CN102653517A - Method for preparing isocyanate from carbamate - Google Patents
Method for preparing isocyanate from carbamate Download PDFInfo
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- CN102653517A CN102653517A CN2011100505835A CN201110050583A CN102653517A CN 102653517 A CN102653517 A CN 102653517A CN 2011100505835 A CN2011100505835 A CN 2011100505835A CN 201110050583 A CN201110050583 A CN 201110050583A CN 102653517 A CN102653517 A CN 102653517A
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Abstract
The invention relates to the field of chemical industry production, particularly a method for preparing isocyanate from carbamate, which comprises the following steps: 1) mixing carbamate with a solvent (of which the boiling point is lower than isocyanate) which does not react with the carbamate and isocyanate, introducing an inert gas, and adjusting the reaction temperature to initiate the decomposition reaction of carbamate under the reaction pressure of 0.1-5.0 MPa while continuously discharging low carbon alcohol gas; and 2) after the reaction, separating the product and the solvent to obtain a crude isocyanate product. In the step 1), the solvent comprises one or more of methylbenzene, xylene, chlorobenzene, orthodichlorobenzene, nitrobenzene, thiophane and N,N-dimethylaniline. The invention has the advantages of simple and accessible pyrolytic technique and low facility request, and can easily implement industrialization; and the reaction is carried out under pressurized condition within a short time, the conversion rate is up to 95%, the yield is higher than 80%, the solvent can be recycled, and thus, the invention is environment-friendly and pollution-free.
Description
Technical field
The present invention relates to chemical production field, particularly, the present invention relates to a kind of method for preparing isocyanic ester by carbamate.
Background technology
Isocyanic ester is a main raw material of producing urethane, has the two-fold advantage of plastics and rubber simultaneously by the urethane of its production, is widely used in industries such as elastomerics, tackiness agent, coating and plastics.Domestic demand to isocyanic ester is increasing year by year, annual from a large amount of isocyanic ester of external import to satisfy the demands, so the application prospect of isocyanic ester is boundless.Isocyanate products on the market mainly contains benzene isocyanic ester (PI), '-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI) and hexamethylene diisocyanate (HDI).
At present, the working method of isocyanic ester is mainly phosgenation both at home and abroad, and this method uses the phosgene of severe toxicity to make raw material; The hydrochloric acid that by-product is a large amount of, production equipment is complicated, and is high to equipment requirements; Process flow is many, and environmental pollution is more serious, and the by product in the product is not easily separated; This method is eliminated just gradually, therefore on the basis of phosgenation, has developed non-phosgene.Progress report about non-phosgene has: the patent of Lyondell chemical company has been introduced a kind of technology of producing MDI with MDA as raw material; It is the operational path of raw material system MDI that Monsanto Company has developed with aniline and carbonic acid gas, and this method is through the finally synthetic MDI of N-phenyl meglumine acid methyl esters, MDU, but the industriallization of all being unrealized; It is the technology of raw material system MDI that Japan company of Asahi Chemical Industry has developed with aniline, ethanol and carbon monoxide, but the weak point of this technology is that the consumption of solvent and acid catalyst is excessive, and it is too high to recycle cost.The TDI production technique of Mitsui East Asia chemical company exploitation; Be through nitro-compound and carbon monoxide synthesis of carbamates; Carbamate pyrolysis again obtains isocyanic ester, but this method exists catalyzer and product separation difficulty and catalyzer equipment to be had problems such as corrosion; ENI chemical company has reported that a kind of is the method (WP 0156977) of raw material production TDI with methylcarbonate (DMC); This method generates carbamate with DMC and tolylene diamine reaction; Carbamate pyrolysis again generates TDI; The weak point of this method is long reaction time and complex equipments, and the pyrolysis temperature of carbamate is higher.
In the non-phosgene, the carbamate pyrolysis generates the step of most critical in the synthetic route that isocyanic ester is an isocyanic ester.Isocyanic ester has chemical property active-NCO group is easy to take place side reaction, and this generates isocyanic ester for the complete pyrolysis of carbamate and has brought huge difficulty and challenge.For the decomposition of carbamate, US5731458 has reported a kind of decompression pyrolytic method, and the operational condition of this method is 1～1000mbar, 150～400 ℃, and the transformation efficiency of carbamate is more than 90%; US 5502244 has reported a kind of under 150～350 ℃, is the normal pressure method for pyrolysis of catalyzer with alkali-metal organic sulfonate; CN 200610012745.5 has reported and a kind ofly under 0.090～0.093MPa, 210～290 ℃ of conditions, has carried out carbamate pyrolytic method that yield is 73.8～93.8%; 201010129064.3 of CN provide a kind of method of microwave-assisted pyrolysis carbamate; This method is to be catalyzer with compound zinc salt; The dimethyl sulphoxide solution that in ion liquid microwave reactor is housed, adds carbamate, reaction obtains isocyanic ester under 5～20mmHg vacuum tightness, 150～280 ℃ of conditions.These methods are to react in decompression or normal pressure basically; The concentration of carbamate is lower, and long reaction time is easy to take place side reaction; The composition of reaction product is comparatively complicated; Solvent for use and isocyanic ester are not easily separated, and the aftertreatment of isocyanic ester has big difficulty, environment is had problems such as bigger pollution; CN 200810173537.2 provides the method for pyrolysis carbamate under a kind of catalyzer condition; This method is combined as catalyzer with one or more of zinc, nickel, copper; Pyrolysis aliphatics or alicyclic diurethanes under the condition of 1～1.5 barometric point and 50～240 ℃; The isocyanic ester productive rate of this method is lower, is up to 57%; US 2005154227 has reported with US 2003162995 and has carried out carbamate pyrolysated process in the thin-film evaporator; The carbamate and the solvent mixture that are about to molten state join in the thin-film evaporator; Keep 150～300 ℃ of temperature, introduce a tubular reactor behind the initial reaction it is decomposed under 300～600 ℃ fully, condensation obtains isocyanic ester; This method is even to heat, yield is high, but exists product to be prone to the too high problem of polymerization, energy consumption.U.S. ARCO company, Olin company, SUMITOMO CHEMICAL chemical company, Mitsubishi change into company etc. and have all launched this The Application of Technology research in addition, and have obtained certain achievement, but all do not see industrialized report.
Summary of the invention
The objective of the invention is to provides a kind of method that is prepared isocyanic ester by carbamate for solving serious, the problems such as operational path is complicated, product concentrating and separating difficulty of environmental pollution in the prior art.
The method for preparing isocyanic ester by carbamate according to the present invention may further comprise the steps:
1) with carbamate and boiling point be lower than isocyanic ester, not with the solvent of carbamate and isocyanate reaction; Feed rare gas element; The conditioned reaction temperature makes carbamate generation decomposition reaction, and wherein reaction pressure is 0.1～5.0MPa, and continues to discharge low-carbon alcohol gas;
2) reaction after with product and separated from solvent, obtain the thick product of isocyanic ester.
Prepared the method for isocyanic ester by carbamate according to the present invention, solvent comprises toluene, YLENE, chlorobenzene, orthodichlorobenzene, oil of mirbane, THTP and N, one or more in the accelerine in the said step 1).
The method for preparing isocyanic ester according to the present invention by carbamate; The mass ratio of carbamate and solvent is 1: 0.2～100 in the said step 1), in this concentration range, not only can effectively control the generation of side reaction but also productive rate and the output of isocyanic ester are improved.
Prepared the method for isocyanic ester by carbamate according to the present invention, temperature of reaction is 100～450 ℃; Reaction times is 0.2～8h.
The method for preparing isocyanic ester according to the present invention by carbamate; Carbamate specifically comprises phenyl urethan (like methyl phenyl carbamate, N-phenylurethane, carbaniloyl butyl ester etc.), diphenyl methane diamino formic ether (like diphenyl methane diamino acid methyl ester, diphenyl methane diamino ethyl formate, diphenyl methane diamino butyl formate) and hexa-methylene diamino manthanoate etc. in the said step 1), and wherein low-carbon alcohol comprises methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol (comprising its isomers).
According to one embodiment of the invention, specific operation process is following:
Add carbamate and solvent in the autoclave according to a certain percentage; Behind the inert gas replacement reaction conditions is transferred to appointment temperature of reaction and pressure; Continue to discharge low-carbon alcohol gas in the reaction process, discharging behind the reaction certain hour, product obtains thick product after separating.
Described solvent is an inert, not with reaction system in any reactant or resultant react, and at a certain temperature carbamate and isocyanic ester are had solvability preferably, dispersed isocyanate preferably.Service condition solvent preferably comprises toluene, YLENE, chlorobenzene, orthodichlorobenzene, oil of mirbane, THTP, N, accelerine etc.
Described product is separated into the mixing solutions cooling after the discharging, filters and obtains carbamate, and straight run distillation obtains the thick product of isocyanic ester, filters the carbamate that obtains and distills the solvent cycle utilization that obtains.
The invention provides the clean and effective synthetic route that a kind of new non-phosgene pyrolysis generates isocyanic ester.The carbamate pyrolysis is that the reaction of isocyanic ester is reversible reaction, and reacts and at high temperature carry out, and the isocyano activity in the product is higher at this moment; Be prone to take place side reaction, for improving the transformation efficiency and the yield of reaction, the solvent that the present invention selects boiling point to be lower than isocyanic ester reacts; And the pressure of strict control reaction in reaction process; Improve the speed of reacting, shortened the reaction times, reduced the possibility that side reaction takes place in the reaction process, and after the reaction completion; Can product be separated with solvent through underpressure distillation; Be the simple of later separation change, therefore reduced the generation of side reaction, improved the selectivity and the transformation efficiency of reaction through method of the present invention.
The present invention has also done following improvement in order further to improve rate of rotation in addition:
(1) with carbamate and solvent by 1: 0.2～100 mass ratio for adding in the high-pressure reactor; The concentration of carbamate and the concentration of reaction product isocyanic ester have been reduced after adding solvent; Reduced the possibility that side reaction takes place in the reaction system; The decarbonylation glycosylation reaction that comprises carbamate generates primary amine and alkene or secondary amine, and isocyanic ester and the reaction of by product secondary amine generate carbamide compound, and isocyanic ester and urethane reaction generate the self-polymerization reaction of allophanate and isocyanic ester etc.; Control through this mass ratio; Not only can reduce the incidence of side reaction, but also can reach higher transformation efficiency and output, reach best net effect;
(2) continue in the reaction process to emit low-carbon alcohol gas, impel reaction to carry out to the decomposition direction of carbamate, bigger raising the transformation efficiency of carbamate;
(3) pyrolytic reaction is carried out under the condition of pressurization, has improved speed of response, has shortened the reaction times, carries out having guaranteed that isocyanic ester exists with monomeric form on the basis completely in reaction, rather than polymerization takes place;
(4) after reaction finishes, the product cooling, the unreacted amino manthanoate is separated out, and filters the back and reclaims, and the filtrate decompression distillation obtains the thick product of isocyanic ester, and solvent utilizes again.
According to the method for the invention, the thermal decomposition time of carbamate is shorter, and used quantity of solvent is less; And the later separation that reaction finishes is handled comparatively simple; Can coincide preferably with existing mature industry technology, raw material can recycling, and economy is higher.
Method of the present invention advantage compared with prior art is:
(1) pyrolytic technique among the present invention is simple, and equipment requirements is lower, is easy to industriallization;
(2) the present invention carries out under pressurized conditions, and the reaction times is short, and transformation efficiency reaches 95%, and yield is more than 80%;
(3) solvent that uses of the present invention is cheap and easy to get, can realize preferably that product separates, and be easy to integrate with existing industrial technology, and solvent can realize recycle that environmental friendliness is pollution-free.
Embodiment
Embodiment 1
Take by weighing the 15g phenyl urethan and put into the 500ml autoclave, add the 300g orthodichlorobenzene, stirring mixes it; Wherein the mass ratio of phenyl urethan and orthodichlorobenzene is 1: 20, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, it is 4.0MPa that Heating temperature rises to 250 ℃, pressure, keeps 1h; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: the carbaniloyl ester conversion rate is 95.6%, and benzene isocyanic ester yield is 83.9%.
Embodiment 2
Take by weighing the 25g phenyl urethan and put into the 500ml autoclave, add 300g oil of mirbane, stirring mixes it; Wherein the mass ratio of phenyl urethan and oil of mirbane is 1: 12, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 200 ℃, 4.0MPa, keeps 3h; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: the carbaniloyl ester conversion rate is 97.1%, and benzene isocyanic ester yield is 86.0%.
Embodiment 3
Take by weighing 10g toluene diurethanes and put into the 500ml autoclave, add 300g YLENE, stirring mixes it; Wherein the mass ratio of toluene diurethanes and YLENE is 1: 30, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 300 ℃, 2.5MPa, keeps 1h; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: toluene diamino acid ester conversion rate is 98.4%, and the tolylene diisocyanate yield is 89.2%.
Embodiment 4
Take by weighing 15g toluene diurethanes and put into the 500ml autoclave, add the 300g chlorobenzene, stirring mixes it; Wherein the mass ratio of toluene diurethanes and chlorobenzene is 1: 20, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 350 ℃, 3.0MPa, keeps 30min; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: toluene diamino acid ester conversion rate is 99.1%, and the tolylene diisocyanate yield is 84.9%.
Embodiment 5
Take by weighing 3g toluene diurethanes and put into the 500ml autoclave, add 300g toluene, stirring mixes it; Wherein the mass ratio of toluene diurethanes and toluene is 1: 100, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 450 ℃, 5.0MPa, keeps 0.2h; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: toluene diamino acid ester conversion rate is 99.2%, and the tolylene diisocyanate yield is 82.1%.
Embodiment 6
Take by weighing 20g toluene diurethanes and put into the 500ml autoclave, add 300gN, accelerine, wherein toluene diurethanes and N; The mass ratio of accelerine is 1: 15, stirs it is mixed, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 400 ℃, 4.0MPa, keeps 30min; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: toluene diamino acid ester conversion rate is 99.4%, and the tolylene diisocyanate yield is 87.8%.
Embodiment 7
Take by weighing the 10g diphenyl methane diamino formic ether and put into the 500ml autoclave, add the 300g orthodichlorobenzene, wherein the mass ratio of diphenyl methane diamino formic ether and orthodichlorobenzene is 1: 30; Stirring mixes it, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 250 ℃, 1.2MPa, keeps 3h; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: the diphenyl methane diamino formic ether transformation efficiency is 97.2%, and the '-diphenylmethane diisocyanate yield is 90.1%.
Embodiment 8
Take by weighing the 5g diphenyl methane diamino formic ether and put into the 500ml autoclave, add the stirring of 300g toluene it is mixed, wherein the mass ratio of diphenyl methane diamino formic ether and toluene is 1: 60; The reaction kettle sealing, behind nitrogen replacement air 3 times, punching press 1MPa; Heating temperature rises to 280 ℃, 1.8MPa, keeps 30min, and reaction finishes directly discharging of back; Cooling is analyzed.
Reaction result: the diphenyl methane diamino formic ether transformation efficiency is 98.1%, and the '-diphenylmethane diisocyanate yield is 83.8%.
Embodiment 9
Take by weighing the 30g diphenyl methane diamino formic ether and put into the 500ml autoclave, add 300g oil of mirbane, stirring mixes it; Wherein the mass ratio of diphenyl methane diamino formic ether and oil of mirbane is 1: 10, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 220 ℃, 0.8MPa, keeps 5h; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: the diphenyl methane diamino formic ether transformation efficiency is 98.1%, and the '-diphenylmethane diisocyanate yield is 92.1%.
Embodiment 10
Take by weighing the 6g diphenyl methane diamino formic ether and put into the 500ml autoclave, add the 300g THTP, stirring mixes it; Wherein the mass ratio of diphenyl methane diamino formic ether and THTP is 1: 50, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 300 ℃, 2.5MPa, keeps 20min; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: the diphenyl methane diamino formic ether transformation efficiency is 99.4%, and the '-diphenylmethane diisocyanate yield is 82.9%.
Embodiment 11
Take by weighing 40g hexa-methylene diamino manthanoate and put into the 500ml autoclave, add 300gN, accelerine, stirring mixes it; Wherein hexa-methylene diamino manthanoate and N, the mass ratio of accelerine is 1: 7.5, the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 100 ℃, 0.1MPa, keeps 8h; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: hexa-methylene carboxylamine ester conversion rate is 95.1%, and the hexamethylene diisocyanate yield is 93.2%.
Embodiment 12
Take by weighing 100g hexa-methylene diamino manthanoate and put into the 500ml autoclave, add the 20g THTP, stirring mixes it; Wherein the mass ratio of hexa-methylene diamino manthanoate and THTP is 1: 0.2, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 150 ℃, 0.4MPa, keeps 4h; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: hexa-methylene diamino manthanoate transformation efficiency is 97.2%, and the hexamethylene diisocyanate yield is 83.7%.
Embodiment 13
Take by weighing 8g hexa-methylene diamino manthanoate and put into the 500ml autoclave, add the 300g chlorobenzene, stirring mixes it; Wherein the mass ratio of hexa-methylene diamino manthanoate and chlorobenzene is 1: 37.5, and the reaction kettle sealing is behind nitrogen replacement air 3 times; Punching press 1MPa, Heating temperature rises to 210 ℃, 0.7MPa, keeps 1h; Reaction finishes directly discharging of back, and cooling is analyzed.
Reaction result: hexa-methylene diamino manthanoate transformation efficiency is 96.4%, and the hexamethylene diisocyanate yield is 87.6%.
Claims (8)
1. one kind prepares the method for isocyanic ester by carbamate, it is characterized in that, said method comprising the steps of:
1) with carbamate and boiling point be lower than isocyanic ester, not with the solvent of carbamate and isocyanate reaction; Feed rare gas element; The conditioned reaction temperature makes carbamate generation decomposition reaction, and wherein reaction pressure is 0.1～5.0MPa, and continues to discharge low-carbon alcohol gas;
2) reaction after with product and separated from solvent, obtain the thick product of isocyanic ester.
2. the method for preparing isocyanic ester by carbamate according to claim 1; It is characterized in that; Solvent comprises toluene, YLENE, chlorobenzene, orthodichlorobenzene, oil of mirbane, THTP and N, one or more in the accelerine in the said step 1).
3. according to claim 1ly prepare the method for isocyanic ester, it is characterized in that the mass ratio of carbamate and solvent is 1: 0.2～100 in the said step 1) by carbamate.
4. according to claim 1ly prepare the method for isocyanic ester, it is characterized in that temperature of reaction is 100～450 ℃ in the said step 1) by carbamate.
5. according to claim 1ly prepare the method for isocyanic ester, it is characterized in that the reaction times is 0.2～8h in the said step 1) by carbamate.
6. the method for preparing isocyanic ester by carbamate according to claim 1; It is characterized in that carbamate comprises one or both in methyl phenyl carbamate, N-phenylurethane, carbaniloyl butyl ester, diphenyl methane diamino acid methyl ester, diphenyl methane diamino ethyl formate, diphenyl methane diamino butyl formate and the hexa-methylene diamino manthanoate in the said step 1).
7. according to claim 1ly prepare the method for isocyanic ester, it is characterized in that inert gasses comprises nitrogen, helium, argon gas and carbonic acid gas in the said step 1) by carbamate.
8. according to claim 1ly prepare the method for isocyanic ester, it is characterized in that said step 2 by carbamate) in underpressure distillation separates with solvent with product.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964272A (en) * | 2012-11-09 | 2013-03-13 | 中国科学院过程工程研究所 | Method for preparing hexamethylene-1,6-diisocyanate (HDI) by heterocatalytic pyrolysis in liquid phase |
| CN104418773A (en) * | 2013-09-02 | 2015-03-18 | 上海龙翔生物医药开发有限公司 | Synthetic method of 2,4,5-trifluoro-benzene isocyanate and intermediate thereof |
| CN105837471A (en) * | 2015-01-16 | 2016-08-10 | 中国科学院过程工程研究所 | Two-stage pyrolysis device for preparation of polymethylene polyphenyl polyisocyanate by liquid phase pressurization thermal decomposition method and pyrolysis method |
| CN110423208A (en) * | 2019-08-15 | 2019-11-08 | 中国科学院过程工程研究所 | A kind of preparation method of '-diphenylmethane diisocyanate |
| CN110467546A (en) * | 2018-05-10 | 2019-11-19 | 中国科学院过程工程研究所 | A method of preparing m-xylylene diisocyanate |
| CN114456091A (en) * | 2021-12-29 | 2022-05-10 | 中国石油化工股份有限公司 | Device and method for preparing hexamethylene diisocyanate by pyrolysis in mixed solvent |
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| CN101492397A (en) * | 2008-01-22 | 2009-07-29 | 中国科学院成都有机化学有限公司 | Method for continuous preparation of 1,6-hexamethylene diisocyanate |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964272A (en) * | 2012-11-09 | 2013-03-13 | 中国科学院过程工程研究所 | Method for preparing hexamethylene-1,6-diisocyanate (HDI) by heterocatalytic pyrolysis in liquid phase |
| CN104418773A (en) * | 2013-09-02 | 2015-03-18 | 上海龙翔生物医药开发有限公司 | Synthetic method of 2,4,5-trifluoro-benzene isocyanate and intermediate thereof |
| CN105837471A (en) * | 2015-01-16 | 2016-08-10 | 中国科学院过程工程研究所 | Two-stage pyrolysis device for preparation of polymethylene polyphenyl polyisocyanate by liquid phase pressurization thermal decomposition method and pyrolysis method |
| CN105837471B (en) * | 2015-01-16 | 2018-01-12 | 中国科学院过程工程研究所 | A kind of liquid phase pressurization thermal decomposition method prepares the two level pyrolysis installation and method for pyrolysis of poly methylene poly phenyl poly isocyanate |
| CN110467546A (en) * | 2018-05-10 | 2019-11-19 | 中国科学院过程工程研究所 | A method of preparing m-xylylene diisocyanate |
| CN110467546B (en) * | 2018-05-10 | 2021-03-19 | 中国科学院过程工程研究所 | Method for preparing m-xylylene diisocyanate |
| CN110423208A (en) * | 2019-08-15 | 2019-11-08 | 中国科学院过程工程研究所 | A kind of preparation method of '-diphenylmethane diisocyanate |
| WO2021027953A1 (en) * | 2019-08-15 | 2021-02-18 | 中国科学院过程工程研究所 | Preparation method for diphenylmethane diisocyanate |
| CN114456091A (en) * | 2021-12-29 | 2022-05-10 | 中国石油化工股份有限公司 | Device and method for preparing hexamethylene diisocyanate by pyrolysis in mixed solvent |
| CN114456091B (en) * | 2021-12-29 | 2023-11-10 | 中国石油化工股份有限公司 | Device and method for preparing hexamethylene diisocyanate by pyrolysis in mixed solvent |
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Application publication date: 20120905 |