CN1931834A - Synthesis process of phenyl dimethylene diisocyanate - Google Patents
Synthesis process of phenyl dimethylene diisocyanate Download PDFInfo
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- CN1931834A CN1931834A CN 200510060764 CN200510060764A CN1931834A CN 1931834 A CN1931834 A CN 1931834A CN 200510060764 CN200510060764 CN 200510060764 CN 200510060764 A CN200510060764 A CN 200510060764A CN 1931834 A CN1931834 A CN 1931834A
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- xylylene diisocyanate
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Abstract
The synthesis process of phenyl dimethylene diisocyanate belongs to the field of isocyanate synthesizing technology. In inert liquid medium, phenyl dimethylamine or its hydrochloride or carbonate reacts with bis(trichloromethyl) carbonate at the temperature of -20 deg.c to -60 deg.c, before heating and reflux reaction for 0.5-5 hr to synthesize phenyl dimethylene diisocyanate. The amount of bis(trichloromethyl) carbonate is 0.5-15 times that of phenyl dimethylamine or its hydrochloride or carbonate. The present invention has stable solid crystal materials, and is environment friendly and suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of isocyanate synthesis, and particularly relates to a method for synthesizing xylylene diisocyanate by reacting xylylenediamine or hydrochloride or carbonate thereof with bis (trichloromethyl) carbonate.
Background
Xylylene diisocyanate is an important diisocyanate and is used as a raw material for producing materials such as polyurethanes, polyureas, polyimidines, polyisocyanurates and the like in the industries such as coatings, resins and the like.
Phosgenation processes for preparing isocyanates by reacting primary organic amines with phosgene in inert solvents are known from the prior art. The phosgene method can be divided into a direct method and a salt-forming method, wherein the direct method is to prepare corresponding isocyanate by directly reacting primary amine with phosgene; the salt-forming method is to react the corresponding amine with an acidic gas such as hydrogen chloride, carbon dioxide, etc. to prepare an amine salt, and then to react the amine salt with phosgene.
Chinese patent CN1038503C "method for preparing xylylene diisocyanate" discloses that xylylenediamine is reacted with phosgene in the presence of an ester reaction solvent to prepare xylylene diisocyanate, and chlorine-derived by-products generated by the deamination reaction can be reduced. Chinese patent CN1062857 "preparation method of ester polyisocyanate" proposes an improved method of filling inert gas into the reaction system while the reaction is proceeding, which can reduce the amount of phosgene and increase the yield of the product.
However, the phosgenation method requires excessive amount of highly toxic phosgene in the preparation process, and phosgene is strictly limited in the generation, storage, transportation and use processes, so that the requirements on operation, equipment and management are extremely high, the environmental impact is serious, the potential safety hazard is large, and the post-treatment is complicated.
Disclosure of Invention
In order to overcome the defects of complex post-treatment and environmental pollution of the existing synthesis process of the xylylene diisocyanate, the invention aims to provide the synthesis method of the xylylene diisocyanate, which has the advantages of mild reaction conditions, easy control, simple operation, low production cost and clean production realization
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for synthesizing xylylene diisocyanate, xylylenediamine or hydrochloride or carbonate thereof reacts with bis (trichloromethyl) carbonate in an inert liquid medium to synthesize xylylene diisocyanate, wherein the usage amount of the bis (trichloromethyl) carbonate is 0.5-15 times, preferably 1-10 times, by weight of the xylylenediamine or the hydrochloride or carbonate thereof.
The synthesis reaction equation of the invention is as follows:
the raw material bis (trichloromethyl) carbonate used in the invention is solid at normal temperature, is easy to store and transport, has accurate reaction metering and is easy for process operation.
The xylylenediamine used in the method for synthesizing xylylene diisocyanate according to the present invention is m-xylylenediamine, p-xylylenediamine, o-xylylenediamine or a mixture of these isomers in various ratios.
Xylylenediamine may be used as it is as a raw material for the reaction with bis (trichloromethyl) carbonate, or xylylenediamine may be reacted with bis (trichloromethyl) carbonate after forming carbonate or hydrochloride to obtain the corresponding diisocyanate.
Dropwise adding an inert liquid medium solution of xylylenediamine intoan inert liquid medium solution of bis (trichloromethyl) carbonate at the temperature of-20-60 ℃, stirring, carrying out reflux reaction for 0.5-5 hours after dropwise addition, filtering to remove insoluble substances, carrying out reduced pressure distillation to recover the solvent, and purifying to obtain the xylylene diisocyanate.
The invention can also use hydrochloride or carbonate of xylylenediamine as raw material to synthesize xylylene diisocyanate with bis (trichloromethyl) carbonate, namely two-step reaction, the first step reaction is to inject hydrogen chloride gas or carbon dioxide gas into the inert liquid medium of xylylenediamine, make xylylenediamine transform into xylylenediamine hydrochloride or carbonate, the preferred temperature for salification is in 0 duC-50 duC, obviously lower than 0 duC or higher than 50 duC salification reaction can go on smoothly too, but the energy consumption is uneconomical; and secondly, dropwise adding an inert liquid medium solution of bis (trichloromethyl) carbonate into the reaction at the temperature of between 20 ℃ below zero and 180 ℃, stirring, carrying out reflux reaction for 0.5 to 5 hours after dropwise adding, filtering to remove insoluble substances, carrying out reduced pressure distillation to recover the solvent, and purifying to obtain the xylylene diisocyanate.
Adding the inert liquid medium solution of the bis (trichloromethyl) carbonate into a reactor in batches for reaction, dropwise adding a part of the inert liquid medium solution into the reaction solution at room temperature, and stirring for reaction for 0.5-2 hours; and dropwise adding the rest solution within 5-20 hours under the reflux state, and completing the reflux reaction for 0.5-5 hours.
Dropwise adding the inert liquid medium solution of the bis (trichloromethyl) carbonate at the reflux temperature, namely the reaction temperature, wherein the dropwise adding time can be controlled to be 5-20 hours, preferably 10-15 hours, and the dropwise adding time has influence on the product yield.
According to the synthesis method of the xylylene diisocyanate, the using amount of an inert liquid medium is calculated by weight, and the weight percentage concentration of a xylylenediamine or hydrochloride and carbonate inert liquid medium solution is 2-25%; the weight percentage concentration of the inert liquid medium solution of the bis (trichloromethyl) carbonate is 1 to 70 percent, and the preferred weight percentage concentration is 30 to 50 percent.
The inert liquid medium means a hydrocarbon, halogenated hydrocarbon, ester, ether, ketone and the like organic solvent which is liquid at the reaction temperature and does not react with xylylenediamine, xylylene diisocyanate, bis (trichloromethyl) carbonate, hydrogen chloride and carbon dioxide under the reaction conditions. Such as: petroleum ether, cyclohexane, n-hexane, mixed xylene, o-xylene, m-xylene, p-xylene, toluene, benzene xylene, 1, 2-dichloroethane, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, ethyl acetate, propyl acetate, amyl acetate, isoamyl acetate, butyl acetate, isobutyl acetate, phenyl acetate, ethyl propionate, propyl propionate, amyl propionate, isoamyl propionate, butyl propionate, isobutyl propionate, amyl formate, ethyl isovalerate, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, anisole, cyclohexanone, and the like. These media may be used alone or in combination of several. Xylene, chlorobenzene, o-dichlorobenzene, isoamyl acetate are particularly preferred.
According to the method for synthesizing the xylylene diisocyanate, the catalyst which causes or partially causes the activation of the bis (trichloromethyl) carbonate is added into the reaction solution, so that the reaction can be promoted to be rapidly carried out.
The catalyst can promote the activation or partial activation of the di (trichloromethyl) carbonate in a reaction temperature range, and comprises an adsorbent with high surface activity and organic bases, such as activated clay, activated carbon, trimethylamine, triethylamine, N-dimethylaniline, pyridine, N-dimethylformamide and the like. The addition amount of the catalyst is 0 to 10 percent, preferably 1 to 5 percent of the weight of the bis (trichloromethyl) carbonate.
The invention provides a method for synthesizing xylylene diisocyanate, which comprises the following process steps:
preparing 20-50% of bis (trichloromethyl) carbonate solution; adding a chlorobenzene solution of triethylamine with the concentration of 5-20% at the temperature of 20-30 ℃, and stirring and activating for 1 hour;
dropwise adding a chlorobenzene solution of xylylenediamine into the reaction liquid at the temperature of-20 ℃, stirring, heating to reflux reaction for 0.5-5 hours after dropwise adding, filtering to remove insoluble substances, carrying out reduced pressure distillation to recover chlorobenzene, and purifying to obtain the xylylene diisocyanate.
Compared with the existing method for synthesizing the xylylene diisocyanate, the method has the following beneficial effects:
1. the raw material of the bis (trichloromethyl) carbonate is a stable solid crystal at normal temperature, is convenient to store and transport, is safe to use and is environment-friendly;
2. the synthesis method has accurate reaction measurement and reduced raw material consumption;
3. the process saves relevant equipment for generating and using phosgene, can be used for production by adopting conventional reaction equipment, has simple, safe and easily controlled operation process and low operation cost, and is suitable for industrial production.
Detailed Description
The invention is further illustrated by the following examples
Specific examples of the present invention are as follows, but the present invention is not limited to only the following examples.
Example 1
1300 ml of chlorobenzene and 136.2 g (1.0mol) of xylylenediamine were introduced into a 3000 ml reaction flask equipped with a reflux condenser, a gas-guide tube, a thermometer, a dropping funnel for liquids, and a high-performance stirrer, and the stirring was started.
After being stirred evenly, dry carbon dioxide gas is introduced through the gas guide tube, the aeration speed is 0.5L/min, the temperature is maintained at 20-30 ℃, the aeration is stopped after the reaction is carried out for 3 hours, and the stirring and the aging are continued for 30 minutes.
Adding a solution consisting of 300 g (1.01mol) of bis (trichloromethyl) carbonate and 300 ml of chlorobenzene at normal temperature, stirring and reacting for 30 minutes, heating to 130-135 ℃, reacting for 1 hour, dropwise adding a solution consisting of 300 g of bis (trichloromethyl) carbonate (1.01mol) and 300 ml of chlorobenzene for 10 hours under a reflux state, continuing reflux reaction for 1 hour after adding, evaporating the solvent, and distilling under reduced pressure to obtain 142.5 g of xylylene diisocyanate with the yield of 75.8%.
Example 2
1300 ml of chlorobenzene and 136.2 g (1.0mol) of xylylenediamine were introduced into a 3000 ml reaction flask equipped with a reflux condenser, a gas-guide tube, a thermometer,a dropping funnel for liquids, and a high-performance stirrer, and the stirring was started.
After being stirred evenly, dry carbon dioxide gas is introduced through the gas guide tube, the aeration speed is 0.5L/min, the temperature is maintained at 20-30 ℃, the aeration is stopped after the reaction is carried out for 3 hours, and the mixture is continuously stirred and aged for 30 minutes for standby.
300 g (1.01mol) of bis (trichloromethyl) carbonate (1.01mol) were dissolved in 500 ml of chlorobenzene, 6 g of activated carbon and 6 g of triethylamine were added thereto, stirred and activated at 30 ℃ for 30 minutes,
adding the solution into xylylenediamine carbonate solution at the temperature of 20-30 ℃, continuously reacting for 30 minutes, heating to 130-135 ℃ for reacting for 1 hour, dropwise adding a solution consisting of 300 g (1.01mol) of bis (trichloromethyl) carbonate and 300 ml of chlorobenzene for 7 hours under a reflux state, continuously refluxing for reacting for 1 hour, evaporating the solvent, and distilling under reduced pressure to obtain 152.5 g of xylylene diisocyanate with the yield of 81.1 percent.
Example 3
1300 ml of isoamyl acetate and 109.0 g (0.8mol) of xylylenediamine were added to the reaction apparatus used in example 1, and after stirring the mixture uniformly, dry carbon dioxide gas was introduced through a gas-guide tube at a rate of 0.4L/min while maintaining the temperature at 0 ℃ to 10 ℃ to react for 2.5 hours, then the gas introduction was stopped, and the mixture was further stirred and aged for 30 minutes.
Dropwise adding a solution prepared by uniformly mixing 300 g (1.01mol) of bis (trichloromethyl) carbonate and 400 ml of isoamyl acetate into the solution at normal temperature, and stirring for reacting for 30 minutes after dropwise adding; heating to 140-145 ℃ for reaction for 1 hour, dripping a solution consisting of 401 g of bis (trichloromethyl) carbonate (1.35mol) and 500 ml of isoamyl acetate for 12 hours under the reflux state, continuing reflux reaction for 1 hour after the dripping, evaporating the solvent, and distilling under reduced pressure to obtain 125.6 g of xylylene diisocyanate with the yield of 83.5 percent.
Example 4
Using the reaction apparatus as in example 1, 800 ml of isoamyl acetate and 68.1 g (0.5mol) of xylylenediamine were added, and after stirring uniformly, dry hydrogen chloride gas was introduced through a gas-guide tube at a rate of 0.3L/min, the temperature was maintained at 30 to 50 ℃, and after 2.5 hours of reaction, the gas introduction was stopped, and the stirring and aging were continued for 30 minutes.
Heating the reaction solution to 125-135 ℃, dropwise adding a solution consisting of 712 g (2.4mol) of bis (trichloromethyl) carbonate and 1000 ml of isoamyl acetate for 15 hours under a reflux state, continuing reflux reaction for 1 hour after the addition, evaporating the solvent, and carrying out reduced pressure distillation to obtain 83.4 g of xylylene diisocyanate with the yield of 88.7%.
Example 5
68.1 g (0.5mol) of xylylenediamine as a raw material, 104 g (0.35mol) of bis (trichloromethyl) carbonate, 8 mass percent of o-dichlorobenzene solution of xylylenediamine and 40 mass percent of o-dichlorobenzene solution of bis (trichloromethyl) carbonate as an inert solvent.
The other steps and the process steps are the same as in example 4, and 47.8 g of xylylene diisocyanate is obtained with a yield of 50.8%.
Example 6
1300 ml of o-dichlorobenzene and 136.2 g (1.0mol) of xylylenediamine were added into the reaction apparatus as in example 1, and after stirring the mixture uniformly, dry hydrogen chloride gas was introduced through a gas-guide tube at a rate of 0.3L/min while maintaining the temperature at 10 ℃ to 15 ℃ to react for 4 hours, then the gas introduction was stopped, and the mixture was stirred and aged for 30 minutes. Heating to 160-170 ℃, dropwise adding a solution consisting of 401 g (1.35mol) of bis (trichloromethyl) carbonate and 600 ml of o-dichlorobenzene within 12 hours, continuously carrying out reflux reaction for 1 hour after the addition, evaporating the solvent, and carrying out reduced pressure distillation to obtain 155.8 g and 82.8% of xylylene diisocyanate.
Example 7
1000 ml of chlorobenzene and 300 g (1.01mol) of bis (trichloromethyl) carbonate were added to a 3000 ml reaction flask equipped with a reflux condenser, a gas-guide tube, a thermometer, a liquid dropping funnel and a high-efficiency stirrer, and after stirring and dissolution, 50 g of a chlorobenzene solution of triethylamine (containing 10 g of triethylamine) was added dropwise at 30 ℃ and stirring was continued for 1 hour. Cooling to 10-20 deg.c, dropping solution of 136.2 g (1.0mol) of xylylenediamine and 500 ml of chlorobenzene while stirring vigorously, and stirring for 30 min.
Heating the reaction solution to 130-135 ℃ for reaction for 1 hour, controlling the reaction solution to be about 10 hours under a reflux state, dropwise adding a solution consisting of 297 g (1.0mol) of bis (trichloromethyl) carbonate and 300 ml of chlorobenzene, continuing reflux reaction for 1 hour after the addition is finished, evaporating the solvent, and distilling under reduced pressure to obtain 125.3 g of xylylene diisocyanate, wherein the yield is 66.6%.
Example 8
68.1 g (0.5mol) of xylylenediamine as a raw material, 743 g (2.5mol) of bis (trichloromethyl) carbonate as a consumption, and xylene as an inert solvent, wherein the mass percent concentration of a xylene solution of the xylylenediamine is 10% and the mass percent concentration of a xylene solution of the bis (trichloromethyl) carbonate is 50%.
The other steps and the process steps were the same as in example 4, whereby 66.8 g of xylylene diisocyanate was obtained in a yield of 71%.
Claims (10)
1. A method for synthesizing xylylene diisocyanate is characterized in that xylylenediamine or hydrochloride or carbonate thereof reacts with bis (trichloromethyl) carbonate in an inert liquid medium at the temperature of-20-60 ℃, and then the temperature is raised to reflux reaction for 0.5-5 hours to synthesize the xylylene diisocyanate, wherein the usage amount of the bis (trichloromethyl) carbonate is 0.5-15 times of that of the xylylene diamine or the hydrochloride or carbonate thereof by weight.
2. The method according to claim 1, wherein the hydrochloride or carbonate of xylylenediamine is prepared by introducing hydrogen chloride gas or carbon dioxide gas into a solution of xylylenediamine in an inert liquid medium at a temperature of 0 ℃ to 50 ℃; dropwise adding an inert liquid medium solution of bis (trichloromethyl) carbonate at the temperature of between 20 ℃ below zero and 180 ℃, stirring, carrying out reflux reaction for 0.5 to 5 hours after the dropwise adding is finished, filtering to remove insoluble substances, carrying out reduced pressure distillation to recover the inert liquid medium, and purifying to obtain the xylylene diisocyanate.
3. The method for synthesizing xylylene diisocyanate according to claim 2, wherein the concentration of xylylenediamine or hydrochloride and carbonate in the inert liquid medium is 2 to 25% by weight; the weight percentage concentration of the inert liquid medium solution of the bis (trichloromethyl) carbonate is 1 to 70 percent.
4. The method for synthesizing xylylene diisocyanate according to claim 3, wherein the concentration of the solution of bis (trichloromethyl) carbonate in the inert liquid medium is 30-50% by weight.
5. The method for synthesizing xylylene diisocyanate according to claim 1 to 4, wherein the catalyst causing or partially causing the activation of bis (trichloromethyl) carbonate is added to the reaction solution in an amount of 0 to 10% by weight based on the weight of bis (trichloromethyl) carbonate.
6. The method for synthesizing xylylene diisocyanate according to claim 5, wherein the catalyst is one or more selected from the group consisting of diethylamine, trimethylamine, triethylamine, N-dimethylaniline, pyridine and dimethylformamide.
7. The method for synthesizing xylylene diisocyanate according to claim 6, wherein the amount of the catalyst is 1 to 5% by weight based on the bis (trichloromethyl) carbonate.
8. The method for synthesizing xylylene diisocyanate as claimed in any one of claims 1 to 4, wherein the inert liquid medium is selected from the group consisting of petroleum ether, cyclohexane, n-hexane, mixed xylene, o-xylene, m-xylene, p-xylene, toluene, xylene, 1, 2-dichloroethane, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, ethyl acetate, propyl acetate, amyl acetate, isoamyl acetate, butyl acetate, isobutyl acetate, phenyl acetate, ethyl propionate, propyl propionate, amyl propionate, isoamyl propionate, butyl propionate, isobutyl propionate, amyl formate, ethyl isovalerate, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, anisole and cyclohexanone.
9. The method according to claim 1, wherein the xylylenediamine comprises m-xylylenediamine and/or p-xylylenediamine and o-xylylenediamine.
10. The method for synthesizing xylylene diisocyanate as claimed in claim 1, which comprises the following steps:
preparing 20-50% of bis (trichloromethyl) carbonate solution; adding a chlorobenzene solution of triethylamine with the concentration of 5-20% at the temperature of 20-30 ℃, and stirring and activating for 1 hour;
dropwise adding a chlorobenzene solution of xylylenediamine into the reaction liquid at the temperature of-20 ℃, stirring, heating to reflux reaction for 0.5-5 hours after dropwise adding, filtering to remove insoluble substances, carrying out reduced pressure distillation to recover chlorobenzene, and purifying to obtain the xylylene diisocyanate.
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