CN102382294B - Preparation method for series products of polyether amine - Google Patents
Preparation method for series products of polyether amine Download PDFInfo
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- CN102382294B CN102382294B CN2011102593968A CN201110259396A CN102382294B CN 102382294 B CN102382294 B CN 102382294B CN 2011102593968 A CN2011102593968 A CN 2011102593968A CN 201110259396 A CN201110259396 A CN 201110259396A CN 102382294 B CN102382294 B CN 102382294B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a preparation method for series products of polyether amine, which belongs to the technical field of organic chemical industry. Polypropylene glycol, catalyst and promoter are fed into a high-pressure autoclave which is filled with ammonia gas and hydrogen gas in specific quantity, the high-pressure autoclave is heated to a preset temperature and a preset pressure and reacts for multiple hours on the condition of preserving heat, and the materials in the high-pressure autoclave are discharged and filtered after the reaction, filter cakes can be recovered, and colorless transparent polyether amine is obtained after filter liquid is subjected to dewatering. The preparation method is simple in procedures, milder in reaction conditions, low in cost, high in yield of reaction products, selectivity and conversion rate, light in appearance color and easy to be industrialized, and the catalyst can be circularly mechanically used.
Description
Technical field
The invention belongs to organic chemical industry's technical field, particularly the preparation method of series products of polyether amine.
Background technology
Polyetheramine is called again Amino Terminated polyether(ATPE), polyethers polyamine, it is the polyalkylene oxide hydrocarbon compound by primary amine groups or secondary amine end-blocking, be a kind of important Organic Chemicals and fine chemical product, can be applied to the fields such as epoxy resin cure, tensio-active agent, lubricating oil, seal gum.At present, international main manufacturer is the graceful and BASF of Hensel two companies, and domestic several families is only arranged, and scale is all very little, can not satisfy the demand of domestic market at all.
The synthetic method of polyetheramine mainly contains high pressure catalytic ammoniation method, leavings group method, amino-butenate method, polyethers nitrile alkylation process etc.Catalytic ammoniation method synthesizing polyether amine is present most advanced, the constant product quality of technique and more meet the method for environmental requirement in the world, is also the main method of external polyetheramine suitability for industrialized production.
Patent CN101522607 has described and has used the method that comprises at least 80% metal that is selected from cobalt and aluminium, prepares polyetheramine lower than the catalyzer of 5% bronze medal from corresponding polyether glycol, but the method needs the reaction pressure of 16MPa left and right, and the primary amine poor selectivity is only 96～98%; US2003139289 has described from alcohol, aldehyde or ketone, comprising also that except nickel, copper and chromium the catalyzer of tin prepares the Innovative method of polyetheramine, yet the method adopts from controlling catalyst under high-temperature and high-pressure conditions, the ammonification hydrogenation reaction has prepared polyetheramine, but conversion rate of products is lower, and reaction produces a large amount of by products; US50003107 described a kind of under the effect of ammonia nickel catalyzator polyetheramine is selected the method for hydrogenation, the yield of its target product is only 75%; CN101921392 has described take the polyethers nitrile as raw material, makes Primary Catalysts at two titanocene complexes, has synthesized polyetheramine, but operational path is complicated, also needs simultaneously the first promotor and the second promotor, and product yield is on the low side.
Summary of the invention
The object of the invention is to propose the preparation method of the series products of polyether amine that a kind of flow process is simple, reaction conditions is relatively gentle, cost is low, transformation efficiency is high.
Method steps of the present invention is as follows:
1) polypropylene glycol, catalyzer and promotor are dosed in sealing autoclave; Contain mass percent in described catalyzer and be respectively 1～5% aluminium, 90～95% nickel and 1～3% tin, perhaps contain mass percent in described catalyzer and be respectively 10～15% aluminium, 80～90% nickel, 3～6% iron and 1～3% chromium; Described promotor is any one in sodium carbonate, sodium bicarbonate, sodium hydroxide, salt of wormwood, saleratus, potassium hydroxide, calcium hydroxide or potassium primary phosphate;
2) be filled with ammonia and hydrogen in described sealing autoclave;
3) heating described sealing autoclave to temperature in the kettle is that 150～300 ℃, pressure are 5～15MPa, carries out insulation reaction 1～30h;
4) after reaction finishes, material is emitted, filter, reclaim filter cake, then filtrate is carried out processed, obtain the product polyetheramine.
The present invention adopt molecular weight be 200～8000 polypropylene glycol under high-temperature and high-pressure conditions, the syntheti c route of Study on Catalytic Amination of Alcohols method one-step synthesis series products of polyether amine, reaction environment is gentle, has reduced facility investment, reduced produce dangerous; The present invention introduces a small amount of promotor, can significantly improve the catalytic efficiency of catalyzer; The present invention carries out negative pressure processed way with filtrate, removes raw material and moisture in product, can obtain the colourless transparent liquid polyetheramine.The filter cake that reclaims also can carry out recycled, is beneficial to reduce production costs.Production cost of the present invention is low, catalyst recirculation is applied mechanically, the reaction product yield is high, selectivity is high, transformation efficiency is high, appearance color is shallow, is easy to realization of industrialization.
Be the transformation efficiency and the reduction raw materials cost that improve reaction, the mass ratio that feeds intake of described catalyzer and polypropylene glycol is 1～80 ︰ 100, preferred 10～30 ︰ 100.
The preferred promotor of the present invention is any one in sodium carbonate, sodium bicarbonate or sodium hydroxide.
For improving reaction conversion ratio, reducing catalyst levels, the mass ratio that feeds intake of described promotor and polypropylene glycol is 0.1～5 ︰ 100.
Be the security of guaranteeing to react, the mass ratio that feeds intake of described ammonia and polypropylene glycol is 20～60 ︰ 100, preferred 25～40 ︰ 100
In addition, every input 100g polypropylene glycol uses hydrogen 0.1～10Mpa, preferred 0.3～3MPa.
Described processed is: under the vacuum degree condition of 2～20kPa, and 40～150 ℃ of thermal treatment 1～10h.
Temperature of reaction of the present invention preferably is controlled to be 180～250 ℃.
Reaction pressure of the present invention preferably is controlled to be 7～12MPa.
Soaking time of the present invention preferably is controlled to be 10～20h.
Embodiment
The molecular weight of the polypropylene glycol that adopts in the embodiment of the present invention is any one in 200,400 or 2000.
Embodiment 1:
(1) be that polypropylene glycol, 25g catalyzer (containing 3% aluminium, 95% nickel, 2% tin), the promotor sodium carbonate 0.15g of 200g/mol is dosed in the autoclave of 1L sealing with the 120g molar mass;
(2) be filled with ammonia 55g, hydrogen 0.7MPa in sealing autoclave;
(3) heating, after making high pressure temperature in the kettle to 220 ℃, pressure 9MPa, insulation reaction 18h;
(4) after reaction finishes, material is emitted, filters, reclaim filter cake, then with filtrate under the vacuum degree condition of 10kPa, 100 ℃ of thermal treatment 2h carry out processed, obtain product 119g polyetheramine.
Obtain polyetheramine D230 through reaction, outward appearance is colourless transparent liquid.By determining amine value and hydroxyl value, can record 94.34% transformation efficiency.The selectivity to primary amine by titration measuring is 99.63%, based on total amine value content meter.
The comparative example: do not add promotor sodium carbonate, other operational condition is identical.
Obtain 119g polyetheramine D230 through reaction, outward appearance is colourless transparent liquid.By determining amine value and hydroxyl value, can record 87.62% transformation efficiency.The selectivity to primary amine by titration measuring is 92.74%, based on total amine value content meter.
Embodiment 2:
(1) be that polypropylene glycol, 15g catalyzer (comprising 3% aluminium, 96% nickel, 1% tin), the promotor sodium bicarbonate 0.15g of 400g/mol is dosed in the autoclave of 1L sealing with the 150g molar mass;
(2) be filled with ammonia 40g, hydrogen 0.5MPa in sealing autoclave;
(3) after heating high-pressure temperature in the kettle to 200 ℃, pressure 8MPa, insulation reaction 12h;
(4) after reaction finishes, material is emitted, filters, reclaim filter cake, then with filtrate under the vacuum degree condition of 10kPa, 100 ℃ of thermal treatment 2h carry out processed, obtain the product polyetheramine.
Obtain 148 g polyetheramine D400 through reaction, outward appearance is colourless transparent liquid.By determining amine value and hydroxyl value, can record 95.17% transformation efficiency.The selectivity to primary amine by titration measuring is 99.50%, based on total amine value content meter.
Embodiment 3:
(1) be that polypropylene glycol, 20g catalyzer (comprising 4% aluminium, 94% nickel, 2% tin), the promotor sodium carbonate 0.15g of 2000g/mol is dosed in the autoclave of 1L sealing with the 150g molar mass;
(2) be filled with ammonia 40g, hydrogen 0.7MPa in sealing autoclave;
(3) be heated to high pressure temperature in the kettle to 200 ℃, pressure 8MPa after, insulation reaction 10h;
(4) after reaction finishes, material is emitted, filters, reclaim filter cake, then with filtrate under the vacuum degree condition of 10kPa, 100 ℃ of thermal treatment 2h carry out processed, obtain the product polyetheramine.
Obtain 148 g polyetheramine D2000 through reaction, outward appearance is colourless transparent liquid.By determining amine value and hydroxyl value, can record 95.09% transformation efficiency.The selectivity to primary amine by titration measuring is 99.47%, based on total amine value content meter.
Embodiment 4:
(1) be that polypropylene glycol, 35g catalyzer (comprising 12% aluminium, 81% nickel, 4% iron, 3% chromium), the promotor sodium bicarbonate 0.35g of 200g/mol is dosed in the autoclave of 1L sealing with the 120g molar mass;
(2) be filled with ammonia 50g, hydrogen 0.7MPa in sealing autoclave;
(3) heating, after making high pressure temperature in the kettle to 250 ℃, pressure 10MPa, insulation reaction 18h;
(4) after reaction finishes, material is emitted, filters, reclaim filter cake, then with filtrate under the vacuum degree condition of 10kPa, 100 ℃ of thermal treatment 2h carry out processed, obtain the product polyetheramine.
Obtain 118 g polyetheramine D230 through reaction, outward appearance is colourless transparent liquid.By determining amine value and hydroxyl value, can record 93.87% transformation efficiency.The selectivity to primary amine by titration measuring is 99.65%, based on total amine value content meter.
Embodiment 5:
(1) be that polypropylene glycol, 25g catalyzer (comprising 11% aluminium, 82% nickel, 2% iron, 5% chromium), the promotor sodium hydroxide 0.15g of 400g/mol is dosed in the autoclave of 1L sealing with the 150g molar mass;
(2) be filled with ammonia 50g, hydrogen 0.5MPa in sealing autoclave;
(3) heating, after making high pressure temperature in the kettle to 230 ℃, pressure 11MPa, insulation reaction 10h;
(4) after reaction finishes, material is emitted, filters, reclaim filter cake, then with filtrate under the vacuum degree condition of 10kPa, 100 ℃ of thermal treatment 2h carry out processed, obtain the product polyetheramine.
Obtain 149g polyetheramine D400 through reaction, outward appearance is colourless transparent liquid.By determining amine value and hydroxyl value, can record 92.19% transformation efficiency.The selectivity to primary amine by titration measuring is 99.56%, based on total amine value content meter.
Embodiment 6:
(1) be that polypropylene glycol, 15g catalyzer (comprising 11% aluminium, 85% nickel, 3% iron, 1% chromium), the promotor sodium carbonate 0.20g of 2000g/mol is dosed in the autoclave of 1L sealing with the 150g molar mass;
(2) be filled with ammonia 35g, hydrogen 0.74MPa in sealing autoclave;
(3) heating, after making high pressure temperature in the kettle to 190 ℃, pressure 7.5MPa, insulation reaction 15h;
(4) after reaction finishes, material is emitted, filters, reclaim filter cake, then with filtrate under the vacuum degree condition of 10kPa, 100 ℃ of thermal treatment 2h carry out processed, obtain the product polyetheramine.
Obtain 148 g polyetheramine D2000 through reaction, outward appearance is colourless transparent liquid.By determining amine value and hydroxyl value, can record 92.86% transformation efficiency.The selectivity to primary amine by titration measuring is 99.35%, based on total amine value content meter.
Embodiment 7～11:
Operational condition is applied mechanically with embodiment 2 catalyst recirculation that filter cake reclaims, and acquired results is as shown in the table:
| Embodiment | Weight | Selectivity (%) | Transformation efficiency (%) | Outward appearance |
| 7 | 148 | 99.54 | 95.13 | Water white transparency |
| 8 | 148 | 99.49 | 94.82 | Water white transparency |
| 9 | 149 | 99.81 | 93.97 | Water white transparency |
| 10 | 148 | 99.74 | 94.21 | Water white transparency |
| 11 | 148 | 99.19 | 93.65 | Water white transparency |
Claims (9)
1. the preparation method of series products of polyether amine is characterized in that step is as follows:
1) be that 200～8000 polypropylene glycol, catalyzer and promotor are dosed in sealing autoclave with molecular weight; Contain mass percent in described catalyzer and be respectively 1～5% aluminium, 90～95% nickel and 1～3% tin, in described catalyzer, each component total mass is 100%, perhaps contain mass percent in described catalyzer and be respectively 10～15% aluminium, 80～90% nickel, 3～6% iron and 1～3% chromium, in described catalyzer, each component total mass is 100%; Described promotor is any one in sodium carbonate, sodium bicarbonate, sodium hydroxide, salt of wormwood, saleratus, potassium hydroxide, calcium hydroxide or potassium primary phosphate;
2) be filled with ammonia and hydrogen in described sealing autoclave;
3) heating described sealing autoclave to temperature in the kettle is that 150～300 ℃, pressure are 5～15MPa, carries out insulation reaction 1～30h;
4) after reaction finishes, material is emitted, filter, reclaim filter cake, then filtrate is carried out processed, obtain the product polyetheramine.
2. the preparation method of series products of polyether amine according to claim 1, the molecular weight that it is characterized in that described polypropylene glycol is any one in 200,400 or 2000.
3. the preparation method of series products of polyether amine according to claim 1, the mass ratio that feeds intake that it is characterized in that described catalyzer and polypropylene glycol is 1～80 ︰ 100.
4. the preparation method of series products of polyether amine according to claim 1, is characterized in that described promotor is any one in sodium carbonate, sodium bicarbonate or sodium hydroxide.
5. the preparation method of according to claim 1 or 4 described series products of polyether amines, the mass ratio that feeds intake that it is characterized in that described promotor and polypropylene glycol is 0.1～5 ︰ 100.
6. the preparation method of series products of polyether amine according to claim 1, the mass ratio that feeds intake that it is characterized in that described ammonia and polypropylene glycol is 20～60 ︰ 100.
7. the preparation method of series products of polyether amine according to claim 1, is characterized in that every input 100g polypropylene glycol uses hydrogen 0.1～10MPa.
8. the preparation method of series products of polyether amine according to claim 1 is characterized in that described processed is: under the vacuum degree condition of 2～20kPa, and 40～150 ℃ of thermal treatment 1～10h.
9. the preparation method of series products of polyether amine according to claim 1 is characterized in that at temperature in the kettle being that 180～250 ℃, pressure are insulation reaction 10～20h under 7～12MPa.
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| CN103012769B (en) * | 2013-01-05 | 2015-01-21 | 扬州晨化新材料股份有限公司 | Continuous hydro-ammonization or amination reaction method |
| CN104387578B (en) * | 2014-12-08 | 2016-07-13 | 广州腾威科技有限公司 | Polyetheramine compositions, preparation method and its usage |
| CN106669731A (en) | 2015-11-09 | 2017-05-17 | 万华化学集团股份有限公司 | Catalyst applied to amination of polyether polyol, preparation method thereof and method for preparing polyether amine by using catalyst |
| CN108003041A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of method for separating Aethoxy Sklerol and polyetheramine |
| CN110218307A (en) * | 2019-06-19 | 2019-09-10 | 美瑞新材料股份有限公司 | A kind of preparation system of polyetheramine |
| CN112759758A (en) * | 2020-12-31 | 2021-05-07 | 淄博正大聚氨酯有限公司 | Method for preparing polyether amine by intermittent catalytic amination |
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| CN102161822B (en) * | 2010-12-29 | 2013-10-30 | 东莞市科道玛电子复合材料有限公司 | Preparation method for polyether amine composite material |
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