CN114436896A - Preparation method and preparation device of 1-naphthyl isocyanate - Google Patents
Preparation method and preparation device of 1-naphthyl isocyanate Download PDFInfo
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- CN114436896A CN114436896A CN202210100919.2A CN202210100919A CN114436896A CN 114436896 A CN114436896 A CN 114436896A CN 202210100919 A CN202210100919 A CN 202210100919A CN 114436896 A CN114436896 A CN 114436896A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
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- 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
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- 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
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- 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
- B01J19/24—Stationary reactors without moving elements inside
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- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
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- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
Abstract
The invention discloses a preparation method and a preparation device of 1-naphthyl isocyanate, which respectively prepare methyl naphthylamine and a solvent into methyl naphthylamine solutions with different gradient concentrations, and add solid phosgene and the solvent into a reaction kettle; when the temperature in the reaction kettle reaches 100-130 ℃, sequentially dripping a low-concentration menaphthylamine solution and a high-concentration menaphthylamine solution; the total dripping time is 1-2 h, and the reflux heat preservation time is 0.5-1.5 h; the reaction process is monitored by a DCS control system; the reaction mixture is purified by high vacuum distillation. The preparation device comprises a first mixing kettle, a second mixing kettle, a reaction kettle, a solvent reflux unit, a rectifying tower, a first condenser, a second condenser, a product storage tank and a vacuum unit. The invention adopts green process preparation, one-step synthesis and gradient concentration dropwise addition reaction, so that the initial reaction is more moderate and sufficient, the reaction stability is improved, and the side reaction is reduced; the product purification adopts a high vacuum distillation technology, and the product quality and the yield are improved.
Description
Technical Field
The invention relates to a preparation method and a preparation device of 1-naphthyl isocyanate, belonging to the field of chemical equipment.
Background
The 1-naphthyl isocyanate is an important intermediate of medicines, pesticides and high polymer materials, and is widely applied to synthesis of novel fluorescent dyes and medicines. The 1-naphthyl isocyanate can be synthesized by a one-step reaction of menaphthylamine and phosgene in an inert solvent medium; phosgene is used as an acylation reagent, and phosgene is a highly toxic chemical substance, so that strict precaution and regulation are provided in production, transportation, storage and use, and the protection of operators is also very strict in production.
In recent years, non-phosgenation of isocyanate synthesis has been a new technological development trend. The reaction activity of the solid phosgene is similar to that of phosgene and diphosgene, and the solid phosgene can replace phosgene, diphosgene and various compounds such as alcohol, aldehyde, amine, amide, carboxylic acid, phenol, hydroxylamine and the like to react. The solid phosgene is soluble in organic solvents such as diethyl ether, tetrahydrofuran, benzene, hexane, chloroform and the like, is stable at room temperature, has high thermal stability, and is decomposed only in a very small amount even at the distillation temperature, so that the solid phosgene is extremely safe in the transportation and use processes. In the Chinese invention patent CN1475480A, aromatic amine and solid phosgene are used as raw materials to prepare aryl isocyanate through catalytic reaction in an organic solvent, and the reaction yield is generally over 80 percent. But in the reaction process, catalysts such as triethylamine, pyridine, N-methylpyrrole or tetrabutyl urea and the like are used, so that the difficulty of post-treatment is increased.
Disclosure of Invention
In order to solve the defects in the prior art, the invention mainly aims to provide a preparation method and a preparation device of 1-naphthyl isocyanate, wherein 1-naphthyl isocyanate is prepared by adopting a green process, low-toxicity chemical solid phosgene and a solvent are adopted at the source, and the measurement, the conveying and the operating parameters of materials are controlled by DCS (distributed control System); the synthesis process adopts a one-step method, adopts gradient concentration dropwise addition reaction, makes the initial reaction more mild and sufficient, improves the reaction stability, and reduces the side reaction; the product purification adopts a high vacuum distillation technology, reduces the purification temperature and reduces the occurrence of polymerization, thereby improving the product quality and yield.
The technical scheme adopted by the invention for solving the technical problem is as follows: a preparation method of 1-naphthyl isocyanate mainly comprises the following steps:
1) uniformly mixing a part of menaphthylamine and a solvent in a first mixing kettle according to a certain mass ratio to prepare a first menaphthylamine solution for later use;
2) uniformly mixing the rest part of the menaphthylamine and the solvent in a second mixing kettle according to a certain mass ratio to prepare a second menaphthylamine solution for later use;
3) adding solid phosgene and a solvent in a certain mass ratio into a reaction kettle, and heating to dissolve;
4) dropwise adding the first menaphthylamine solution prepared in the step 1) into the reaction kettle when the temperature in the reaction kettle reaches 100-130 ℃, and continuously dropwise adding the second menaphthylamine solution prepared in the step 2) after the first menaphthylamine solution is completely dropwise added; enabling the menaphthylamine and the solid phosgene to generate an unstable intermediate product 1-naphthalimide chloride in a solvent medium, and removing hydrogen chloride from the intermediate product 1-naphthalimide chloride to obtain 1-naphthyl isocyanate; the total dripping time is 1-2 h, and after dripping is finished, reflux and heat preservation are carried out for 0.5-1.5 h; the reaction process is monitored by a DCS control system; obtaining a reaction mixed solution containing the product 1-naphthyl isocyanate;
5) purifying the reaction mixed solution of the 1-naphthyl isocyanate by adopting a high vacuum distillation mode, and separating high-boiling-point byproducts, products and low-boiling-point byproducts;
wherein the concentration of the menaphthylamine in the first menaphthylamine solution is lower than the concentration of the menaphthylamine in the second menaphthylamine solution.
Further, the molar ratio of the menaphthylamine in the first mixing kettle to the menaphthylamine in the second mixing kettle is 1.5-2.5: 2.5 to 3.5.
Further, in the first mixing kettle, the mass ratio of the menaphthylamine to the solvent is 1: 6-8; in the second mixing kettle, the mass ratio of the menaphthyl amine to the solvent is 1: 3-5; in the reaction kettle, the mass ratio of the solid phosgene to the solvent is 1: 2-5; the molar ratio of the menaphthylamine to the solid phosgene is 1:0.34 to 0.5.
Further, in the step 4), when the second naphthylamine solution is dripped, a solvent reflux device at the top of the reaction kettle is started, and the solvent in the reaction kettle continuously returns to the reaction kettle after passing through the solvent reflux device; a negative pressure environment is formed in the reaction kettle, and the pressure is-0.04 MPa to-0.064 MPa; at the moment, the reaction temperature in the reaction kettle is set to be 80-90 ℃.
Further, in the step 4), after the second naphthylamine solution is completely dripped, the solvent reflux device at the top of the reaction kettle closes the reflux mode, the solvent recovery mode is started, the solvent distilled from the top of the reaction kettle is collected, and the collected recovered solvent serves as an eluent in the distillation purification process.
Further, in the step 5), the 1-naphthyl isocyanate reaction mixed liquid is injected into a rectifying tower, and the rectifying tower adopts a mode of bottom reflux and top solvent eluent washing to ensure that high-boiling point byproducts, products and low-boiling point byproducts are separated in the same rectifying tower.
A preparation device of 1-naphthyl isocyanate comprises a first mixing kettle, a second mixing kettle, a reaction kettle, a solvent reflux device, a rectifying tower, a first condenser, a second condenser, a product storage tank and a vacuum unit; the discharge port of the first mixing kettle is connected with the feed port of the reaction kettle through a first metering pump, and the discharge port of the second mixing kettle is connected with the feed port of the reaction kettle through a second metering pump; the top of the reaction kettle is provided with the solvent reflux device; the discharge hole of the reaction kettle is connected with the feed inlet of the rectifying tower; the top, the middle part and the bottom of the rectifying tower are respectively provided with a low-boiling-point byproduct outlet, a product outlet and a high-boiling-point byproduct outlet; the low-boiling-point byproduct outlet is sequentially connected with the first condenser and the second condenser, and the second condenser is connected with the vacuum unit; the product outlet is connected with the product storage tank.
Further, the rectifying tower comprises a first packing area, a second packing area and a bottom heating area from top to bottom, the feed inlet and the product outlet of the rectifying tower are arranged between the first packing area and the second packing area and are positioned on opposite sides; the top of the rectifying tower is provided with an eluent inlet; the bottom heating zone is connected to a reboiler.
Further, the solvent reflux device comprises a reflux tower, a condenser, a vacuum system and a solvent recovery storage tank; the reflux tower with the reation kettle top is connected, the discharge gate of condenser divides into two the tunnel, wherein is connected to the reation kettle top through the pipeline all the way, and another way is connected to through the pipeline solvent recovery storage tank.
Further, the liquid phase outlet of the second condenser is connected with the solvent recovery storage tank, the discharge hole of the solvent recovery storage tank is connected to the eluent inlet at the top of the rectifying tower through a third metering pump, and the end part of the eluent inlet is provided with a spray header.
The working principle of the preparation method and the preparation device is as follows: firstly, respectively preparing a certain amount of menaphthylamine and a solvent into menaphthylamine solutions with different concentrations in a first mixing kettle and a second mixing kettle, adding a certain amount of solid phosgene and the solvent into a reaction kettle, and heating to dissolve; the prepared first naphthylamine solution with lower concentration and the second naphthylamine solution with higher concentration are sequentially dripped into the reaction kettle, so that the naphthylamine reacts with the solid phosgene in the reaction kettle, and the solid phosgene is always excessive in the reaction process, thereby being beneficial to improving the reaction efficiency and reducing the occurrence of side reactions; when the second naphthylamine solution is dripped, a solvent reflux device at the top of the reaction kettle is started, and the solvent is in a reflux state; the reaction kettle is in a negative pressure state, and the reaction raw materials in the reaction kettle react at a relatively low temperature, so that the possibility of side reaction is further reduced; and because the solvent is in a reflux state, the possibility of contact between reaction raw materials is higher, the reaction efficiency is higher, and the reaction is more sufficient. And after the second naphthylamine solution is dripped, collecting the solvent in the solvent reflux device into a solvent recovery storage tank.
The reaction mixed liquid in the reaction kettle is conveyed to a feed inlet in the middle of a rectifying tower through a pipeline, the reaction mixed liquid is separated according to the boiling point in the rectifying tower, low-boiling-point byproducts (including a solvent and the low-boiling-point reaction byproducts generated by the reaction) enter a first condenser from a low-boiling-point byproduct outlet at the top of the rectifying tower, the low-boiling-point reaction byproducts generated by the reaction with relatively high boiling point are condensed and collected in the first condenser, the solvent with relatively low boiling point continuously enters a second condenser in a gas phase manner, and the solvent with relatively low boiling point is condensed and collected in the second condenser; the recovered solvent collected in the second condenser is sent to a solvent recovery storage tank in the solvent reflux device, and the solvent distilled from the top of the reaction kettle in the reaction process is collected in the solvent recovery storage tank. The recovered solvent is sprayed into the rectifying tower through a leacheate inlet at the top of the rectifying tower through a spray header to further leach a packing area in the rectifying tower, so that the separation and purification effect of the product is better and the yield is higher. The bottom of the rectifying tower is a bottom heating area, the reaction mixed liquid in the bottom heating area is mainly a high-boiling-point byproduct and a small amount of products, the separation and purification effect between the high-boiling-point byproduct and the products is further improved after the reaction mixed liquid is heated by the reboiler, and the yield is increased.
The invention has the beneficial effects that: compared with the prior art, the preparation method and the preparation device of the 1-naphthyl isocyanate provided by the invention adopt a green process to prepare the 1-naphthyl isocyanate, adopt low-toxicity chemical solid phosgene and solvents (such as toluene, xylene, chlorobenzene and dichlorobenzene) at the source, and adopt DCS to control the metering, conveying and operating parameters of materials; the synthesis process adopts a one-step method, adopts gradient concentration dropwise addition reaction, makes the initial reaction more mild and sufficient, improves the reaction stability, and reduces the side reaction; the product purification adopts a high vacuum distillation technology, reduces the purification temperature and reduces the occurrence of polymerization, thereby improving the product quality and yield. The yield of the 1-naphthyl isocyanate prepared by the preparation method and the preparation device provided by the invention can reach 91%, and the product content is more than or equal to 99%.
Drawings
FIG. 1 is a schematic structural diagram of a 1-naphthyl isocyanate preparation device provided by the invention.
Wherein, 1-a first mixing kettle; 2-a first metering pump; 3-a second mixing kettle; 4-a second metering pump; 5-a reaction kettle; 6-reflux column; 7-a condenser; 8-solvent recovery storage tank; 9-a first packing region; 10-a third metering pump; 11-a feed inlet; 12-a second packing region; 13-bottom heating zone; 14-a high boiling by-product outlet; 15-a reboiler; 16-a product outlet; 17-a rectification column; 18-a shower head; 19-low boiling by-product outlet; 20-a first condenser; 21-a second condenser; 22-product storage tank; 23-vacuum unit.
Detailed Description
The invention is further illustrated by the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
A preparation method of 1-naphthyl isocyanate mainly comprises the following steps:
1) uniformly mixing the menaphthylamine and xylene of 2/5 in a first mixing kettle 1 according to the mass ratio of 1:6 to prepare a first menaphthylamine solution for later use;
2) uniformly mixing the menaphthylamine and xylene in the 2/5 ratio of 1:3 in a second mixing kettle 3 to prepare a second menaphthylamine solution for later use;
3) adding solid phosgene and xylene in a mass ratio of 1:4 into a reaction kettle 5, and heating to dissolve; the molar ratio of the menaphthylamine to the solid phosgene is 1: 0.5;
4) dropwise adding the first naphthylamine solution prepared in the step 1) into the reaction kettle 5 when the temperature in the reaction kettle 5 reaches 100-130 ℃, and continuously dropwise adding the second naphthylamine solution prepared in the step 2) after the first naphthylamine solution is completely dropwise added; enabling the menaphthylamine and the solid phosgene to generate an unstable intermediate product 1-naphthalimide chloride in a solvent medium, and removing hydrogen chloride from the intermediate product 1-naphthalimide chloride to obtain 1-naphthyl isocyanate; the total dripping time is 1.5h, and the reflux and heat preservation are carried out for 1h after the dripping is finished; the reaction process is monitored by a DCS control system; obtaining a reaction mixed solution containing the product 1-naphthyl isocyanate;
5) and purifying the reaction mixed solution of the 1-naphthyl isocyanate by adopting a high vacuum distillation mode, and separating high-boiling-point byproducts, products and low-boiling-point byproducts. The product yield is 89.5%, and the product content is more than or equal to 98%.
In the step 4), when the second naphthylamine solution is dropwise added, starting a solvent reflux device at the top of the reaction kettle 5, and continuously returning the solvent in the reaction kettle 5 to the reaction kettle 5 after passing through the solvent reflux device; a negative pressure environment is formed in the reaction kettle 5, and the pressure is-0.04 MPa to-0.064 MPa; at this time, the reaction temperature in the reaction kettle 5 is set to 80-90 ℃.
In order to match the production method of the invention, the invention also designs a preparation device of the 1-naphthyl isocyanate, which is shown in figure 1. The preparation device comprises a first mixing kettle 1, a second mixing kettle 3, a reaction kettle 5, a solvent reflux device, a rectifying tower 17, a first condenser 20, a second condenser 21, a product storage tank 22 and a vacuum unit 23; the discharge hole of the first mixing kettle 1 is connected with the feed inlet of the reaction kettle 5 through a first metering pump 2, and the discharge hole of the second mixing kettle 3 is connected with the feed inlet of the reaction kettle 5 through a second metering pump 4; the top of the reaction kettle 5 is provided with the solvent reflux device; the discharge hole of the reaction kettle 5 is connected with the feed inlet 11 of the rectifying tower 17; the top, the middle part and the bottom of the rectifying tower 17 are respectively provided with a low-boiling point byproduct outlet 19, a product outlet 16 and a high-boiling point byproduct outlet 14; the low-boiling-point byproduct outlet 19 is sequentially connected with the first condenser 20 and the second condenser 21, and the second condenser 21 is connected with the vacuum unit 23; the product outlet 16 is connected to the product reservoir 22.
The rectifying tower 17 comprises a first packing area 9, a second packing area 12 and a bottom heating area 13 from top to bottom, and a feed inlet 11 and a product outlet 16 of the rectifying tower 17 are arranged between the first packing area 9 and the second packing area 12 and are positioned on opposite sides; the top of the rectifying tower 17 is provided with an eluent inlet; the bottom heating zone 13 is connected to a reboiler 15. The solvent reflux device comprises a reflux tower 6, a condenser 7, a vacuum system and a solvent recovery storage tank 8; reflux tower 6 with 5 tops of reation kettle are connected, the discharge gate of condenser 7 falls into two the tunnel, wherein is connected to 5 tops of reation kettle through the pipeline all the way, another way through the pipeline connection to solvent recovery storage tank 8. The liquid phase outlet of the second condenser 21 is connected with the solvent recovery storage tank 8, the discharge hole of the solvent recovery storage tank 8 is connected to the eluent inlet at the top of the rectifying tower 17 through a third metering pump 10, and the end part of the eluent inlet is provided with a spray header 18.
The working principle of the preparation method and the preparation device is as follows: firstly, preparing a certain amount of naphthylamine and a solvent into naphthylamine solutions with different concentrations in a first mixing kettle 1 and a second mixing kettle 3 respectively, adding a certain amount of solid phosgene and a solvent into a reaction kettle 5, and heating to dissolve; the prepared first naphthylamine solution with lower concentration and the second naphthylamine solution with higher concentration are dripped into the reaction kettle 5 in sequence, so that the naphthylamine reacts with the solid phosgene in the reaction kettle 5, and the solid phosgene is always excessive in the reaction process, thereby being beneficial to improving the reaction efficiency and reducing the occurrence of side reactions; when the second naphthylamine solution is dripped, a solvent reflux device at the top of the reaction kettle 5 is started, and the solvent is in a reflux state; the reaction kettle 5 is in a negative pressure state, and the reaction raw materials in the reaction kettle 5 react at a relatively low temperature, so that the possibility of side reaction is further reduced; and because the solvent is in a reflux state, the possibility of contact between reaction raw materials is higher, the reaction efficiency is higher, and the reaction is more sufficient. After the second naphthylamine solution is added dropwise, the solvent in the solvent reflux device is collected into the solvent recovery storage tank 8.
The reaction mixed liquid in the reaction kettle 5 is sent to a feeding hole 11 in the middle of a rectifying tower 17 through a pipeline, the reaction mixed liquid is separated according to the boiling point in the rectifying tower 17, low-boiling-point byproducts (including a solvent and the low-boiling-point reaction byproducts generated by the reaction) enter a first condenser 20 from a low-boiling-point byproduct outlet 19 at the top of the rectifying tower 17, the low-boiling-point reaction byproducts generated by the reaction with relatively higher boiling point are condensed and collected in the first condenser 20, the solvent with relatively lower boiling point continuously enters a second condenser 21 in a gas phase form, and are condensed and collected in the second condenser 21; the recovered solvent collected in the second condenser 21 is sent to the solvent recovery tank 8 in the solvent reflux unit, and the solvent distilled off from the top of the reaction vessel 5 during the reaction is collected in the solvent recovery tank 8. The recovered solvent is sprayed into the rectifying tower 17 through a leacheate inlet at the top of the rectifying tower 17 and a spray header 18, and a filler area in the rectifying tower 17 is further leached, so that the separation and purification effect of the product is better, and the yield is higher. The bottom of the rectifying tower 17 is a bottom heating zone 13, and is heated by a reboiler 15, and the reaction mixed liquid in the bottom heating zone 13 mainly comprises high-boiling by-products and a small amount of products, and the separation and purification effects between the high-boiling by-products and the products are further improved after the reaction mixed liquid is heated by the reboiler 15, so that the yield is increased.
Example 2
A method for producing 1-naphthyl isocyanate, wherein in a first naphthylamine solution, the mass ratio of naphthylamine to dimethylbenzene is 1: 7; in the second naphthylamine solution, the mass ratio of naphthylamine to dimethylbenzene is 1: 4; the mass ratio of the solid phosgene to the dimethylbenzene is 1:4, and the molar ratio of the menaphthylamine to the solid phosgene is 1: 0.5. The rest is the same as example 1. The production apparatus was the same as in example 1. The yield of the prepared 1-naphthyl isocyanate is 91 percent, and the product content is more than or equal to 99 percent.
Example 3
A method for producing 1-naphthyl isocyanate, wherein in a first naphthylamine solution, the mass ratio of naphthylamine to dimethylbenzene is 1: 8; in the second naphthylamine solution, the mass ratio of naphthylamine to dimethylbenzene is 1: 5; the mass ratio of the solid phosgene to the dimethylbenzene is 1:4, and the molar ratio of the menaphthylamine to the solid phosgene is 1: 0.5. The rest is the same as example 1. The production apparatus was the same as in example 1. The yield of the prepared 1-naphthyl isocyanate is 90.3 percent, and the product content is more than or equal to 98.5 percent.
Example 4
A method for producing 1-naphthyl isocyanate, wherein in a first naphthylamine solution, the mass ratio of naphthylamine to dimethylbenzene is 1: 7; in the second naphthylamine solution, the mass ratio of naphthylamine to dimethylbenzene is 1: 4; the mass ratio of the solid phosgene to the dimethylbenzene is 1:4, and the molar ratio of the menaphthylamine to the solid phosgene is 1: 0.4. The rest is the same as example 1. The production apparatus was the same as in example 1. The yield of the prepared 1-naphthyl isocyanate is 88 percent, and the product content is more than or equal to 96 percent.
Example 5
A method for producing 1-naphthyl isocyanate, wherein in a first naphthylamine solution, the mass ratio of naphthylamine to dimethylbenzene is 1: 7; in the second naphthylamine solution, the mass ratio of naphthylamine to dimethylbenzene is 1: 4; the mass ratio of the solid phosgene to the dimethylbenzene is 1:4, and the molar ratio of the menaphthylamine to the solid phosgene is 1: 0.34. The rest is the same as example 1. The production apparatus was the same as in example 1. The yield of the prepared 1-naphthyl isocyanate is 87 percent, and the product content is more than or equal to 95.8 percent.
The above embodiments are only for illustrating the invention and are not to be construed as limiting the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention, therefore, all equivalent technical solutions also belong to the scope of the invention, and the scope of the invention is defined by the claims.
Claims (10)
1. The preparation method of the 1-naphthyl isocyanate is characterized by mainly comprising the following steps:
1) uniformly mixing a part of menaphthylamine and a solvent in a first mixing kettle according to a certain mass ratio to prepare a first menaphthylamine solution for later use;
2) uniformly mixing the rest part of the menaphthylamine and the solvent in a second mixing kettle according to a certain mass ratio to prepare a second naphthylamine solution for later use;
3) adding solid phosgene and a solvent in a certain mass ratio into a reaction kettle, and heating to dissolve;
4) dropwise adding the first menaphthylamine solution prepared in the step 1) into the reaction kettle when the temperature in the reaction kettle reaches 100-130 ℃, and continuously dropwise adding the second menaphthylamine solution prepared in the step 2) after the first menaphthylamine solution is completely dropwise added; enabling the menaphthylamine and the solid phosgene to generate an unstable intermediate product 1-naphthalimide chloride in a solvent medium, and removing hydrogen chloride from the intermediate product 1-naphthalimide chloride to obtain 1-naphthyl isocyanate; the total dripping time is 1-2 h, and after dripping is finished, reflux and heat preservation are carried out for 0.5-1.5 h; the reaction process is monitored by a DCS control system; obtaining a reaction mixed solution containing the product 1-naphthyl isocyanate;
5) purifying the reaction mixed solution of the 1-naphthyl isocyanate by adopting a high vacuum distillation mode, and separating high-boiling-point byproducts, products and low-boiling-point byproducts;
wherein the concentration of the menaphthylamine in the first menaphthylamine solution is lower than the concentration of the menaphthylamine in the second menaphthylamine solution.
2. The process for preparing 1-naphthyl isocyanate according to claim 1, wherein: the molar ratio of the menaphthylamine in the first mixing kettle to the menaphthylamine in the second mixing kettle is 1.5-2.5: 2.5 to 3.5.
3. The process for preparing 1-naphthyl isocyanate according to claim 2, wherein: in the first mixing kettle, the mass ratio of the menaphthylamine to the solvent is 1: 6-8; in the second mixing kettle, the mass ratio of the menaphthylamine to the solvent is 1: 3-5; in the reaction kettle, the mass ratio of the solid phosgene to the solvent is 1: 2-5; the molar ratio of the menaphthylamine to the solid phosgene is 1:0.34 to 0.5.
4. The process for preparing 1-naphthyl isocyanate according to claim 1, wherein: in the step 4), when the second naphthylamine solution is dripped, a solvent reflux device at the top of the reaction kettle is started, and the solvent in the reaction kettle continuously returns to the reaction kettle after passing through the solvent reflux device; a negative pressure environment is formed in the reaction kettle, and the pressure is-0.04 MPa to-0.064 MPa; at the moment, the reaction temperature in the reaction kettle is set to be 80-90 ℃.
5. The process for preparing 1-naphthyl isocyanate according to claim 4, wherein: in the step 4), after the second naphthylamine solution is dropwise added, the solvent reflux device at the top of the reaction kettle closes the reflux mode, the solvent recovery mode is started, the solvent distilled from the top of the reaction kettle is collected, and the collected recovered solvent serves as an eluent in the distillation and purification process.
6. The process for preparing 1-naphthyl isocyanate according to claim 5, wherein: and 5), injecting the 1-naphthyl isocyanate reaction mixed liquid into a rectifying tower, wherein the rectifying tower adopts a mode of bottom reflux and top solvent eluent washing to ensure that a high-boiling point byproduct, a product and a low-boiling point byproduct are separated in the same rectifying tower.
7. A production apparatus of 1-naphthyl isocyanate according to any one of claims 1 to 6, characterized in that: the preparation device comprises a first mixing kettle, a second mixing kettle, a reaction kettle, a solvent reflux device, a rectifying tower, a first condenser, a second condenser, a product storage tank and a vacuum unit; the discharge port of the first mixing kettle is connected with the feed port of the reaction kettle through a first metering pump, and the discharge port of the second mixing kettle is connected with the feed port of the reaction kettle through a second metering pump; the top of the reaction kettle is provided with the solvent reflux device; the discharge hole of the reaction kettle is connected with the feed inlet of the rectifying tower; the top, the middle part and the bottom of the rectifying tower are respectively provided with a low-boiling point byproduct outlet, a product outlet and a high-boiling point byproduct outlet; the low-boiling-point byproduct outlet is sequentially connected with the first condenser and the second condenser, and the second condenser is connected with the vacuum unit; the product outlet is connected with the product storage tank.
8. The apparatus for preparing 1-naphthyl isocyanate according to claim 7, wherein: the rectifying tower comprises a first packing area, a second packing area and a bottom heating area from top to bottom, a feed inlet and a product outlet of the rectifying tower are arranged between the first packing area and the second packing area, and the first packing area and the second packing area are positioned on opposite sides; the top of the rectifying tower is provided with an eluent inlet; the bottom heating zone is connected to a reboiler.
9. The apparatus for preparing 1-naphthyl isocyanate according to claim 7, wherein: the solvent reflux device comprises a reflux tower, a condenser, a vacuum system and a solvent recovery storage tank; the reflux tower with the reation kettle top is connected, the discharge gate of condenser divides into two the tunnel, wherein is connected to the reation kettle top through the pipeline all the way, and another way is connected to through the pipeline solvent recovery storage tank.
10. The apparatus for preparing 1-naphthyl isocyanate according to claim 9, wherein: the liquid phase outlet of the second condenser is connected with the solvent recovery storage tank, the discharge port of the solvent recovery storage tank is connected to the eluent inlet at the top of the rectifying tower through a third metering pump, and the end part of the eluent inlet is provided with a spray header.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819285A (en) * | 2022-10-28 | 2023-03-21 | 宁夏瑞泰科技股份有限公司 | Method for treating distillation still residues containing 1,5-naphthalene diisocyanate |
| CN116023300A (en) * | 2022-12-12 | 2023-04-28 | 浙江丽水有邦新材料有限公司 | Preparation method and preparation device of octadecyl isocyanate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292170A (en) * | 2014-09-22 | 2015-01-21 | 广西师范大学 | Quinazolinyl-aryl urea derivatives with antitumor function and application thereof |
| CN206045451U (en) * | 2016-08-31 | 2017-03-29 | 山东崇舜化工有限公司 | A kind of 1,5 naphthalene diisocyanate purifying plants |
| CN107915662A (en) * | 2017-12-20 | 2018-04-17 | 青岛科技大学 | Separation, the device and method of purification m-xylylene diisocyanate |
| CN111848455A (en) * | 2020-08-17 | 2020-10-30 | 万华化学集团股份有限公司 | Method for reducing chromaticity of isocyanate product and automatic control method for gas-phase extraction flow of isocyanate rectifying tower |
| CN112552209A (en) * | 2020-12-09 | 2021-03-26 | 浙江丽水有邦新材料有限公司 | Method and device for preparing cyclohexyl isocyanate |
-
2022
- 2022-01-27 CN CN202210100919.2A patent/CN114436896A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292170A (en) * | 2014-09-22 | 2015-01-21 | 广西师范大学 | Quinazolinyl-aryl urea derivatives with antitumor function and application thereof |
| CN206045451U (en) * | 2016-08-31 | 2017-03-29 | 山东崇舜化工有限公司 | A kind of 1,5 naphthalene diisocyanate purifying plants |
| CN107915662A (en) * | 2017-12-20 | 2018-04-17 | 青岛科技大学 | Separation, the device and method of purification m-xylylene diisocyanate |
| CN111848455A (en) * | 2020-08-17 | 2020-10-30 | 万华化学集团股份有限公司 | Method for reducing chromaticity of isocyanate product and automatic control method for gas-phase extraction flow of isocyanate rectifying tower |
| CN112552209A (en) * | 2020-12-09 | 2021-03-26 | 浙江丽水有邦新材料有限公司 | Method and device for preparing cyclohexyl isocyanate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819285A (en) * | 2022-10-28 | 2023-03-21 | 宁夏瑞泰科技股份有限公司 | Method for treating distillation still residues containing 1,5-naphthalene diisocyanate |
| CN116023300A (en) * | 2022-12-12 | 2023-04-28 | 浙江丽水有邦新材料有限公司 | Preparation method and preparation device of octadecyl isocyanate |
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