CN102964272B - Method for preparing hexamethylene-1,6-diisocyanate (HDI) by heterocatalytic pyrolysis in liquid phase - Google Patents
Method for preparing hexamethylene-1,6-diisocyanate (HDI) by heterocatalytic pyrolysis in liquid phase Download PDFInfo
- Publication number
- CN102964272B CN102964272B CN201210448301.1A CN201210448301A CN102964272B CN 102964272 B CN102964272 B CN 102964272B CN 201210448301 A CN201210448301 A CN 201210448301A CN 102964272 B CN102964272 B CN 102964272B
- Authority
- CN
- China
- Prior art keywords
- hexa
- methylene
- pyrolysis
- hdi
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention belongs to the technical field of organic chemical engineering, and relates to a method for preparing hexamethylene-1,6-diisocyanate (HDI) by heterocatalytic pyrolysis in a liquid phase. A low-boiling solvent and a supported solid catalyst are adopted, the reaction temperature is 180-250 DEG C, the pressure is kept at 0.2-2 MPa, and alkyl alcohol generated by the reaction is transferred out of the system along with nitrogen. The conversion rate of the hexamethylene diamino acid ester is higher than 96%, and the product yield is up to higher than 88%. The invention is simple to operate, and has the advantages of high production safety and reliability, and no environment pollution; and the catalyst and solvent can be easily separated from the product, thereby having high recycling performance.
Description
Technical field
The invention belongs to technical field of organic chemistry, relate to one heterogeneous catalysis pyrolysis in liquid phase and prepare hexa-methylene-1, the method for 6-vulcabond.
Background technology
Isocyanic ester is the important organic chemistry intermediate of a class, has a wide range of applications in fields such as coating, dyestuff, urethane, medicine, industrial chemicals.Isocyanic ester main products on market has '-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), phenylisocyanate (PI) and hexa-methylene-1,6-vulcabond (HDI).Particularly because HDI belongs to saturated straight chain aliphatic isocyanates, its polyurethane coating of preparing has the features such as not yellowing, sun-proof, guarantor's color and luster, oil resistant, wear-resisting and anti-efflorescence, it is mainly used in high-grade automobile and aircraft coating and retouching paint, lagging material, water-proof material, the derivative products such as sound insulating sheet material, adhesive for polyurethane, refrigerator sealed strip, protection against corrosion japanning, wood furniture japanning, polyurethane fiber.
The main phosgenation of current industrial production isocyanic ester, adopts phosgene and the reaction of amine salt compound to make.Phosgenation operation condition requires harsh, technical process complexity is loaded down with trivial details, and adopt hypertoxic phosgene as raw material, the life security that can produce a large amount of by-product hydrochloric acid meeting severe corrosion equipments and contaminate environment in production process and threaten operator, in the isocyanate products of producing, containing a large amount of acyl chlorides can affect the quality of product.Growing along with world economy, worldwide problem of environmental pollution is more and more serious, and various countries all carry out environmental practice with the formal compulsion of law, to control discharge of poisonous waste in environment.
Because phosgenation environmental pollution is serious, make non-phosgene prepare hexa-methylene-1,6-vulcabond has broad prospects.At present hexa-methylene-1 is all prepared in research energetically in countries in the world, the non-phosgene of 6-vulcabond, and found the method for many non-phosgenes.Industrial of Asahi Chemical Industry of Japan has successfully developed with CO, O
2under catalyzer existence condition, react the method for preparing HDI with hexanediamine, but CO causes poisoning of catalyst and inactivation under High Temperature High Pressure; Monsanto company of the U.S. utilizes CO
2, hexanediamine is prepared carbaminate, then carries out dehydration reaction and make the technique of HDI with the dewatering agents such as phosphorus oxychloride and carbaminate, and adding of dewatering agent makes later separation operation sequence complexity; American Cyanamid Company utilizes nitro-compound and CO direct reaction to generate HDI, and this reaction pressure is 19.6 ~ 29.4MPa, to equipment requirement of withstand voltage harshness; The technique of HDI is prepared in Germany's BASF exploitation taking dibutyl carbonate and hexanediamine as raw material, but dibutyl carbonate expensive raw material price makes to produce HDI cost high.
Prepare in the method for isocyanic ester at many non-phosgenes, what have industrial prospect most is the pyrolysis method of carbamate preparing isocyanate by pyrolyzing.Urethylane can carry out pyrolysis under the condition that has catalyst-free, and wherein pyrolysis method can be divided into vapour-phase pyrolysis method and liquid phase pyrolysis method.But vapour-phase pyrolysis method pyrolysis temperature is higher, generally, more than 300 DEG C, easily there is coking in pyrolytic process, and operation condition is difficult to control.And liquid phase pyrolysis method pyrolysis temperature is lower, reaction is comparatively gentle, easy handling control.First carbamate pyrolysis can remove a part alkyl alcohol and produce intermediate single-amido acid ester, then single-amido acid ester again pyrolysis slough another molecular alkyl alcohol and produce vulcabond, the alkyl alcohol of deviating from can be recycled, and therefore this technique is green chemistry process.
The Patents of existing report carbamate preparing isocyanate by pyrolyzing is a lot, but the method for mostly mentioning is confined to carry out in laboratory, generally emphasis is placed upon studying in conversion unit, catalyzer or successive reaction.In English Patent No.1247451, the toluencediamine base methyl-formiate in gas phase is that tolylene diisocyanate is prepared in 400 DEG C ~ 600 DEG C pyrolysis in temperature, and its shortcoming is at high temperature easy polymerization coking of isocyanic ester, makes productive rate extremely low, and amount of by-products is large.In world patent WO8805430, adopt sodium alkoxide as catalyzer, with methylcarbonate and the synthetic own diamino-methyl formate of hexanediamine, further HDI is prepared in pyrolysis again, this method yield is very low is only 9%, and sodium alkoxide forms homogeneous phase with solution and brings difficulty to separating, and pyrolysis temperature, 250 DEG C of left and right, easily makes side reaction increase; In US Patent No. 4547322, it is filler that Tomonari adopts the Raschig ring of aluminium or zinc, in the vertical reaction tubes of stainless steel, MDC is decomposed in pressurization, MDI yield is 89.2%wt, although tubular reactor can obviously improve reaction yield, but life-time service easily causes line clogging, is not easy to suitability for industrialized production; Japanese Patent JP2001-398911 openly adopt carbonic acid aminomethyl phenyl ester and the synthetic own diamino-methyl formate of hexanediamine, use again dibutyl tin laurate catalyse pyrolysis hexanediamine base methyl-formiate, preparation HDI, pyrolysis temperature is 250 DEG C, although aminolysis rate can reach 99.9%, total yield of products is 74%, and aminolysis rate and yield are greatly improved, but need to use the carbonic acid aminomethyl phenyl ester that price is higher is raw material, and product cost is higher; In Chinese patent CN101195590A, adopt ionic liquid as reaction solvent, with the supported catalyst of nickel oxide-zirconium white/aluminum oxide, pyrolysis under 10mmHg, obtains the yield 74% ~ 88% of HDI, but ionic liquid expensive and and the later stage be difficult to process, make to realize industrialization and hindered; In Chinese patent CN101011657A, adopt element bismuth simple substance, oxide compound, sulfide, halogenide as catalyzer, pyrolysis MDC at 260 DEG C, the yield of MDI can reach 82.8%, but adopt bismuth as catalyzer, in reaction process, easily make to live, catalyzer repeatability; In Chinese patent CN101492397A, the solution that is dissolved with HDC is passed into continuously and in scraped falling-film evaporator, forms falling liquid film, controlling vaporizer inner wall temperature is 220 ~ 245 DEG C, reaction pressure is between 0.2 ~ 0.6MPa, and the yield of HDI can reach 90%, but the method is to carry out on falling-film evaporator inwall, after low boiling point solvent evaporation, make the concentration of material raise, under hot conditions, easily coking is adsorbed on wall, and the reaction times is short, operational condition harshness.
More than invention all uses high boiling solvent, and dispersiveness and the heat-transfer effect of solvent are poor, large with product, catalyst separating difficulty, and the polymkeric substance producing in reaction is difficult to separate from solvent, makes the repeatability of solvent poor.
Summary of the invention
Technology of the present invention is dealt with problems: overcome the deficiencies in the prior art, provide one heterogeneous catalysis pyrolysis in liquid phase to prepare hexa-methylene-1, the method of 6-vulcabond, wherein hexa-methylene diamino manthanoate transformation efficiency and HDI product yield are high, and preparation method is simple to operate, production safety is reliable, environmentally safe, and recycling is strong.
Technical solution of the present invention: hexa-methylene 1 is prepared in one heterogeneous catalysis pyrolysis in liquid phase, the method of 6-vulcabond (HDI), described hexa-methylene diamino manthanoate carries out catalyse pyrolysis and prepares hexa-methylene-1 under pressurized conditions, 6-vulcabond, separate solvent by falling film evaporation and obtain straight product, specific implementation is: by hexa-methylene diamino manthanoate, low boiling point solvent, loaded solid catalyst adds in reactor, use the air in nitrogen replacement system, maintain pyrolysis hexa-methylene diamino manthanoate under 0.1 ~ 2.0MPa pressure, the concentration range of described hexa-methylene diamino manthanoate is 0.1 ~ 50wt%, the amount of loaded solid catalyst is 0.1 ~ 30% of hexa-methylene diamino manthanoate mass percent, loaded solid catalyst concentration is 0.2 ~ 10wt ‰, and temperature of reaction is at 200 ~ 250 DEG C, and the reaction times is at 0.5 ~ 4h, the alcohols producing in reaction process is followed nitrogen from overhead extraction, and the filtrate of generation is from extraction at the bottom of tower, after will filtrate filtering, separate through falling-film evaporator, respectively solvent and product being carried out to refrigerated separation, to obtain purity be more than 96% HDI product.
The preferred concentration range of described hexa-methylene diamino manthanoate is 1 ~ 20wt%.
Described hexa-methylene diamino manthanoate is hexa-methylene diamino-methyl formate, hexa-methylene diamino ethyl formate or hexa-methylene diamino butyl formate.
Described low boiling point solvent: refer to inert, be the solvent of boiling point lower than reaction raw materials, be selected from the one, two or three in nonane, chlorobenzene, orthodichlorobenzene, hexachloroethane, toluene, dimethylbenzene dipropylene glycol dme, tetraline, oil of mirbane, methyl-phenoxide.
In described loaded solid catalyst, the carrier of catalyzer is selected from silicon-dioxide, zirconium white, diatomite or molecular sieve, the active ingredient of catalyzer is selected from the one, two or three in zinc oxide, aluminum oxide, nickel oxide, tricobalt tetroxide, molybdenum oxide, titanium oxide, chromium sesquioxide, cerium oxide, cobalt oxide, stannic oxide, manganese oxide, weisspiessglanz, cobalt sesquioxide, and the loading of active ingredient is 5 ~ 40wt%.
Described nitrogen flow rate, purging amount is 50 ~ 2000ml/min.
Described falling-film evaporator Heating temperature is 130 ~ 170 DEG C, and vacuum tightness is 0.05 ~ 0.1Mpa, 60 ~ 120 DEG C of product cooling temperatures.
Described method is to realize by continuous method or mode intermittently.
In the present invention, adopt catalyzer to carry out the heterogeneous catalysis pyrolysis of hexa-methylene diamino manthanoate, hexa-methylene diamino manthanoate is after being dissolved in inert, after the certain temperature that is rapidly heated, keep for some time to carry out catalyse pyrolysis and prepare HDI, after question response finishes, can realize by filtration the separation of catalyzer, realize separating of product and solvent by falling film evaporation.The reaction process the present invention relates to is as follows;
The pyrolysis of hexa-methylene diamino manthanoate is the reversible reaction of a height, is having under catalyst-free condition and can react.First, the alkyl alcohol of hexa-methylene diamino manthanoate first pyrolysis one end under heating condition generates monoisocyanates, and this reactions steps is easy to realize; Then monoisocyanates carries out degree of depth pyrolysis and goes out the other end alkyl alcohol and produce HDI under heating condition.Wherein, a rear step degree of depth pyrolysis is the committed step of this reaction, and the amount of temperature of reaction and catalyzer need to controlled well is controlled the generation of side reaction and improved pyrolysis rate.The simultaneously existence meeting of alkyl alcohol react with monoisocyanates, HDI and is generated carbamate to reacting unfavorable, thereby the alkyl alcohol that removes in time pyrolysis generation is conducive to improve yield.
Feature of the present invention is reaction conditions gentleness, and catalyzer is easy to and solution separating, do not run off and recycling strong, the easy separating-purifying of solvent and product.
The inventive method is compared tool with prior art with patent and is had the following advantages:
(1) low boiling point solvent that the present invention adopts is cheap and easy to get, and easy and product separation, compares with ionic liquid solution with high boiling solvent, more easily purifies, reuses and aftertreatment, environmentally friendly.
(2) catalyst activity that adopts in the present invention is high, selectivity good, side reaction is had to restraining effect, be not dissolved in solution and cause loss, and catalyzer to reuse the life-span long.
(3) the present invention carries out under pressurization and catalyzer condition, and the reaction times is short, and the conversion of hexa-methylene diamino manthanoate reaches more than 96%, and HDI yield can reach more than 88%.
(4) method and technology in the present invention is simple to operate, to equipment require lowly, be easy to automatization and industrialization.
Embodiment
Introduce in detail the present invention below in conjunction with specific embodiment.But following embodiment only limits to explain the present invention, and protection scope of the present invention should comprise the full content of claim, is not limited only to the present embodiment.
Embodiment 1
Get 600g toluene and put into the reactor of 1L, add 16g hexa-methylene diamino-methyl formate, 0.5g manganese oxide/molecular sieve (loading is 10wt%), liquid agitation is even, use the air in nitrogen replacement system, temperature is elevated to rapidly to 220 DEG C, keep system pressure 0.8MPa, nitrogen purging amount is 200ml/min, pyrolysis 2h.After reaction finishes, reacting liquid filtering is carried out to falling liquid film separation again, film evaporator Heating temperature is 130 DEG C, and vacuum tightness is 0.05Mpa, and 80 DEG C of product cooling temperatures are collected product and carried out through gas chromatographic analysis, are converted into 96.1%, and yield is 88.6%, and purity is 96%.
Embodiment 2
Get 600 chlorobenzenes and put into 1L reactor, add 20g hexa-methylene diamino ethyl formate, 0.7g manganese oxide/molecular sieve (loading is 10wt%), stirred liq is even, use the air in nitrogen replacement system, temperature is elevated to rapidly to 230 DEG C, keep pressure 1.0MPa, nitrogen flow 300ml/min, pyrolysis 4h, after reaction finishes, reacting liquid filtering is carried out to falling liquid film separation again, film evaporator Heating temperature is 130 DEG C, vacuum tightness is 0.08Mpa, 110 DEG C of product cooling temperatures, collecting product carries out through gas chromatographic analysis, transformation efficiency is 100%, yield is 90%, purity 98%.
Embodiment 3
Get 500g orthodichlorobenzene and put into 1L reactor, add 20g hexa-methylene diamino ethyl formate, 1.0g cobalt oxide/zirconium white (loading is 20wt%), stirred solution is even, use the air in nitrogen replacement system, temperature is elevated to rapidly to 240 DEG C, keep pressure 1.2MPa, nitrogen flow 350ml/min, pyrolysis 2.5h, after reaction finishes, reacting liquid filtering is carried out to falling liquid film separation again, film evaporator Heating temperature is 170 DEG C, vacuum tightness is 0.1Mpa, 120 DEG C of product cooling temperatures, collecting product carries out through gas chromatographic analysis, transformation efficiency is 99.2%, yield is 90%, purity is 98.2%.
Embodiment 4
Get 300g tetraline and 300g chlorobenzene is put into 1L reactor, add 30g hexa-methylene diamino-methyl formate, (stannic oxide loading is 10wt% to 1.5g stannic oxide-bismuth oxide/aluminium sesquioxide, bismuth oxide loading is 6wt%), stirred solution is even, use the air in nitrogen replacement system, temperature is elevated to rapidly to 230 DEG C, keep pressure 1.1MPa, nitrogen flow 150ml/min, pyrolysis 2h, after reaction finishes, reacting liquid filtering is carried out to falling liquid film separation again, film evaporator Heating temperature is 150 DEG C, vacuum tightness is 0.09Mpa, 60 DEG C of product cooling temperatures, collecting product carries out through gas chromatographic analysis, transformation efficiency is 98%, yield is 89.5%, purity is 96.3%.
Embodiment 5
Get 200g nonane and 400g hexachloroethane is put into 1L reactor, add 50g hexa-methylene diamino butyl formate, (chromic oxide loading is 8wt% to 2g chromic oxide-tricobalt tetroxide-stannic oxide/aluminium sesquioxide, tricobalt tetroxide loading is 5wt%, stannic oxide loading is 6wt%), stirred solution is even, use the air in nitrogen replacement system, temperature is elevated to rapidly to 210 DEG C, keep pressure 0.8MPa, nitrogen flow 300ml/min, pyrolysis 2.5h, after reaction finishes, reacting liquid filtering is carried out to falling liquid film separation again, film evaporator Heating temperature is 140 DEG C, vacuum tightness is 0.05Mpa, 60 DEG C of product cooling temperatures, collecting product carries out through gas chromatographic analysis, transformation efficiency is 96.4%, yield is 88%, purity is 96.6%.
Example 6
By 200g chlorobenzene, 200g toluene and 200g orthodichlorobenzene are put into 1L reactor, add 100g hexa-methylene diamino butyl formate, (chromium sesquioxide loading is 10wt% to 6g chromium sesquioxide-cobalt oxide/aluminium sesquioxide, cobalt oxide loading is 8wt%), stirred solution is even, use the air in nitrogen replacement system, temperature is elevated to rapidly to 230 DEG C, keep pressure 0.9MPa, nitrogen flow 500ml/min, pyrolysis 3h, after reaction finishes, reacting liquid filtering is carried out to falling liquid film separation again, film evaporator Heating temperature is 160 DEG C, vacuum tightness is 0.09Mpa, 90 DEG C of product cooling temperatures, collecting product carries out through gas chromatographic analysis, transformation efficiency is 99%, yield is 89%, purity 97.7%.
Embodiment 7
Example 2 is reacted to thermal barrier and the catalyzer of rear recovery and put into 1L reactor, add 20g hexa-methylene diamino ethyl formate, stirred solution is even, use the air in nitrogen replacement system, temperature is elevated to rapidly to 230 DEG C, keep pressure 1.0MPa, nitrogen flow 300ml/min, pyrolysis 2.h, coldly go rear sampling after gas chromatographic analysis reaction finishes, reacting liquid filtering is carried out to falling liquid film separation again, film evaporator Heating temperature is 140 DEG C, vacuum tightness is 0.03Mpa, 70 DEG C of product cooling temperatures, collecting product carries out through gas chromatographic analysis, transformation efficiency is 97%, yield is 88.6%, purity 96.8%.
Embodiment 8
The tetraline that 500g is circulated throughout to 5 times adds in 1L reactor, add 40g hexa-methylene diamino-methyl formate, (cerium oxide loading is 15wt% to 2g cerium oxide-cobalt sesquioxide/molecular sieve, cobalt sesquioxide loading is 5wt%), stirred solution is even, use the air in nitrogen replacement system, temperature is elevated to rapidly to 230 DEG C, keep pressure 1.1MPa, nitrogen flow 200ml/min, pyrolysis 2h, after reaction finishes, reacting liquid filtering is carried out to falling liquid film separation again, film evaporator Heating temperature is 170 DEG C, vacuum tightness is 0.09Mpa, 80 DEG C of product cooling temperatures, collecting product carries out through gas chromatographic analysis, transformation efficiency is 97%, yield is 88.3%, purity is 98%.
Embodiment 9
Get 600g chlorobenzene and put into 1L reactor, add 50g hexa-methylene diamino-methyl formate, add 2g to be circulated throughout the catalyzer of 10 times through example 3, stirred solution is even, use the air in nitrogen replacement system, temperature is elevated to rapidly to 230 DEG C, keep pressure 1.2MPa, nitrogen flow 350ml/min, pyrolysis 2.0h, after reaction finishes, film evaporator Heating temperature is 150 DEG C, vacuum tightness is 0.09Mpa, 60 DEG C of product cooling temperatures, collecting product carries out through gas chromatographic analysis, collecting product carries out through gas chromatographic analysis, transformation efficiency is 97.3%, yield is 89%, purity is 97%.
Embodiment 10
Get example 9 and put into 1L reactor through the solvent 600g of 10 circulations, add 50g hexa-methylene diamino butyl formate, add 2g to be circulated throughout the catalyzer of 10 times through example 5, stirred solution is even, use the air in nitrogen replacement system, temperature is elevated to rapidly to 220 DEG C, keep pressure 1.1MPa, nitrogen flow 300ml/min, pyrolysis 2.5h, after reaction finishes, film evaporator Heating temperature is 150 DEG C, vacuum tightness is 0.07Mpa, 80 DEG C of product cooling temperatures, collecting product carries out through gas chromatographic analysis, collecting product carries out through gas chromatographic analysis, transformation efficiency is 97%, yield is 89.3%, purity is 97.4%.
In a word, in the present invention, hexa-methylene diamino manthanoate transformation efficiency is more than 96%, and product yield can reach more than 88%, and simple to operate, production safety is reliable, environmentally safe, and catalyzer, solvent and product is easy separates, recycling is strong.
It should be noted that, according to the various embodiments described above of the present invention, those skilled in the art are the four corners that can realize independent claim of the present invention and appurtenance completely, implementation procedure and method same the various embodiments described above; And non-elaborated part of the present invention belongs to techniques well known.
The above; be only part embodiment of the present invention, but protection scope of the present invention is not limited to this, in the technical scope that any those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.
Claims (4)
- One kind in liquid phase heterogeneous catalysis pyrolysis prepare hexa-methylene 1, the method of 6-vulcabond (HDI), it is characterized in that: described hexa-methylene diamino manthanoate carries out catalyse pyrolysis and prepares hexa-methylene-1 under pressurized conditions, 6-vulcabond, separate solvent by falling film evaporation and obtain straight product, specific implementation is: hexa-methylene diamino manthanoate, low boiling point solvent, loaded solid catalyst are added in reactor, use the air in nitrogen replacement system, maintain pyrolysis hexa-methylene diamino manthanoate under 0.1～2.0MPa pressure; The concentration range of described hexa-methylene diamino manthanoate is 0.1～40wt%, loaded solid catalyst concentration is 0.1～10wt ‰, the amount of loaded solid catalyst is 0.1～30% of hexa-methylene diamino manthanoate mass percent, temperature of reaction is at 200～250 DEG C, and the reaction times is at 0.5～4h; The alcohols producing in reaction process is followed nitrogen from overhead extraction, and the filtrate of generation is from extraction at the bottom of tower; After filtrate is filtered, separate through falling-film evaporator, it is more than 96% HDI product that product is carried out to the cooling purity that obtains;Described hexa-methylene diamino manthanoate is hexa-methylene diamino-methyl formate, hexa-methylene diamino ethyl formate or hexa-methylene diamino butyl formate;Described low boiling point solvent is selected from the one, two or three in nonane, chlorobenzene, orthodichlorobenzene, hexachloroethane, toluene, dimethylbenzene dipropylene glycol dme, tetraline, oil of mirbane, methyl-phenoxide;In described loaded solid catalyst, the carrier of catalyzer is selected from silicon-dioxide, zirconium white, diatomite or molecular sieve, the active ingredient of catalyzer is selected from the one, two or three in zinc oxide, aluminum oxide, nickel oxide, tricobalt tetroxide, molybdenum oxide, titanium oxide, chromium sesquioxide, cerium oxide, cobalt oxide, stannic oxide, manganese oxide, weisspiessglanz, cobalt sesquioxide, and the loading of active ingredient is 5～40wt%.
- According to claim 1 in liquid phase heterogeneous catalysis pyrolysis prepare hexa-methylene 1, the method for 6-vulcabond (HDI), is characterized in that: the concentration range of described hexa-methylene diamino manthanoate is 1～40wt%.
- According to claim 1 in liquid phase heterogeneous catalysis pyrolysis prepare hexa-methylene 1, the method for 6-vulcabond (HDI), is characterized in that: described nitrogen flow rate, purging amount is 50～2000ml/min.
- According to claim 1 in liquid phase heterogeneous catalysis pyrolysis prepare hexa-methylene 1, the method of 6-vulcabond (HDI), it is characterized in that: the Heating temperature of described falling-film evaporator is 130～170 DEG C, vacuum tightness is 0.05～0.1Mpa, 60～120 DEG C of product cooling temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210448301.1A CN102964272B (en) | 2012-11-09 | 2012-11-09 | Method for preparing hexamethylene-1,6-diisocyanate (HDI) by heterocatalytic pyrolysis in liquid phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210448301.1A CN102964272B (en) | 2012-11-09 | 2012-11-09 | Method for preparing hexamethylene-1,6-diisocyanate (HDI) by heterocatalytic pyrolysis in liquid phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102964272A CN102964272A (en) | 2013-03-13 |
| CN102964272B true CN102964272B (en) | 2014-06-04 |
Family
ID=47794740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210448301.1A Active CN102964272B (en) | 2012-11-09 | 2012-11-09 | Method for preparing hexamethylene-1,6-diisocyanate (HDI) by heterocatalytic pyrolysis in liquid phase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102964272B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108339566B (en) * | 2017-01-22 | 2021-04-30 | 中国科学院过程工程研究所 | Metal supported catalyst and preparation method and application thereof |
| CN107488132A (en) * | 2017-09-25 | 2017-12-19 | 陕西煤业化工技术开发中心有限责任公司 | A kind of method that heterogeneous catalysis pyrolysis prepares toluene di-isocyanate(TDI) |
| CN110721744B (en) * | 2019-09-19 | 2022-02-22 | 江苏国立化工科技有限公司 | Solid acid catalyst with high reaction activity and preparation method and application thereof |
| CN113831264B (en) * | 2021-09-16 | 2023-03-31 | 中国科学院过程工程研究所 | Method for preparing 1, 6-hexamethylene dicarbamate |
| 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 |
| CN115010627B (en) * | 2022-07-05 | 2023-07-25 | 中国科学院过程工程研究所 | Catalytic synthesis method of glutarimide |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10209095A1 (en) * | 2002-03-01 | 2003-09-11 | Basf Ag | Process for the preparation of isocyanates |
| DE10260027A1 (en) * | 2002-12-19 | 2004-07-08 | Basf Ag | Process for the separation and purification of solvents from a reaction mixture from an isocyanate synthesis |
| DE102006057118A1 (en) * | 2006-12-04 | 2008-06-05 | Wacker Chemie Ag | Cleavage of carbamato-organosilane to isocyanato-organosilane for use e.g. in prepolymer production for coating material, involves heating the liquid with a catalyst in an evaporator and evaporating the product |
| CN101195590A (en) * | 2006-12-09 | 2008-06-11 | 中国科学院兰州化学物理研究所 | Method for producing 1,6-hexamethylene diisocyanate with hexa-methylene diamino-methyl formate liquid phase thermal cracking |
| CN101011657A (en) * | 2007-01-25 | 2007-08-08 | 中国科学院成都有机化学有限公司 | Catalyst for preparing isocyanate by thermal decomposition of aryl (alkyl) carbamic acid ester and use thereof |
| 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 |
| CN101870666B (en) * | 2010-05-23 | 2013-04-10 | 青岛科技大学 | Refining and reclaiming technology of tail gas absorption solvent in production of toluene diisocyanate |
| CN102653517A (en) * | 2011-03-02 | 2012-09-05 | 中国科学院过程工程研究所 | Method for preparing isocyanate from carbamate |
-
2012
- 2012-11-09 CN CN201210448301.1A patent/CN102964272B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102964272A (en) | 2013-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102964272B (en) | Method for preparing hexamethylene-1,6-diisocyanate (HDI) by heterocatalytic pyrolysis in liquid phase | |
| EP4206186A1 (en) | Preparation method for 1,5-pentane diisocyanate | |
| CN103936623B (en) | Process for preparing toluene diisocyanate (TDI) by using toluenediamine and dimethyl carbonate | |
| CN103896811A (en) | Method for preparing 1,6-hexamethylene diurethane through heterogeneous catalysis | |
| CN103922931B (en) | A kind of method of a step catalytically synthesizing glycol ether acetate | |
| CN102653517A (en) | Method for preparing isocyanate from carbamate | |
| CN103804236A (en) | Equipment and method for preparing isocyanate through compression pyrolysis | |
| CN1683326A (en) | Process for producing methyl carbamate | |
| CN102260193B (en) | Method and reaction device for preparing isocyanate through thermal decomposition of carbamate by molecular distillation technology | |
| CN103044491A (en) | Dimethyl carbonate synthesis method by using methanol and carbon dioxide | |
| CN105294541B (en) | The synthetic method of 2,2,6,6 tetramethyl piperidines | |
| CN103086959A (en) | Novel process for producing 3,5,6-sodium trichloropyrindinol | |
| CN103772240B (en) | Method for preparation of methylene diphenyl diisocyanate (MDI) | |
| CN101130508B (en) | Process for synthesizing phenyl urethane in atmospheric condition | |
| CN103694141A (en) | A method of synthesizing phenylcarbamate | |
| CN100415712C (en) | Process for producing methyl carbamate by low pressure solvation homogeneous phase reaction | |
| CN111393402B (en) | N & lt/EN & gt acid/quaternary ammonium salt composite catalytic CO 2 Method for preparing cyclic carbonate by cycloaddition with epoxide | |
| CN111620812B (en) | Synthetic method of 2, 3-dichloropyridine | |
| CN102464588A (en) | Synthesis method of di-n-butyl carbonate | |
| CN102731351B (en) | Preparation method for 1-methyl-5-[3-methyl-4-(4-trifluoromethylthio-phenoxy)-phenyl]-biuret, and application thereof | |
| CN117181254B (en) | Preparation method of bismuth-based catalyst, bismuth-based catalyst and application | |
| CN105418358A (en) | Method for preparing o-chlorotoluene | |
| CN105126804B (en) | A kind of catalyst for synthesizing 1,6 hexa-methylene diamino-methyl formates and preparation method and application | |
| CN101530785B (en) | Composite catalyst for preparing isocyanate by pyrolyzing aminoalkyl esters | |
| CN101665411B (en) | Alcohol-lead compound, preparation method thereof and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |