CN102161822B - Preparation method for polyether amine composite material - Google Patents
Preparation method for polyether amine composite material Download PDFInfo
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- CN102161822B CN102161822B CN 201010623376 CN201010623376A CN102161822B CN 102161822 B CN102161822 B CN 102161822B CN 201010623376 CN201010623376 CN 201010623376 CN 201010623376 A CN201010623376 A CN 201010623376A CN 102161822 B CN102161822 B CN 102161822B
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Abstract
The invention discloses a novel preparation method for a polyether amine composite material, which comprises the following preparation steps: (1) preparing refined polyether polyol; and (2) preparing polyether amine. In the invention, upstream raw materials are used as starting raw materials, various monomer raw materials are used to produce a hydroxyl polyol with a multi-functional group structure, a high-activity catalyst is combined, the activity of the catalyst is improved, many tests are carried out, the tested product has high comprehensive performance, production cost is reduced, and the product is suitable to be used in more industries. In the invention, new varieties of upstream raw materials of the polyether amine product are added, the polyether products are diversified, the application adaptability of the product in the composite material is improved, product quality is improved, product cost is reduced, reaction pressure and temperature are lowered, the production safety coefficient is high, equipment manufacturing cost is lowered, energy consumption is reduced, and continuous large-scale production is promoted.
Description
Technical field
The invention belongs to the new chemical materials technical field, more specifically relate to the preparation method that a kind of matrix material is used polyetheramine.
Background technology
Present domestic polyetheramine end-use is wide, but the polyetheramine product of usefulness relies on import substantially, it is basic chain that imported product is substantially all used finished product polyoxypropyleneglycol or polyoxytrimethylene triol. primary hydroxyl and the secondary hydroxyl of polyoxypropyleneglycol or polyoxytrimethylene triol are formed in the lower reaction of hydrogen and hydrogenation/dehydrogenation catalyzer (the thunder Buddhist nun is carrier) existence, exist raw material single, this kind hydrogenation catalyst exists the hydrogenation temperature high, production cycle is long, the drawback that refining cost rises, all demand of satisfying the market application.
Cause the major cause raw material of above-mentioned drawback single and be that hydrogenation/dehydrogenation catalyst reaction activity is not high, make the production cycle long, temperature is high, and is refining inconvenient.
The present invention sets about from upstream raw material, with various of monomer raw material production polyfunctional group structural hydroxyl polyvalent alcohol, compound high high activated catalyst, improve catalyst activity, through test of many times, the product of test, over-all properties is superior, also is born and produces low cost, is applicable to the more application of conglomerate.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, a kind of preparation method of matrix material polyetheramine is provided.
The present invention is achieved through the following technical solutions:
The present invention mainly generates various polyfunctional group polyether glycols with raw material monomer by polyfunctional group initiator and catalyzer, by neutralization, and absorbent charcoal fine purification, water-removal agent filters.Refining polyfunctional group polyether glycol in the presence of hydrogen, with the effect of the ammoniation agent such as liquefied ammonia by the compound nanocatalyst of activation again under certain pressure and the temperature hydrogenation produce polyetheramine, by absorbent charcoal fine purification, the refining polyetheramine product such as filter.
Concrete preparation method is described below:
The new preparation process of matrix material polyetheramine is comprised of following technological step:
(1) preparation of refining Aethoxy Sklerol
Polyfunctional group initiator and dewatering agent are added in the polymerization reaction kettle control temperature; Add catalyzer after 30 minutes; Vacuumize desolvation and air after 10-30 minute, fill again the high pure nitrogen replacement reaction kettle; Keep temperature, slowly add monomer, control reaction pressure and temperature of reaction are surveyed molecular weight and are reached termination reaction behind the prescribed value, cooling, and neutralization adds the absorbent charcoal fine purification decolouring, removes catalyzer, filters, and gets refining Aethoxy Sklerol;
(2) preparation of polyetheramine
Refining Aethoxy Sklerol is shifted in the high-pressure hydrogenation still, and the nanometer hydrogenation catalyst with activation adds inflated with nitrogen again, put out the air in the high-pressure hydrogenation still, when hydrogenation reaches 0.8MPa-1MPa to hydrogen pressure, stop hydrogenation, high-pressure pump slowly is pressed into ammoniation agent, 100 ℃-180 ℃ of control temperature of reaction, control reaction pressure 10MPa-18MPa carried out hydrogenation, according to product requirement control reaction times 2-10 hour, reach requirement, first cooling, cooling, impurity screening, reclaim catalyzer, vacuumize and remove excessive free unreacted amine, decolorizing and refining gets the polyetheramine finished product again, add at last stablizer, the stability of product storage is provided;
Described polyfunctional group initiator is ethylene glycol, propylene glycol, 1,6-hexylene glycol, 1,5-PD, neopentyl glycol, glycerine, Xylitol, TriMethylolPropane(TMP), N.F,USP MANNITOL or sucrose; Dewatering agent is triethyl orthoformate, trimethyl orthoformate or molecular sieve; Catalyzer is potassium hydroxide, potassium alkoxide solution, perchloric acid, chlorsulfonic acid, alchlor or barium carbonate; Raw material monomer is oxyethane, propylene oxide, tetrahydrofuran (THF), butylene oxide ring, divinyl or vinyl cyanide; The nanometer hydrogenation catalyst is the compound of a kind of of nano level cuprous chloride, nano level copper powder or two kinds; Ammoniation agent is liquid amine or hexahydroaniline.
Dewatering agent is the 0.3%-0.8% of initiator weight consumption.
The functional group that the present invention produces polyetheramine can be 1-8, and molecular weight can be 90-8000.
Compared with prior art, the present invention has following beneficial effect:
The present invention is formed, is contained on the molecular backbone chain each sense ehter bond terminal hydroxyl generation NH of ehter bond-R-O-R '-(R and R ' are the aliphatic ethers of alkyl) by synthesis of epoxy compounds
2Base, as follows:
HO-R-(OR) n-OH or HO-R-[OCO-R] n-OH
NH
2-R-(OR) n-NH
2Or NH
2-R-[OCO-R] n-NH
2
Polyfunctional group polyetheramine product of the present invention is mainly used various composite curing agents, composite casting material and composite modification etc., adopt the polyetheramine of different monomer production to have than simple polyoxytrimethylene structure and have stronger usability, example: PTMG amine increases product fatigue resistance flexural strength, the warm nature of anti-the end, resistance to deterioration, and the consistency of low molecular composite material.Example: the polyetheramine take butylene oxide ring as monomer production has the higher interior shearing resistance of polyetheramine of producing as monomer than propylene oxide, better aging, ultraviolet light, lower viscosity, better transparency.Consumption was few when the polyetheramine of 4 above functional groups used, and high with the matrix material reactive behavior, curing speed is fast, and it is few to add consumption, the high serial advantage of hardness.
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment
Preparation example 1:
The new preparation process of matrix material polyetheramine is comprised of following technological step:
The initiator glycerine 105g of functional group and dewatering agent triethyl orthoformate 0.7g are added in the polymerization reaction kettle, be warmed up to 100 ℃-110 ℃ of heating, add 70% concentration potassium alcoholate catalyzer 22g after 30 minutes, vacuumize 30 minutes desolvations and air after 30 minutes, the pure nitrogen gas replacement reaction kettle of leaping high again, keep 90 ℃-100 ℃ of temperature, slowly add 765g oxyethane, control reaction pressure 0.25-0.3MPa, 100 ℃-120 ℃ reactions of temperature are after 3 hours, survey molecular weight 400 termination reactions, cooling, neutralization, add the absorbent charcoal fine purification decolouring, remove catalyzer, filter, get the refining polyether-tribasic alcohol of 820 grams.
Above-mentioned dewatering agent triethyl orthoformate consumption is the 0.5%-0.8% of initiator glycerine.
820 refining gram polyether-tribasic alcohols are shifted in the high-pressure hydrogenation still, nano combined hydrogenation catalyst with 120 gram activation adds again, inflated with nitrogen, put out the air in the high-pressure hydrogenation still, when hydrogenation reaches 0.8MPa-1MPa to hydrogen pressure, stop hydrogenation, high-pressure metering pump slowly is pressed into 980ml liquid amine, 140 ℃-180 ℃ of control temperature of reaction, control reaction pressure 16MPa-18MPa carries out hydrogenation, according to product requirement control reaction times 4-5 hour, reach requirement, first cooling, cooling, release, impurity screening reclaims catalyzer, takes out and really removes excessive free unreacted amine, decolorizing and refining again, get 1.72Kg trifunctional polyetheramine finished product, add at last stablizer, the stability of product storage is provided.
Preparation example 2:
The new preparation process of matrix material polyetheramine is comprised of following technological step:
The initiator N.F,USP MANNITOL 85g of functional group and dewatering agent trimethyl orthoformate 0.6g are added in the polymerization reaction kettle, be warmed up to 90 ℃-100 ℃ of heating, add 18g after 30 minutes and enter the potassium alcoholate catalyzer, vacuumize 30 minutes desolvations and air after 30 minutes, be filled with again the high pure nitrogen replacement reaction kettle, keep 100 ℃-110 ℃ of temperature, slowly add the 720g propylene oxide, control reaction pressure 0.1-0.3MPa, 110 ℃-120 ℃ of temperature, survey molecular weight 1000 termination reactions, cooling, neutralization, add the absorbent charcoal fine purification decolouring, remove catalyzer, filter, get the refining polyethers hexavalent alcohol of 775g.
Above-mentioned dewatering agent trimethyl orthoformate consumption is the 0.5%-0.8% of initiator glycerine.
The polyethers hexavalent alcohol that 775g is refining shifts in the high-pressure hydrogenation still, nano combined hydrogenation catalyst with the 115g activation adds again, inflated with nitrogen, put out the air in the high-pressure hydrogenation still, when hydrogenation reaches 0.8MPa-1MPa to hydrogen pressure, stop hydrogenation, high-pressure pump slowly is pressed into 1800g liquid amine, 170 ℃-180 ℃ of control temperature of reaction, control reaction pressure 16MPa-18MPa carried out hydrogenation, according to product requirement control reaction times 5-6 hour, reach requirement, first cooling, cooling, impurity screening, reclaim catalyzer, take out and really remove excessive free unreacted amine, decolorizing and refining gets six stable functional polyethers amine finished products of 2000g thermal oxidation again, add at last stablizer, the stability of product storage is provided.
Preparation example 3:
The new preparation process of matrix material polyetheramine is comprised of following technological step:
Tetrahydrofuran (THF) 1000g and dewatering agent trimethyl orthoformate 3g are added in the polymerization reaction kettle, temperature controls to-10 ℃-5 ℃, add cationic catalyst after 30 minutes, vacuumize after 10 minutes and remove air, be filled with again the high pure nitrogen replacement reaction kettle, keep temperature-5 ℃, slowly drip the 20g nitrosonitric acid, control reaction pressure 0.1MPa, temperature is surveyed molecular weight 400 termination reactions below 0 ℃, is warmed up to 70-90 ℃ of decompression distilled and goes out the complete tetrahydrofuran monomers of unreacted, leave standstill, neutralization, catalyzer is removed in refining decolouring, filter, get the refining PTMG of 920g.
Above-mentioned dewatering agent trimethyl orthoformate consumption is the 0.3%-0.4% of initiator glycerine.
The PTMG that 920g is refining shifts in the high-pressure hydrogenation still, nano combined hydrogenation catalyst with the 198g activation adds again, inflated with nitrogen, put out the air in the high-pressure hydrogenation still, when hydrogenation reaches 0.8MPa-1MPa to hydrogen pressure, stop hydrogenation, high-pressure pump slowly is pressed into 1120g liquid amine, 150 ℃-160 ℃ of control temperature of reaction, control reaction pressure 15MPa-16MPa carried out hydrogenation, according to product requirement control reaction times 6-7 hour, reach requirement, first cooling, cooling, impurity screening, reclaim catalyzer, take out and really remove excessive free unreacted amine, decolorizing and refining gets anti-aging good 1800g PTMG amine finished product again, add at last stablizer, the stability of product storage is provided.
Claims (2)
1. the preparation method of matrix material polyetheramine is characterized in that, is comprised of following technological step:
(1) preparation of refining Aethoxy Sklerol
Polyfunctional group initiator and dewatering agent are added in the polymerization reaction kettle control temperature; Add catalyzer after 30 minutes; Vacuumize desolvation and air after 10-30 minute, fill again the high pure nitrogen replacement reaction kettle; Keep temperature, slowly add monomer, control reaction pressure and temperature of reaction are surveyed molecular weight and are reached termination reaction behind the prescribed value, cooling, and neutralization adds the absorbent charcoal fine purification decolouring, removes catalyzer, filters, and gets refining Aethoxy Sklerol;
(2) preparation of polyetheramine
Refining Aethoxy Sklerol is shifted in the high-pressure hydrogenation still, and the nanometer hydrogenation catalyst with activation adds inflated with nitrogen again, put out the air in the high-pressure hydrogenation still, when hydrogenation reaches 0.8MPa-1MPa to hydrogen pressure, stop hydrogenation, high-pressure pump slowly is pressed into ammoniation agent, 100 ℃-180 ℃ of control temperature of reaction, control reaction pressure 10MPa-18MPa carried out hydrogenation, according to product requirement control reaction times 2-10 hour, reach requirement, first cooling, cooling, impurity screening, reclaim catalyzer, vacuumize and remove excessive free unreacted amine, decolorizing and refining gets the polyetheramine finished product again, add at last stablizer, the stability of product storage is provided;
Described polyfunctional group initiator is ethylene glycol, propylene glycol, 1,6-hexylene glycol, 1,5-PD, neopentyl glycol, glycerine, Xylitol, TriMethylolPropane(TMP), N.F,USP MANNITOL or sucrose; Dewatering agent is triethyl orthoformate, trimethyl orthoformate or molecular sieve; Catalyzer is potassium hydroxide, potassium alkoxide solution, perchloric acid, chlorsulfonic acid, alchlor or barium carbonate; Raw material monomer is oxyethane, propylene oxide, tetrahydrofuran (THF), butylene oxide ring, divinyl or vinyl cyanide; The nanometer hydrogenation catalyst is the compound of a kind of of nano level cuprous chloride, nano level copper powder or two kinds; Ammoniation agent is liquid amine or hexahydroaniline.
2. the preparation method of matrix material polyetheramine according to claim 1, it is characterized in that: dewatering agent is the 0.3%-0.8% of initiator weight consumption.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102382294B (en) * | 2011-09-05 | 2013-11-06 | 江苏扬农化工集团有限公司 | Preparation method for series products of polyether amine |
| CN102389802B (en) * | 2011-09-20 | 2013-08-28 | 中国石油化工集团公司 | Amine-terminated polyether synthetic catalyst and preparation method thereof |
| CN102634006A (en) * | 2012-03-28 | 2012-08-15 | 浙江皇马科技股份有限公司 | Polyether amine for textile printing and dyeing auxiliary and preparation method for polyether amine |
| CN104341299B (en) * | 2013-07-29 | 2016-08-24 | 漳州金富顺生物科技有限公司 | A kind of esterification of deodorised fat acid |
| CN103408747B (en) * | 2013-08-22 | 2015-12-23 | 南京博特新材料有限公司 | A kind of preparation method of Amino Terminated polyether(ATPE) |
| 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 |
| CN105367779B (en) * | 2015-12-17 | 2017-08-01 | 上海多纶化工有限公司 | The process for purification of isomery alcohol polyethers |
| 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 |
| CN106832251B (en) * | 2017-03-30 | 2018-11-02 | 浙江皇马表面活性剂研究有限公司 | A kind of method of normal pressure catalyzed preparation of poly ether amines |
| CN111499858B (en) * | 2020-04-24 | 2022-11-11 | 浙江皇马科技股份有限公司 | Refining method of high-viscosity polymer crude product |
| CN112521595B (en) * | 2020-12-04 | 2022-08-12 | 淄博正大聚氨酯有限公司 | Synthetic method for preparing amino-terminated polyether polyol through hydrogen catalytic amination |
| CN116003775B (en) * | 2021-10-22 | 2024-04-02 | 中国石油化工股份有限公司 | Triamine polyether compound, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1042718A (en) * | 1988-11-16 | 1990-06-06 | 三井东压化学株式会社 | The polyoxyalkylene polyamines preparation method of tool secondary amino group end |
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| JP2006518776A (en) * | 2003-01-17 | 2006-08-17 | クラリアント インターナショナル リミティド | Polymer ether amines, their production and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042718A (en) * | 1988-11-16 | 1990-06-06 | 三井东压化学株式会社 | The polyoxyalkylene polyamines preparation method of tool secondary amino group end |
Non-Patent Citations (1)
| Title |
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| 乔迁.聚醚胺的合成.《聚醚胺的合成》.2002,第23卷第80－82页. * |
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