CN101195590A - Method for producing 1,6-hexamethylene diisocyanate with hexa-methylene diamino-methyl formate liquid phase thermal cracking - Google Patents

Method for producing 1,6-hexamethylene diisocyanate with hexa-methylene diamino-methyl formate liquid phase thermal cracking Download PDF

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Publication number
CN101195590A
CN101195590A CNA2006101052973A CN200610105297A CN101195590A CN 101195590 A CN101195590 A CN 101195590A CN A2006101052973 A CNA2006101052973 A CN A2006101052973A CN 200610105297 A CN200610105297 A CN 200610105297A CN 101195590 A CN101195590 A CN 101195590A
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oxide
methyl
tetrafluoroboric acid
hexa
loading
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邓友全
郭晓光
张庆华
马昱博
马祥元
田雄
王利国
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The invention relates to a method for preparing corresponding 1, 6-hexadiisocyanate heated and cracked by hexamethylene aminomethyl formate liquid phase, which adopts ion liquid as reaction solvent and supported metal oxide as catalyst. The main character of the method is mild, clean and green in reaction condition, little in volatility, high in purity of the separated and obtained product and relatively less in by-product.

Description

The hexa-methylene diamino-methyl formate liquid phase thermal cracking prepares the method for hexamethylene diisocyanate
Technical field
The present invention relates to a kind of hexa-methylene diamino-methyl formate (HDC) liquid phase thermal cracking in the presence of appropriate catalyst and prepare the method for corresponding hexamethylene diisocyanate.
Background technology
Isocyanic ester has purposes very widely as the important organic reaction intermediate of a class at industry, agricultural, medical and health everyway.This compounds is widely used in the synthetic of polymeric polyisocyanate, polyurethanes, polyureas, superpolymer adhesive, Insecticides (tech) ﹠ Herbicides (tech) etc.Wherein 1, hexamethylene-diisocyanate (HDI) belongs to not flavescence aliphatic diisocyanate, and it is mainly used in the polyurethane adhesive of automotive OEM coating and retouching paint, aircraft OEM coating and retouching paint, anticorrosive coating, wood furniture lacquer, wire enamel, train retouching paint, good light stability and rocket propellant etc.
At present, isocyanic ester mainly is to make with corresponding aminated compounds and phosgene reaction.Phosgene is a kind of deadly poisonous compound, and, there are a large amount of severe corrosive hydrogenchloride to generate in the reaction process.Therefore, often cause equipment corrosion, phosgene is revealed, and causes environmental pollution and personnel injury.
Along with increasing the weight of day by day of world wide environment pollution, national governments all constantly implement environmental practice with the formal compulsion of legislation, with the generation and the discharging of control hazardous and noxious substances.The research and development of no phosgene system isocyanic ester chemistry product clearer production technology have become the focus of countries in the world scientific research institution and chemical enterprise concern.Non-phosgene legal system isocyanation esterification is learned product and is not only helped environment protection, and not chloride in the production medium, can produce more high-quality product.
Over twenties years, people have carried out number of research projects in order to seek a kind of safe, inexpensive, eco-friendly isocyanic ester synthetic method, and have found the route of many non-phosgene synthesizing isocyanates.1967, Bennet has realized the reaction of nitroaromatic compounds thing reduction carbonylation one-step synthesis isocyanic ester first.But this reaction often needs exacting terms such as high temperature, high pressure, causes problems such as side reaction is many, product is complicated, separation difficulty, thereby does not possess practical value.Simultaneously, use nitro-compound in the presence of pure and mild carbon monoxide, to reduce carbonylation, make carbamate; Or earlier nitro-compound is made aminated compounds, carry out oxidative carbonylation again and make carbamate.Then, the method that the thermo-cracking carbamate obtains isocyanic ester under comparatively high temps has also obtained excellent research.But also relate to the use of high temperature, high pressure and deleterious carbon monoxide in this building-up process, the easy inactivation of catalyzer, this has just limited its application and popularization.And using amine to be raw material, carbonic acid gas is that carbonylating agent carries out carbonylation and dewaters through dewatering agent then and obtain the method for corresponding isocyanic ester, but such reaction solvent consumption is big, and a large amount of abraum salts of generation are difficult to handle.Use amine to carry out the synthetic corresponding carbamate of carbonylation with carbonic ether as carbonylating agent in addition, the method that then the carbamate thermo-cracking is obtained corresponding isocyanate and alcohol has industrial application value preferably.
This thermal cracking processes comprises gas phase and two kinds of thermal-cracking methods of liquid phase.It is a pyroprocess that vapor phase cracking is separated, and general temperature will be higher than 300 ℃, and liquid phase method thermal cracking processes temperature generally is lower than 300 ℃, needs to add catalyzer and high boiling solvent usually.Often be accompanied by a lot of side reactions in the thermal cracking processes and take place, this has not only reduced yield, and can stop up reactor and miscellaneous equipment.At English Patent No.1, in 247,451, toluene diamino-methyl formate thermo-cracking prepares tolylene diisocyanate in gas phase, and the thermo-cracking temperature is 400 ℃～600 ℃, and its shortcoming is the low and a large amount of by product of productive rate.The method that obtains corresponding isocyanic ester under the liquid-phase reaction condition of ionic liquid as solvent has overcome above mentioned shortcoming, has that reaction conditions gentleness, ionic liquid are reused often (80～100 times), selectivity and yield height, green, cleaning, safety and people's extensive concern extremely.
Ionic liquid at room temperature is meant mainly by organic cation and inorganic or organic anion constitutes in room temperature or be bordering on the salt that is liquid under the room temperature.Their principal feature is: non-volatile or zero vapour pressure, low melting point, wide liquid journey, strong electrostatic field, wide electrochemical window, good ionic conduction thermal conductivity, high heat capacity and thermal energy storage density, high thermostability all has good dissolving ability, designability to multiple organic and inorganic materials.These unique advantages make ionic liquid receive the acceptance and the concern of countries in the world catalysis circle and petroleum chemical enterprise circle as eco-friendly " cleaning " solvent and new catalyst system, and have obtained using widely in catalysis and organic synthesis.
Summary of the invention
The purpose of this invention is to provide the method that a kind of hexa-methylene diamino-methyl formate (HDC) liquid phase thermal cracking in the presence of appropriate catalyst, ion liquid solvent prepares corresponding hexamethylene diisocyanate.
Key of the present invention is to seek a kind of appropriate catalyst, requires its catalytic performance to get well, and low price, and we select loaded metal oxide as catalyzer.
A kind of hexa-methylene diamino-methyl formate liquid phase thermal cracking preparation 1, the method of hexamethylene-diisocyanate, it is characterized in that this method with hexa-methylene diamino-methyl formate as reactant, ionic liquid is as reaction solvent, under catalyst action, control absolute reaction pressure 0～0.1Mpa, temperature of reaction generates hexamethylene diisocyanate for 100～400 ℃; Wherein the carrier of catalyzer is selected from silicon oxide or aluminum oxide, the activity of such catalysts component be selected from cupric oxide, nickel oxide, zinc oxide, zirconium white, the molybdenum oxide a kind of, two or three, the loading of active ingredient is 1-15wt%; Ionic liquid is selected from a kind of in N-trimethylammonium-butyl Tetrafluoroboric acid, 4-butyl-phosphonium Tetrafluoroboric acid ionic liquid, 1-methyl-3 ethyl imidazol(e) Tetrafluoroboric acid, 1-methyl-3 butyl imidazole Tetrafluoroboric acid, 1-methyl-2 ethyl pyrazoles Tetrafluoroboric acid, 1-methyl-2 butyl pyrazoles Tetrafluoroboric acid, the N-methyl-ethyl pyrrolidine Tetrafluoroboric acid.
Hexa-methylene diamino-methyl formate of the present invention and ion liquid mass ratio are 1: 1～20.
The mass ratio of catalyzer of the present invention and hexa-methylene diamino-methyl formate is 1: 10～100.
Preparation method of ionic liquid that the present invention is used and character can be referring to Deng Youquan. ionic liquid-character, preparation and application [M]. and the .2006 of Sinopec press, 7,1.
Principal feature of the present invention is that reaction conditions gentleness, cleaning, green, little, the separating obtained product purity height of volatility and by product are less relatively.
Answer technological process to compare with classical inverse, principal feature of the present invention is for to use ionic liquid to be solvent, compares with the high boiling solvent that prior art is used to have following advantage:
1, solvent and previously used solvent phase ratio, it is a kind of solvent of green, have as non-volatile or zero vapour pressure, wide liquid journey, good ionic conduction thermal conductivity, high heat capacity and thermal energy storage density, high thermostability, multiple organic and inorganic materials all there is good dissolving ability, the physicochemical property that designability etc. are good;
2, solvent for use and previously used solvent phase ratio, volatilization hardly is beneficial in the product separation purification process and improves product purity and quality;
3, solvent for use and previously used solvent phase ratio needn't add stopper in addition again.
Embodiment
Embodiment 1
Stir in the round-bottomed flask at 2000 milliliters magnetic, add N-trimethylammonium-butyl Tetrafluoroboric acid ionic liquid (N 1114BF 4) 500ml, at 200 ℃, under 10mmHg and the 200 rev/mins of conditions, add hexa-methylene diamino-methyl formate 200 grams, cupric oxide/silicon oxide (loading is 5wt%) 20g, keep the temperature and pressure reaction after 1.5 hours, obtain one by hexa-methylene one isocyano one Urethylane, hexa-methylene diamino-methyl formate and 1, the mixed solution that hexamethylene-diisocyanate is formed, stratographic analysis 1, the hexamethylene-diisocyanate yield is 88%, separation yield be 82% and purity be 85%～90%, can reach 98% through a rectifying, can be repeatedly used after adding raw material HDC then.
Embodiment 2
Step is with embodiment 1, still with 4-butyl-phosphonium Tetrafluoroboric acid ionic liquid (P 444BF 4) replacement N 1114BF 4, the mixed solution that obtains, stratographic analysis hexamethylene diisocyanate yield 80%, separation yield be 76% and purity be 81%～84%, can reach 96% through a rectifying, can be repeatedly used after adding raw material HDC.
Embodiment 3
Step is with embodiment 1, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/silicon oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, the mixed solution that obtains, stratographic analysis hexamethylene diisocyanate yield 80%, separation yield be 77% and purity be 81%～85%, can reach 97% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 4
Step is with embodiment 1, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/aluminum oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, the mixed solution that obtains, stratographic analysis hexamethylene diisocyanate yield 82%, separation yield be 78% and purity be 81%～85%, can reach 95% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 5
Step is with embodiment 2, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/silicon oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, the mixed solution that obtains, stratographic analysis hexamethylene diisocyanate yield 81%, separation yield be 76% and purity be 81%～85%, can reach 97% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 6
Step is with embodiment 2, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/aluminum oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, the mixed solution that obtains, stratographic analysis hexamethylene diisocyanate yield 79%, separation yield be 75% and purity be 79%～83%, can reach 95% through a rectifying, can be repeatedly used behind the adding raw material HDC polymerization does not take place.
Embodiment 7
Step is with embodiment 1, still with 1-methyl-3 ethyl imidazol(e) Tetrafluoroboric acid ionic liquid (EMImBF 4) replacement N 1114BF 4, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 80%, separation yield be 74% and purity be 77%～85%, can reach 95% through a rectifying, can be repeatedly used after adding raw material HDC.
Embodiment 8
Step is with embodiment 1, still with 1-methyl-3 butyl imidazole Tetrafluoroboric acid ionic liquid (BMImBF 4) replacement N 1114BF 4, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 82%, separation yield be 76% and purity be 77%～85%, can reach 95% through a rectifying, can be repeatedly used after adding raw material HDC.
Embodiment 9
Step is with embodiment 7, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/silicon oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 79%, separation yield be 75% and purity be 77%～85%, can reach 95% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 10
Step is with embodiment 7, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/aluminum oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 80%, separation yield be 76% and purity be 77%～85%, can reach 95% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 11
Step is with embodiment 8, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/silicon oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 82%, separation yield be 78% and purity be 79%～85%, can reach 95% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 12
Step is with embodiment 8, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/aluminum oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 81%, separation yield be 75% and purity be 77%～85%, can reach 95% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 13
Step is with embodiment 1, still with 1-methyl-2 ethyl pyrazoles Tetrafluoroboric acid ionic liquid (EMPyBF 4) replacement N 1114BF 4, the mixed solution that obtains, stratographic analysis hexamethylene diisocyanate yield is 72%, separation yield be 64% and purity be 70%～80%, can reach 90% through a rectifying, can be repeatedly used after adding raw material HDC.
Embodiment 14
Step is with embodiment 1, still with 1-methyl-2 butyl pyrazoles Tetrafluoroboric acid ionic liquid (BMPyBF 4) replacement N 1114BF 4, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 74%, separation yield be 69% and purity be 70%～80%, can reach 90% through a rectifying, can be repeatedly used after adding raw material HDC.
Embodiment 15
Step is with embodiment 13, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/silicon oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 71%, separation yield be 65% and purity be 70%～80%, can reach 90% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 16
Step is with embodiment 13, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/aluminum oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 69%, separation yield be 63% and purity be 65%～75%, can reach 90% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 17
Step is with embodiment 14, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/silicon oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 71%, separation yield be 65% and purity be 70%～80%, can reach 90% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 18
Step is with embodiment 14, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/aluminum oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 69%, separation yield be 63% and purity be 65%～75%, can reach 90% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 19
Step is with embodiment 1, but N-methyl-ethyl pyrrolidine Tetrafluoroboric acid ionic liquid (P 1,2BF 4) to replace N 1114BF 4, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 77%, separation yield be 74% and purity be 81%～85%, can reach 96% through a rectifying, can be repeatedly used after adding raw material HDC.
Embodiment 20
Step is with embodiment 19, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/silicon oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 80%, separation yield be 75% and purity be 75%～85%, can reach 96% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 21
Step is with embodiment 19, but (the nickel oxide loading is 3wt% with nickel oxide-zirconium white/aluminum oxide, zirconic loading is 5wt%) replace cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, and other all remains unchanged, obtain mixed solution, stratographic analysis hexamethylene diisocyanate yield 79%, separation yield be 76% and purity be 75%～85%, can reach 96% through a rectifying, can be repeatedly used behind the adding raw material HDC.
Embodiment 22
Step is with embodiment 19, but (the nickel oxide loading is 3wt% with nickel oxide-molybdenum oxide-zinc oxide/silicon oxide, zirconic loading is 5wt%, the loading of zinc oxide is 15wt%) replacement cupric oxide/silicon oxide (loading is 5wt%), catalyst amounts is constant, other all remains unchanged, obtain mixed solution, stratographic analysis 1, hexamethylene-diisocyanate yield 83%, separation yield be 79% and purity be 80%～90%, can reach 97% through a rectifying, can be repeatedly used after adding raw material HDC.

Claims (3)

1. hexa-methylene diamino-methyl formate liquid phase thermal cracking preparation 1, the method of hexamethylene-diisocyanate, it is characterized in that this method with hexa-methylene diamino-methyl formate as reactant, ionic liquid is as reaction solvent, under catalyst action, control absolute reaction pressure 0～0.1Mpa, temperature of reaction generates hexamethylene diisocyanate for 100～400 ℃; Wherein the carrier of catalyzer is selected from silicon oxide or aluminum oxide, the activity of such catalysts component be selected from cupric oxide, nickel oxide, zinc oxide, zirconium white, the molybdenum oxide a kind of, two or three, the loading of active ingredient is 1-15wt%; Ionic liquid is selected from a kind of in N-trimethylammonium-butyl Tetrafluoroboric acid, 4-butyl-phosphonium Tetrafluoroboric acid ionic liquid, 1-methyl-3 ethyl imidazol(e) Tetrafluoroboric acid, 1-methyl-3 butyl imidazole Tetrafluoroboric acid, 1-methyl-2 ethyl pyrazoles Tetrafluoroboric acid, 1-methyl-2 butyl pyrazoles Tetrafluoroboric acid, the N-methyl-ethyl pyrrolidine Tetrafluoroboric acid.
2. the method for claim 1, it is characterized in that: hexa-methylene diamino-methyl formate and ion liquid mass ratio are 1: 1～20.
3. the method for claim 1, it is characterized in that: the mass ratio of catalyzer and hexa-methylene diamino-methyl formate is 1: 10～100.
CNA2006101052973A 2006-12-09 2006-12-09 Method for producing 1,6-hexamethylene diisocyanate with hexa-methylene diamino-methyl formate liquid phase thermal cracking Pending CN101195590A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101792403A (en) * 2010-03-22 2010-08-04 哈尔滨理工大学 Microwave-assisted method for synthesizing 4,4'-diphenylmethane diisocyanate
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
US8809574B2 (en) 2009-07-23 2014-08-19 Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences Method for preparing isocyanates by liquid-phase thermal cracking
JP2016196498A (en) * 2011-07-13 2016-11-24 宇部興産株式会社 Method for producing isocyanate compound

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8809574B2 (en) 2009-07-23 2014-08-19 Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences Method for preparing isocyanates by liquid-phase thermal cracking
CN101792403A (en) * 2010-03-22 2010-08-04 哈尔滨理工大学 Microwave-assisted method for synthesizing 4,4'-diphenylmethane diisocyanate
CN101792403B (en) * 2010-03-22 2013-02-13 哈尔滨理工大学 Microwave-assisted method for synthesizing 4,4'-diphenylmethane diisocyanate
JP2016196498A (en) * 2011-07-13 2016-11-24 宇部興産株式会社 Method for producing isocyanate compound
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

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