CN103896811A - Method for preparing 1,6-hexamethylene diurethane through heterogeneous catalysis - Google Patents
Method for preparing 1,6-hexamethylene diurethane through heterogeneous catalysis Download PDFInfo
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Abstract
The invention relates to a method for preparing 1,6-hexamethylene diurethane through heterogeneous catalysis. The method comprises the steps: with alkyl carbamate and hexamethylenediamine as reactants, by selecting a metal oxide catalyst, and adopting a two-section temperature-varying reaction process, reacting to synthesize the 1,6-hexamethylene diurethane, continuously introducing an inert gas in a reaction process; transferring a byproduct ammonia gas; and after the reaction is ended, filtering when heating to remove the catalyst, wherein the obtained liquid is a white solid hexamethyl carbamate through reduced pressure distillation. The method is mild in reaction conditions, free from pollution, simple and convenient in operation process, and small in potential safety hazards; and the used catalyst is easily separated, and can be repeatedly used, and is better in industrialized application prospect.
Description
Technical field
The invention belongs to a kind of heterogeneous catalysis and prepare the method for hexa-methylene diamino-methyl formate, be particularly related to a kind of with hexanediamine and alkyl formate ester as raw material under metal oxide catalyst effect, adopt the method for two sections of alternating temperature reaction process synthesizing hexamethylene diamino-methyl formates.
Background technology
Isocyanic ester is a kind of important organic intermediate, is widely used in the production of elastomerics, coating, plastics, agricultural chemicals and leather etc.Wherein, hexamethylene diisocyanate (HDI) is to apply wider aliphatic isocyanates, its derivative has not flavescence, anti-efflorescence, the advantage such as wear-resisting, in aspect extensive application such as the binding agents of carplane OEM coating, retouching paint, high-grade wood furniture paint, anticorrosive coating and good light stability.
At present, HDI mainly adopts phosgenation to produce.The method is used hypertoxic phosgene to make raw material, the hydrochloric acid that by-product is a large amount of, and production equipment complexity, high to equipment requirements, process flow is many, and equipment corrosion, phosgene leakage accident very easily occur, serious environment pollution, threat personnel safety.Along with the raising of people's environmental protection consciousness, the green clean synthetic route of various non-phosgenes becomes the focus of research.Wherein, carbamate pyrolysis method is the most promising method.While adopting this method to produce HDI, mainly comprise synthetic and pyrolysis two steps of intermediate hexa-methylene diamino-methyl formate (HDC).
Synthetic about HDC, reporting at present more is hexanediamine (HDA) and methylcarbonate (DMC) aminolysis reaction method, the key of technology is the research of catalyzer.In US5789614 and EP0570070, all adopt sodium methylate to make catalyzer, the method HDA transformation efficiency is high, but side reaction is serious, and target product productive rate is very low.CN1727330A adopts Pb compound, reaction conditions gentleness, and yield and selectivity can reach more than 98%.Although homogeneous catalyst good catalytic activity, its easy inactivation, separates and reclaims difficulty, has limited its use.In order to overcome its drawback, the people such as Lu Ling have studied respectively loading type MgO, ZrO
2/ SiO
2deng the catalytic effect of heterogeneous catalyst, but its yield is lower, there is no industrial application value.In CN02158320, studied solvent and catalyzer that ionic liquid reacts with DMC as amine, shown multiple outstanding performance, HDC yield is more than 98%, but ionic liquid synthesizes difficulty, price is higher, has limited its application.
With small molecules alkyl carbamate such as Urethylane (MC), urethanum (EC) etc. and amine reaction synthesis of carbamates is the synthetic route that another kind has future.EP0018588, WO9717323 have announced a kind of method of being prepared aliphatic carbamate by reactions such as small molecules alkyl carbamate and hexahydroaniline, hexanediamines, but its temperature of reaction is high, and side reaction is serious, and yield is lower.CN101928238A has announced a kind of method that adopts small molecules alkyl carbamate and hexanediamine reaction to prepare HDC, and it adopts the Lewis acid catalysts such as homogeneous phase Yttrium trinitrate, lanthanum nitrate, and difficult separation and recycling, has limited it and further used.Meanwhile, belonging to urea alcoholysis reaction in this reacting quintessence, comprise generation and alcoholysis two steps thereof of oneself two ureas, is a succession of reaction.Wherein, alcoholysis reaction needs temperature higher, between 170-210 ° of C, therefore the higher temperature of whole reaction needed just can reach reasonable effect.But hexanediamine has greater activity, at high temperature easy and alkyl carbamate is produced polyureas, has reduced the selectivity of reaction.Therefore, need to develop novel process reduce by product generation, improve object selectivity of product.
Summary of the invention
The technology of the present invention is dealt with problems: overcome the deficiencies in the prior art, a kind of heterogeneous metal oxide catalyst catalytic amino alkyl formate and the hexanediamine method through the synthetic own diamino-methyl formate of two sections of alternating temperature reaction process is provided, adopt the method reaction conditions gentleness, pollution-free, operating process is easy, and potential safety hazard is little, and catalyzer used is easy to separate, can be repeatedly used, there is good prospects for commercial application.
The present invention is achieved by the following technical solutions:
(1) catalyzer preparation
1. direct roasting method: metal-salt is placed in to retort furnace roasting 2-10h under 200-1000 ° of C air atmosphere, and porphyrize calcining matter, obtains corresponding metal oxide.
2. the precipitator method: metal-salt is dissolved in appropriate amount of deionized water or ethanol, uses Na
2cO
3or ammoniacal liquor slowly adds in solution, aging 2-10h, filters, washing, and gained solid is placed in retort furnace roasting 2-10h under 200-1000 ° of C air atmosphere after drying, and porphyrize calcining matter, obtains corresponding metal oxide.
(2) reaction process
Appropriate alkyl carbamate, hexanediamine, solvent and oxide catalyst are added in the autoclave with condenser, adopt two sections of alternating temperature reaction process to react, in reaction process, constantly pass into rare gas element, shift out byproduct of reaction ammonia.After reaction finishes, filtered while hot is removed catalyzer, and gained liquid obtain the own diamino-methyl formate of white solid after underpressure distillation.Filter gained catalyzer after washing, can repeatedly reuse.
Described alkyl carbamate comprises the alkyl esters such as Urethylane, urethanum, carboxylamine propyl ester, butyl carbamate.
Described metal oxide comprises: CeO
2, TiO
2, MoO
3, ZrO
2, ZnO, Bi
2o
3, Fe
2o
3, La
2o
3, SnO
2, Y
2o
3deng, can be one, two or more oxide compounds wherein.
Described reaction solvent comprises methyl alcohol, ethanol, propyl alcohol, propyl carbinol, chlorobenzene, toluene, dichlorobenzene etc., can be single solvent, can be also two or more mixed solvents.
The mol ratio of described small molecules alkyl carbamate and hexanediamine is 2:1-15:1.
The mol ratio of described solvent and hexanediamine is 5:1-50:1, preferably 10:1-30:1.
The mass ratio of described catalyzer and hexanediamine is 0.5%-20%, preferably 5%-15%.
Two sections of described alternating temperature reaction process specifically comprise: 100-150 ° of C of (one) first paragraph temperature of reaction, reaction times 2-10h; (2) second segment temperature of reaction 170-210 ° C, reaction times 4-8h.
Described rare gas element is to have the gas reacting in not impact system under temperature of reaction condition, comprises nitrogen, helium, argon gas.
The present invention's advantage is compared with prior art:
(1) the present invention adopts alkyl carbamate to replace phosgene, reaction conditions gentleness, and pollution-free, operating process is easy, and potential safety hazard is little.
(2) catalyzer that the present invention uses is heterogeneous catalyst, is easy to reclaim, and has good industrial prospect.
(3) the catalyzer wide material sources that the present invention adopts, preparation is simple, only needs corresponding metal-salt or basic salt to precipitate roasting under alkaline condition.
(4) two sections of alternating temperature reaction process that the present invention adopts, by reducing the generation temperature of oneself two ureas, can significantly reduce the generation of by product polyureas, improve object selectivity of product, and own diamino-methyl formate yield is more than 90%, and hexanediamine transformation efficiency is 100%.
Embodiment
In order to further illustrate details of the present invention, below for some embodiment, but should not be so limited.
Embodiment 1
Get appropriate cerous nitrate in crucible, dry 4h in 110 ° of C baking ovens, and then in retort furnace in 600 ° of C roasting 4h.By calcining matter porphyrize, obtain solid CeO
2catalyzer.Appropriate hexanediamine, Urethylane, methyl alcohol (mol ratio is 1:2:5) are added in the autoclave with prolong, add the CeO of mass ratio 0.5% simultaneously
2, be warming up to 150 ° of C reaction 2h, and then be warming up to 210 ° of C reaction 4h.In reaction process, constantly pass into nitrogen, produce by product ammonia and be constantly discharged from.After reaction finishes, filtered while hot is removed catalyzer, and the underpressure distillation under 60 ° of C, 1KPa condition of gained liquid obtains the own diamino-methyl formate of white solid.Filter gained catalyzer after washing, can repeatedly reuse.
Reaction result: hexanediamine transformation efficiency is 100%, own diamino-methyl formate yield is 96.9%.
Embodiment 2
Get appropriate zirconium nitrate and be dissolved in 100ml deionized water, use 1mol/L Na
2cO
3slowly add in solution, aging 10h, filters, washing, and gained solid is placed in retort furnace roasting 10h under 200 ° of C air atmospheres after drying, and porphyrize calcining matter, obtains ZrO
2oxide compound.Appropriate hexanediamine, Urethylane, methyl alcohol and chlorobenzene mixed solvent (mol ratio is 1:5:10) are added in the autoclave with prolong, add the ZrO of mass ratio 5% simultaneously
2, be warming up to 100 ° of C reaction 10h, and then be warming up to 170 ° of C reaction 8h.In reaction process, constantly pass into helium, produce by product ammonia and be constantly discharged from.After reaction finishes, filtered while hot is removed catalyzer, and the underpressure distillation under 130 ° of C, 15KPa condition of gained liquid obtains the own diamino-methyl formate of white solid.Filter gained catalyzer after washing, can repeatedly reuse.
Reaction result: hexanediamine transformation efficiency is 100%, own diamino-methyl formate yield is 90.9%.
Embodiment 3
Get appropriate nitric acid molybdenum in crucible, dry 4h in 110 ° of C baking ovens, and then in retort furnace in 1000 ° of C roasting 2h.By calcining matter porphyrize, obtain solid MoO
3catalyzer.Appropriate hexanediamine, urethanum, ethanol and toluene Mixed Solvent (mol ratio is 1:7:15) are added in the autoclave with prolong, add the MoO of mass ratio 10% simultaneously
3, be warming up to 140 ° of C reaction 3h, and then be warming up to 200 ° of C reaction 5h.In reaction process, constantly pass into argon gas, produce by product ammonia and be constantly discharged from.After reaction finishes, filtered while hot is removed catalyzer, and the underpressure distillation under 150 ° of C, 30KPa condition of gained liquid obtains the own diamino-methyl formate of white solid.Filter gained catalyzer after washing, can repeatedly reuse.
Reaction result: hexanediamine transformation efficiency is 100%, own diamino-methyl formate yield is 92.9%.
Embodiment 4
Get appropriate zirconium nitrate, cerous nitrate is dissolved in 100ml deionized water, slowly adds in solution aging 10h with 1mol/L ammoniacal liquor, filter, washing, gained solid is placed in retort furnace roasting 6h under 800 ° of C air atmospheres after drying, porphyrize calcining matter, obtains ZrO-CeO
2composite catalyst.Appropriate hexanediamine, Urethylane, methyl alcohol (mol ratio is 1:10:20) are added in the autoclave with prolong, add the ZrO-CeO of mass ratio 15% simultaneously
2composite catalyst, is warming up to 130 ° of C reaction 5h, and then is warming up to 190 ° of C reaction 6h.In reaction process, constantly pass into nitrogen, produce by product ammonia and be constantly discharged from.After reaction finishes, filtered while hot is removed catalyzer, and the underpressure distillation under 90 ° of C, 5KPa condition of gained liquid obtains the own diamino-methyl formate of white solid.Filter gained catalyzer after washing, can repeatedly reuse.
Reaction result: hexanediamine transformation efficiency is 100%, own diamino-methyl formate yield is 91.1%.
Embodiment 5
Get appropriate tetrabutyl titanate and be dissolved in 100ml ethanol, slowly add in solution with 1mol/L ammoniacal liquor, aging 10h, filters, washing, and gained solid is placed in retort furnace roasting 7h under 600 ° of C air atmospheres after drying, and porphyrize calcining matter, obtains TiO
2catalyzer.Appropriate hexanediamine, butyl carbamate, propyl carbinol (mol ratio is 1:15:25) are added in the autoclave with prolong, add the TiO of mass ratio 20% simultaneously
2, be warming up to 110 ° of C reaction 8h, and then be warming up to 180 ° of C reaction 7h.In reaction process, constantly pass into argon gas, produce by product ammonia and be constantly discharged from.After reaction finishes, filtered while hot is removed catalyzer, and the underpressure distillation under 130 ° of C, 15KPa condition of gained liquid obtains the own diamino-methyl formate of white solid.Filter gained catalyzer after washing, can repeatedly reuse.
Reaction result: hexanediamine transformation efficiency is 100%, own diamino-methyl formate yield is 90.5%.
Embodiment 6
Get appropriate zinc nitrate, Bismuth trinitrate, lanthanum nitrate and be dissolved in 100ml deionized water, slowly add in solution aging 10h with 1mol/L ammoniacal liquor, filter, washing, gained solid is placed in retort furnace roasting 6h under 700 ° of C air atmospheres after drying, porphyrize calcining matter, obtains ZnO-Bi
2o
3-La
2o
3composite catalyst.Appropriate hexanediamine, butyl carbamate, propyl carbinol and dichlorobenzene mixed solvent (mol ratio is 1:15:30) are added in the autoclave with prolong, add the ZnO-Bi of mass ratio 7.5% simultaneously
2o
3-La
2o
3, be warming up to 120 ° of C reaction 7h, and then be warming up to 180 ° of C reaction 7h.In reaction process, constantly pass into helium, produce by product ammonia and be constantly discharged from.After reaction finishes, filtered while hot is removed catalyzer, and the underpressure distillation under 120 ° of C, 12KPa condition of gained liquid obtains the own diamino-methyl formate of white solid.Filter gained catalyzer after washing, can repeatedly reuse.
Reaction result: hexanediamine transformation efficiency is 100%, own diamino-methyl formate yield is 94.9%.
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 (8)
1. a method for hexa-methylene diamino-methyl formate is prepared in heterogeneous catalysis, it is characterized in that reaction process is:
A, reactant alkyl carbamate, hexanediamine, metal oxide catalyst and solvent are added in autoclave according to certain mol ratio; The mol ratio of described alkyl carbamate and hexanediamine is 2:1-15:1; The mol ratio of described solvent and hexanediamine is 5:1-50:1; The mass ratio of described metal oxide catalyst and hexanediamine is 0.5%-20%;
B, two sections of alternating temperature reaction process of employing catalyze and synthesize own diamino-methyl formate, detailed process is for being first heated to autoclave first paragraph thermotonus for some time, then autoclave is warming up to second segment temperature and continues reaction for some time, reaction finishes rear cooling and obtains reaction mixture; In reaction process continue stir not open close enter rare gas element, shift out by product ammonia; In described two sections of alternating temperature reaction process, first paragraph temperature of reaction is 100-150 ° of C, reaction times 2-10h; 170-210 ° of C of second segment temperature of reaction, reaction times 4-8h;
After c, reaction finish, filtered while hot reaction solution is removed catalyzer, and gained liquid obtain the own diamino-methyl formate of white solid after underpressure distillation; Catalyzer recycles after washing.
2. method according to claim 1, is characterized in that: described reactant alkyl carbamate is selected from Urethylane, urethanum, carboxylamine propyl ester or butyl carbamate.
3. method according to claim 1, is characterized in that: described metal oxide catalyst is CeO
2, TiO
2, MoO
3, ZrO
2, ZnO, Bi
2o
3, Fe
3o
4, La
2o
3, SnO
2, Y
2o
3one in oxide compound, two or more combinations.
4. method according to claim 1, is characterized in that: described reaction solvent comprises methyl alcohol, ethanol, propyl alcohol, propyl carbinol, chlorobenzene, toluene or dichlorobenzene, can be single solvent, can be also two or more mixed solvents.
5. method according to claim 1, is characterized in that: the mol ratio of described solvent and hexanediamine is 10:1-30:1.
6. method according to claim 1, is characterized in that: the mass ratio of described catalyzer and hexanediamine is 5%-15%.
7. method according to claim 1, is characterized in that: described underpressure distillation separation temperature is 60-150 ° of C, and pressure is 1-30KPa.
8. method according to claim 1, is characterized in that: described rare gas element is to have the gas reacting in not impact system under temperature of reaction condition, comprises nitrogen, helium or argon gas.
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| CN108608543A (en) * | 2018-04-24 | 2018-10-02 | 阜南县宇翔工艺品有限公司 | A kind of wicker products novel mildew resistant method |
| CN112574067A (en) * | 2021-02-24 | 2021-03-30 | 富海(东营)新材料科技有限公司 | Method for preparing high-purity m-xylylene diisocyanate without phosgene |
| CN113603613A (en) * | 2021-04-14 | 2021-11-05 | 中国科学院过程工程研究所 | Catalytic synthesis method of pentanedicarbamic acid ester |
| CN113731398A (en) * | 2020-05-27 | 2021-12-03 | 中国科学院过程工程研究所 | Catalyst for preparing dicarbamate and application thereof |
| CN113831264A (en) * | 2021-09-16 | 2021-12-24 | 中国科学院过程工程研究所 | Method for preparing 1, 6-hexamethylene dicarbamate |
| CN114989044A (en) * | 2022-07-21 | 2022-09-02 | 中国科学院过程工程研究所 | Catalytic synthesis method of dicarbamate |
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| CN108608543A (en) * | 2018-04-24 | 2018-10-02 | 阜南县宇翔工艺品有限公司 | A kind of wicker products novel mildew resistant method |
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| CN112574067A (en) * | 2021-02-24 | 2021-03-30 | 富海(东营)新材料科技有限公司 | Method for preparing high-purity m-xylylene diisocyanate without phosgene |
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| CN115232028A (en) * | 2022-06-24 | 2022-10-25 | 河北工业大学 | Method for synthesizing 1, 6-hexamethylene dicarbamate by using biomass-based furan derivative as raw material |
| CN115232028B (en) * | 2022-06-24 | 2024-01-02 | 河北工业大学 | Method for synthesizing 1, 6-hexamethylene dicarbamate by taking biomass-based furan derivative as raw material |
| CN114989044A (en) * | 2022-07-21 | 2022-09-02 | 中国科学院过程工程研究所 | Catalytic synthesis method of dicarbamate |
| CN117181254A (en) * | 2022-08-30 | 2023-12-08 | 海南华盛水泥投资有限公司 | Preparation method of bismuth-based catalyst, bismuth-based catalyst and application |
| CN117181254B (en) * | 2022-08-30 | 2024-04-12 | 海南华盛水泥投资有限公司 | Preparation method of bismuth-based catalyst, bismuth-based catalyst and application |
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