran are mixed to form a second stock solution, and the mol ratio of the chlorobenzene to all the tetrahydrofuran in the first stock solution and the second stock solution is 1:2.2; mixing magnesium chips and an initiator as a third stock solution, wherein the molar ratio of the magnesium chips to chlorobenzene in the first stock solution is 1.3:1, the initiator is benzene and tetrahydrofuran solution of phenylmagnesium chloride, the dosage is 15% of the volume of the first stock solution, the mass concentration of the phenylmagnesium chloride is 25%, and the mass ratio of benzene to tetrahydrofuran is 5:5;
2) Heating the third stock solution to 85 ℃ in a reaction kettle, putting 20wt% of the first stock solution into the reaction kettle to initiate reaction, dropwise adding 40wt% of the rest first stock solution and 80wt% of the second stock solution into the reaction kettle at the rotating speed of 90rpm and at the kettle temperature of 110 ℃ for 3 hours, stirring and rotating the reaction kettle to 150rpm, continuously dropwise adding the rest first stock solution and the rest second stock solution at the temperature of 90 ℃ for 3 hours, starting an external circulating pump to pump and circulate after the dropwise adding is finished, enabling a pipe orifice of the circulating pipe to enter below the liquid level in the reaction kettle, arranging a tank jet mixer at the pipe orifice, carrying out heat preservation reaction for 4 hours at the temperature of 85 ℃ to obtain a high-yield phenyl magnesium chloride solution, sampling and inspecting, and calculating the chlorobenzene conversion rate of 99.93% and the phenyl magnesium chloride yield of 99.37%.
Example 3
1) Toluene and 2-methyltetrahydrofuran are mixed according to a mass ratio of 5:5, wherein 15% of the toluene and the chlorobenzene are mixed to form a first stock solution, the rest 85% of the toluene and the chlorobenzene are mixed to form a second stock solution, and the mol ratio of the chlorobenzene to all 2-methyltetrahydrofuran in the first stock solution and the second stock solution is 1:2.4; adding magnesium chips into a reaction kettle and mixing with the initiator to obtain a third stock solution, wherein the molar ratio of the magnesium chips to chlorobenzene in the first stock solution is 1.2:1, the initiator is toluene and 2-methyltetrahydrofuran solution of phenylmagnesium chloride, the dosage of the initiator is 15% of the volume of the first stock solution, the mass concentration of the phenylmagnesium chloride is 25%, and the mass ratio of the toluene to the 2-methyltetrahydrofuran is 5:5;
2) Heating the third stock solution to 80 ℃ in a reaction kettle, adding 15wt% of the first stock solution into the reaction kettle to initiate reaction, dropwise adding 50wt% of the rest first stock solution and 70wt% of the second stock solution into the reaction kettle at the rotating speed of 90rpm and the kettle temperature of 95 ℃ for 5 hours, stirring and rotating the reaction kettle to 140rpm, continuously dropwise adding the rest first stock solution and the rest second stock solution at the temperature of 85 ℃ for 3 hours, starting an external circulating pump to pump and circulate after the dropwise adding is finished, enabling a pipe orifice of the circulating pipe to enter below the liquid level in the reaction kettle, arranging a tank jet mixer at the pipe orifice, carrying out heat preservation reaction at 80 ℃ for 3 hours to obtain a high-yield phenyl magnesium chloride solution, sampling and inspecting, and calculating the chlorobenzene conversion rate of 99.91% and the phenyl magnesium chloride yield of 99.34% according to detection results.
Example 4
1) Chlorobenzene is used as a first stock solution, a mixed solution of toluene and tetrahydrofuran with a mass ratio of 5:5 is used as a second stock solution, and the mol ratio of the chlorobenzene in the first stock solution to the tetrahydrofuran in the second stock solution is 1:2.1; mixing magnesium chips and an initiator as a third stock solution, wherein the molar ratio of the magnesium chips to chlorobenzene in the first stock solution is 1.2:1, the initiator is toluene and tetrahydrofuran solution of phenylmagnesium chloride, the dosage is 20% of the volume of the first stock solution, the mass concentration of the phenylmagnesium chloride is 25%, and the mass ratio of toluene to tetrahydrofuran is 5:5;
2) Heating the third stock solution to 75 ℃ in a reaction kettle, adding 10wt% of the first stock solution and 10wt% of the second stock solution into the reaction kettle to initiate reaction, dropwise adding 50wt% of the rest first stock solution and 60wt% of the second stock solution into the reaction kettle within the period of 5 hours at the rotating speed of 100rpm and the kettle temperature of 100 ℃, stirring and rotating the reaction kettle to 125rpm, continuously dropwise adding the rest first stock solution and the rest second stock solution within the period of 2 hours at the temperature of 95 ℃, starting an external circulating pump to circulate after the dropwise adding, enabling a pipe orifice of the circulating pipe to enter below the liquid level in the reaction kettle, arranging a tank jet mixer at the pipe orifice, carrying out heat preservation reaction for 2 hours at the temperature of 85 ℃ to obtain a high-yield phenyl magnesium chloride solution, sampling and checking, and calculating the chlorobenzene conversion rate of 99.93% and the phenyl magnesium chloride yield of 99.42% according to the detection result.
Example 5
1) Chlorobenzene is used as a first stock solution, a mixed solution of toluene and tetrahydrofuran with a mass ratio of 4:6 is used as a second stock solution, and the mol ratio of the chlorobenzene in the first stock solution to the tetrahydrofuran in the second stock solution is 1:2.8; the partial products remained in the reaction kettle in the batch reaction are used as an initiator, magnesium chips are put into the kettle and mixed with the initiator to be used as a third stock solution, the mol ratio of the magnesium chips to chlorobenzene in the first stock solution is 1.4:1, the initiator is toluene and tetrahydrofuran solution of phenylmagnesium chloride, the dosage of the initiator is 20% of the volume of the first stock solution, the mass concentration of the phenylmagnesium chloride is 25%, and the mass ratio of toluene to tetrahydrofuran is 4:6;
2) Heating the third stock solution to 90 ℃ in a reaction kettle, adding 10wt% of the first stock solution and 10wt% of the second stock solution into the reaction kettle to initiate reaction, dropwise adding 40wt% of the rest first stock solution and 80wt% of the second stock solution in the reaction kettle at the rotating speed of 100rpm and the kettle temperature of 110 ℃ for 4 hours, stirring and rotating the reaction kettle to 130rpm, continuously dropwise adding the rest first stock solution and the rest second stock solution in the reaction kettle at the temperature of 90 ℃ for 2 hours, starting an external circulating pump to circulate after the dropwise adding, enabling a pipe orifice of the circulating pipe to enter below the liquid level in the reaction kettle, arranging a tank jet mixer at the pipe orifice, carrying out heat preservation reaction for 2 hours at the temperature of 85 ℃ to obtain a high-yield phenyl magnesium chloride solution, sampling and inspecting, and calculating the chlorobenzene conversion rate of 99.53% and the phenyl magnesium chloride yield of 99.02% according to detection results.
Example 6
1) Toluene and 2-methyltetrahydrofuran are mixed according to a mass ratio of 6:4, wherein 10% of the toluene and the chlorobenzene are mixed to form a first stock solution, the rest 90% of the toluene and the 2-methyltetrahydrofuran are mixed to form a second stock solution, and the mol ratio of the chlorobenzene in the first stock solution to the 2-methyltetrahydrofuran in the second stock solution is 1:3; mixing magnesium chips and an initiator as a third stock solution, wherein the molar ratio of the magnesium chips to chlorobenzene in the first stock solution is 1.3:1, the initiator is toluene and 2-methyltetrahydrofuran solution of phenyl magnesium chloride, the dosage is 20% of the volume of the first stock solution, the mass concentration of the phenyl magnesium chloride is 25%, and the mass ratio of toluene to 2-methyltetrahydrofuran is 6:4;
2) Heating the third stock solution to 80 ℃ in a reaction kettle, adding 5wt% of the first stock solution and 10wt% of the second stock solution into the reaction kettle to initiate reaction, dropwise adding 40wt% of the rest first stock solution and 80wt% of the second stock solution in the reaction kettle at the rotating speed of 100rpm and the kettle temperature of 110 ℃ for 4 hours, stirring and rotating the reaction kettle to 128rpm, continuously dropwise adding the rest first stock solution and the rest second stock solution in the reaction kettle at the temperature of 90 ℃ for 2 hours, starting an external circulating pump to circulate after the dropwise adding, enabling a pipe orifice of the circulating pipe to enter below the liquid level in the reaction kettle, arranging a tank jet mixer at the pipe orifice, carrying out heat preservation reaction for 2 hours at the temperature of 85 ℃ to obtain a high-yield phenyl magnesium chloride solution, sampling and inspecting, and calculating the chlorobenzene conversion rate of 99.83% and the phenyl magnesium chloride yield of 99.62% according to detection results.
Comparative example 1 (modified magnesium turnings excess compared to chlorobenzene according to patent CN 108084225A)
Preparing a mixed solution of chlorobenzene, toluene and tetrahydrofuran according to a mass ratio of 1:2:3.1, and adding magnesium chips into a reaction kettle, wherein the molar ratio of the magnesium chips to the chlorobenzene is 1.15:1, adding 1/10 of the mixed solution of chlorobenzene, toluene and tetrahydrofuran into a kettle, adding toluene and tetrahydrofuran solution of phenylmagnesium chloride as an initiator, heating to 60 ℃ to initiate Grignard reaction, heating to 110 ℃, slowly dripping the rest mixed solution into the kettle through a high-level tank at the temperature within 5.5h, carrying out heat preservation reaction at 110 ℃ for 5.5h after dripping is finished to obtain phenylmagnesium chloride solution, sampling and inspecting, and calculating the chlorobenzene conversion rate of 94.33% and the phenylmagnesium chloride yield of 86.45% according to the detection result.
Claims (8)
1. The preparation process of phenyl magnesium chloride is characterized by comprising the following steps:
1) The method comprises the steps of taking chlorobenzene or a mixed solution of chlorobenzene, a solvent A and a solvent B as a first stock solution, taking a mixed solution of the solvent A and the solvent B as a second stock solution, taking magnesium chips and an initiator as a third stock solution after mixing, wherein the solvent A is toluene or benzene, the solvent B is tetrahydrofuran or 2-methyltetrahydrofuran, and the mol ratio of the chlorobenzene to the magnesium chips is 1:1.0 to 1.4;
2) Heating the third stock solution to 65-90 ℃ in a reaction kettle, adding 2-20wt% of the first stock solution into the reaction kettle to initiate reaction, simultaneously dropwise adding 40-60wt% of the rest first stock solution and 60-100deg.C of the second stock solution within 3-6h at 90-110 ℃, continuously dropwise adding the rest first stock solution and the rest second stock solution within 2-3h at 85-95 ℃, and carrying out heat preservation reaction for 2-5h at 80-90 ℃ after the dropwise adding is completed, thus obtaining the high-yield product phenylmagnesium chloride solution.
2. The process for preparing phenyl magnesium chloride according to claim 1, wherein the total mass ratio of the solvent a to the solvent B in the first and second stock solutions is 4-6.5:6-3.5; the sum of the mass of the solvent A and the solvent B in the first stock solution is 0-30% of the total mass of the solvent A and the solvent B in the first stock solution and the second stock solution; the mole ratio of chlorobenzene to the total amount of solvent B in the first stock solution and the second stock solution is 1:1.9-3.0.
3. The process for preparing phenylmagnesium chloride according to claim 1, wherein the initiator is a mixture of solvent A and solvent B of phenylmagnesium chloride.
4. The process for preparing phenylmagnesium chloride according to claim 1, wherein the initial reaction stage comprises 2 to 20wt% of the first stock solution and 2 to 15wt% of the second stock solution.
5. The process for preparing phenyl magnesium chloride according to claim 1, wherein the reaction kettle is stirred at a speed of 125rpm-250rpm in a heat-preserving reaction stage after the first stock solution and the second stock solution are added dropwise; and in the heat preservation reaction stage, the feed liquid in the reaction kettle is pumped by an external circulating pump to circulate and strengthen the mixing of the feed liquid in the reaction kettle.
6. The process for preparing phenyl magnesium chloride according to any one of claims 1-5, wherein in the thermal insulation reaction stage, the feed liquid in the reaction kettle is pumped and circulated by an external circulating pump to strengthen the mixing of the feed liquid in the reaction kettle, and the pipe orifice of the external circulating pump, which is pumped and circulated into the reaction kettle, is positioned below the liquid level in the reaction kettle.
7. The process for preparing phenyl magnesium chloride according to claim 6, wherein a jet mixer for a tank is arranged in the reaction kettle, a pipe orifice which is circulated into the reaction kettle is inserted into the jet mixer for the tank in the kettle, and the circulation of feed liquid is performed through the jet mixer for the tank.
8. The process for preparing phenyl magnesium chloride according to any one of claims 1 to 5, wherein baffles are arranged in the reaction kettle, the number of the baffles is 3 to 8, and the baffles are uniformly distributed along the wall of the reaction kettle.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887919A (en) * | 2011-07-22 | 2013-01-23 | 山东金泽源工贸有限公司 | Production method of triphenylphosphine |
| CN108084225A (en) * | 2017-12-27 | 2018-05-29 | 安徽金善化工科技有限公司 | A kind of preparation method of triphenylphosphine |
| CN111454292A (en) * | 2020-05-08 | 2020-07-28 | 绍兴华威化工有限公司 | Preparation method of triphenylphosphine |
| CN111675726A (en) * | 2020-05-27 | 2020-09-18 | 江西省驰邦药业有限公司 | Continuous synthesis device and method of triphenylphosphine intermediate phenylmagnesium chloride |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887919A (en) * | 2011-07-22 | 2013-01-23 | 山东金泽源工贸有限公司 | Production method of triphenylphosphine |
| CN108084225A (en) * | 2017-12-27 | 2018-05-29 | 安徽金善化工科技有限公司 | A kind of preparation method of triphenylphosphine |
| CN111454292A (en) * | 2020-05-08 | 2020-07-28 | 绍兴华威化工有限公司 | Preparation method of triphenylphosphine |
| CN111675726A (en) * | 2020-05-27 | 2020-09-18 | 江西省驰邦药业有限公司 | Continuous synthesis device and method of triphenylphosphine intermediate phenylmagnesium chloride |
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