CN103113553A - Pure vegetable oil based polyalcohol and preparation method thereof - Google Patents
Pure vegetable oil based polyalcohol and preparation method thereof Download PDFInfo
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Abstract
The invention relates a pure vegetable oil based polyalcohol and a preparation method thereof. The vegetable oil based polyalcohol is characterized in that the hydroxyl value is 200 mgKOH/g-700 mgKOH/g; the vegetable oil based polyalcohol mainly is prepared from the materials consisting of vegetable oil, glycerol, fatty acid or corresponding derivatives. The materials are reacted under the protection of inert gases, reacted under vacuum and cooled to obtain the pure vegetable oil based polyalcohol product. According to the pure vegetable oil based polyalcohol and the preparation method disclosed by the invention, the performance characteristics of each structural unit in the vegetable oil are sufficiently utilized, so that the prepared pure vegetable oil based polyalcohol not only has the characteristics of the pure vegetable oil base, but also can be widely applied to the preparation of polyurethane materials.
Description
Technical field
The present invention relates to a kind of pure vegetable oil-based polyols and preparation method thereof.
Background technology
The polyurethane material excellent performance, of many uses, goods are of a great variety, are widely used in producing multiple material, as foam, plastics, fiber, tackiness agent and sealing agent etc.Concrete Application Areas comprises refrigerator, freezer, building heat preservation and furniture, clothes, automobile, coating, chemical fibre, plastics, all trades and professions such as gluing.
But, in the process of manufacture urethane, be subject to the restriction of the aspects such as the finiteness of petroleum resources, non-renewable and larger ecological pollution due to traditional polyether glycol, the vegetable oil polyol that possesses the characteristics such as environmental protection and resource recyclability is received publicity more and more and is used.
In October, 2005, by U.S. API(the Alliance for the Polyurethanes Industry) " polyurethanes technology investigation and the trade promotion meeting " initiated hold at Texas-Houston, and an important issue of conference is used vegetable oil-based polyols petroleum replacing polylol exactly.
Successfully developed in 2006 for of the present invention group and directly utilized transesterify to prepare the method for vegetable oil polyol, and applied for patent, publication number is CN1869184.After this in succession applied for again Patents, as: CN101016225, CN200610027353, CN200710046555, CN201110266443 etc.
US6107433 discloses a kind of method for preparing polyvalent alcohol with vegetables oil, is specially: use peroxy acid to carry out epoxidation to vegetables oil, then add fluoroboric acid catalyzer and alcohol mixture and react the epoxidized oil hydroxylation is become polyvalent alcohol.The vegetable oil polyol molecular weight of this preparation method's preparation is large, and hydroxyl value is not suitable for preparing high performance hard polyurethane foam lower than 200mgKOH/g.
Pramod Kandanarachchi, Andrew Guo and Zoran Petrovic(Journal of Molecular Catalysis A:Chemical184 (2002), 65-71) adopt lawrencium as catalyzer, under high-temperature and high-pressure conditions, hydroxylation is carried out in direct and CO, H2 reaction.React required catalyzer expensive, severe reaction conditions, the catalyst recovery difficulty is so be not suitable for industrialized production.Prepared product hydroxyl value is not high simultaneously, has limited its utilization in the field of hard bubbling.
CN1245428C discloses a kind of direct method for preparing polyurethane foam with the air-blowing vegetables oil.The air-blowing vegetables oil that uses in this technique itself is not just to be well suited for preparing polyurethane material, because majority of plant oil itself is without hydroxyl, in the High Temperature Gas oxygen blast, will inevitably produce a lot of side reactions, cause product performance to descend, for example: degraded and charing that carbon connects, the generation of a large amount of peroxies, acid number increases, the isomery of vegetables oil and polymerization etc.The vegetable oil polyol hydroxyl value of simultaneously direct air-blowing oxidation preparation is generally lower than 100mgKOH/g.Above-mentioned drawbacks limit the utilization of air-blowing vegetables oil in polyurethane field.
CN1780867 discloses a kind of polyvalent alcohol, polyamine, amido alcohol or their mixture and plant oil based (VOB) monomer of utilizing and has carried out transesterification reaction, thus the preparation vegetable oil polyol.In this technique, plant oil based (VOB) used preparation complexity, so the integral production cost is very high, be not suitable for industrialization.
In recent years, new occurring about the preparation of vegetable oil polyol and the patent of application arranged constantly, as: CN101054433A, CN101062997A, CN101265157A, US20070123725, WO008675 etc.
But make a general survey of these patents, vegetables oil is just as the part material for preparing the corresponding plants oil polyalcohol, but not whole main raw material.Not yet see the Patent document data of vegetable oil-based polyols completely.
Summary of the invention
The object of the present invention is to provide a kind of pure vegetable oil-based polyols and preparation method thereof, mainly solve the existing defective of above-mentioned prior art, the present invention takes full advantage of the performance characteristics of each structural unit in vegetables oil, thereby prepared vegetable oil polyol, both had pure plant oil based characteristic, can be widely used in again the preparation of polyurethane material.
For achieving the above object, technical scheme of the present invention is:
A kind of pure vegetable oil-based polyols is characterized in that: its hydroxyl value is 200-700mgKOH/g.
A kind of preparation method of pure vegetable oil-based polyols as above; it is characterized in that: main raw material comprises vegetables oil, glycerine, lipid acid or corresponding derived material, and at first above-mentioned raw materials reacts under protection of inert gas, and then reacts under vacuum; cooling, namely get product.
The preparation method of described pure vegetable oil-based polyols is characterized in that: it is to be participated in reaction and prepared by a, b, c, four kinds of components of d; Wherein:
A, vegetables oil and/or epoxidized vegetable oil;
B, glycerine and/or Polyglycerine;
C, basic catalyst;
The small molecules alcohol ester of d, lipid acid and/or lipid acid;
With the total reactant weighing scale, the preferred weight of each component is: vegetables oil and/or epoxidized vegetable oil account for 10 ~ 75% weight; Glycerine and/or Polyglycerine account for 20 ~ 75% weight; Basic catalyst (water is not counted in) accounts for 0.06 ~ 1% weight; Lipid acid and/or lipid acid small molecules alcohol ester account for 0 ~ 35% weight.
At first four kinds of components react under protection of inert gas according to the above ratio, and then react under vacuum, cooling, namely get product.
The preparation method of described pure vegetable oil-based polyols is characterized in that: described vegetables oil is selected from one or more in soybean oil, Semen Maydis oil, sesame oil, peanut oil, sweet oil, Oleum Gossypii semen, rubber seed oil, sunflower seed oil, Thistle oil, tung oil, linseed oil, seed of Papaver somniferum L. powder, Rice pollard oil, Viscotrol C, rape seed oil, plam oil, palm kernel oil; The derivative of vegetables oil after oxidation, i.e. epoxidized vegetable oil, epoxidized vegetable oil are selected from one or more of epoxidized vegetable oil corresponding in above-mentioned vegetables oil.
The preparation method of described pure vegetable oil-based polyols is characterized in that: described glycerine and derivative thereof comprise: glycerine and Polyglycerine; Glycerine is one of product after the vegetables oil hydrolysis, and Polyglycerine is obtained after dehydrating condensation by glycerine.
The preparation method of described pure vegetable oil-based polyols is characterized in that: described lipid acid and derivative thereof comprise: corresponding product lipid acid after the vegetables oil hydrolysis, and the small molecules alcohol ester of the derivative of this lipid acid.
The preparation method of described pure vegetable oil-based polyols, it is characterized in that: described alkaline oxidiser comprises that sodium hydroxide, potassium hydroxide, sodium carbonate, two encircle [4.3.0]-1, the mixture of one or more in 5-phenodiazine-5-hendecene (DBU), triethylene diamine, N-methylmorpholine, sodium methylate, sodium ethylate, or its aqueous solution.
The preparation method of described pure vegetable oil-based polyols is characterized in that: described rare gas element comprises nitrogen or helium.
The preparation method of described pure vegetable oil-based polyols is characterized in that: preferred 2-12 hour described reaction times in rare gas element; The preferred 180-300 of temperature of reaction ℃; Preferred 2-15 of reaction times under vacuum condition hour; The preferred 160-320 of temperature of reaction ℃.
The present invention can obtain the polyvalent alcohol of different hydroxyl values, different functionality by regulating different reaction raw materials, different proportioning raw materials, to adapt to different product demands.
The invention has the advantages that the preparation method is simple, raw material sources are abundant; Product is pure plant oil based, and raw material is renewable, and product is environmental protection more; The controlled hydroxyl scope of product is larger, and the applied range of product is suitable for industrialized production.
Embodiment
The invention discloses a kind of pure vegetable oil-based polyols and preparation method thereof.The structure of vegetables oil is fatty acid triglycercide.This shows, its structural unit comprises glycerine and lipid acid.The present invention takes full advantage of the characteristic of glycerine and lipid acid in the structural unit of vegetables oil, in conjunction with the characteristic of vegetables oil itself, thereby has effectively prepared pure plant oil based polyvalent alcohol; And by selecting and regulating different proportioning raw materials, can in the hydroxyl value scope of 200-700mgKOH/g, as required, prepare the pure vegetable oil-based polyols of corresponding hydroxyl value.
In the present invention, main raw material comprises vegetables oil, glycerine, lipid acid or corresponding derived material.
Vegetables oil in the present invention is selected from one or more in soybean oil, Semen Maydis oil, sesame oil, peanut oil, sweet oil, Oleum Gossypii semen, rubber seed oil, sunflower seed oil, Thistle oil, tung oil, linseed oil, seed of Papaver somniferum L. powder, Rice pollard oil, Viscotrol C, rape seed oil, plam oil, palm kernel oil.Also used the derivative of vegetables oil after oxidation in the present invention, i.e. epoxidized vegetable oil.Epoxidized vegetable oil in the present invention is selected from one or more of epoxidized vegetable oil corresponding in vegetables oil listed above.
In the present invention, glycerine and derivative thereof comprise: glycerine and Polyglycerine.Glycerine is one of product after the vegetables oil hydrolysis.Polyglycerine is obtained after dehydrating condensation by glycerine.
In the present invention, lipid acid and derivative thereof comprise: corresponding product lipid acid after the vegetables oil hydrolysis, and the small molecules alcohol ester of the derivative of this lipid acid such as the lipid acid such as fatty acid methyl ester, fatty-acid ethyl ester.But in final vegetable oil polyol product, the small molecules alcohol ester of lipid acid used has discharged again micromolecular alcohol (as methyl alcohol, ethanol), has namely still only kept plant oil based structural unit in the finished product.Those micromolecular alcohol are just as the recycled transitional material for preparing derivative of fatty acid.
In the present invention, auxiliary material comprises rare gas element, as nitrogen, helium etc.; Also comprise basic catalyst, encircle [4.3.0]-1 as sodium hydroxide, potassium hydroxide, sodium carbonate, two, the mixture of one or more in 5-phenodiazine-5-hendecene (DBU), triethylene diamine, N-methylmorpholine, sodium methylate, sodium ethylate, or the aqueous solution of described alkali.
Concrete preparation process of the present invention is mainly: at first raw material reacts under protection of inert gas, and then reacts under vacuum, cooling, namely gets product.
Such as raw material comprises a, b, c, four kinds of components of d; Wherein:
A, vegetables oil and/or epoxidized vegetable oil;
B, glycerine and/or Polyglycerine;
C, basic catalyst;
The small molecules alcohol ester of d, lipid acid and/or lipid acid;
With the total reactant weighing scale, the preferred weight of each component is: vegetables oil and/or epoxidized vegetable oil account for 10 ~ 75% weight; Glycerine and/or Polyglycerine account for 20 ~ 75% weight; Basic catalyst (water is not counted in) accounts for 0.06 ~ 1% weight; Lipid acid and/or lipid acid small molecules alcohol ester account for 0 ~ 35% weight;
At first four kinds of components react under protection of inert gas according to the above ratio, and then react under vacuum, cooling, namely get product.
Vegetables oil in the present invention is one or more in soybean oil, Viscotrol C, rubber seed oil, sunflower seed oil, Thistle oil, tung oil, oleum lini, Semen Maydis oil, sesame oil, peanut oil, rape seed oil or plam oil preferably.Abundant, the lower-cost soybean oil of output more preferably.And epoxidized vegetable oil is epoxidized oil corresponding to corresponding vegetables oil.
Basic catalyst in the present invention is the mixture of one or more in sodium hydroxide, potassium hydroxide, triethylene diamine, sodium carbonate, sodium methylate, sodium ethylate preferably, or the aqueous solution of these alkali.But consider cost factor, and the power of catalytic performance, so more preferably sodium hydroxide or potassium hydroxide.
Fatty acid methyl ester preferably in lipid acid in the present invention, fatty acid ester.Because the fatty acid methyl ester raw materials cost is low, and be conducive to Reaction time shorten.
The preferred more general nitrogen that more easily obtains of rare gas element in the present invention.
Preferred 2-12 of reaction times in rare gas element hour; The preferred 180-300 of temperature of reaction ℃.
Preferred 2-15 of reaction times under vacuum condition hour; The preferred 160-320 of temperature of reaction ℃.
Reaction process of the present invention is: at first react certain hour in rare gas element, then close rare gas element, vacuumize, continue reaction at vacuum condition again, make to react completely the cooling product that namely gets.Preferred condition is that the temperature of reaction in nitrogen is 180-300 ℃, reacts 2-12 hour; Close nitrogen, vacuumizing temperature of reaction is 160-320 ℃, reacts 2-15 hour; Cooling reaction solution namely gets product.Therefore, preparation method's reaction process of the present invention is simple, and aftertreatment is easy, is suitable for industrialized production.
Below further introduce the present invention by embodiment again:
Embodiment 1
Above-mentioned each component is fed intake, under nitrogen protection, be warming up to 7 hours (water outlet is 110 grams approximately) of 240 ℃ of reactions.Close nitrogen, vacuumize, be warming up to 260 ℃ of reactions 4 hours (the oil material of water outlet and part approximately 85 grams) again.Cooling, namely get approximately 2130g of product.The product hydroxyl value is about 260mgKOH/g.
Embodiment 2
Said components (except the epoxy soybean oil) is fed intake, under nitrogen protection, be warming up to 9 hours (water outlet is 410 grams approximately) of 250 ℃ of reactions.Slightly cooling, close nitrogen, vacuumize, add epoxy soybean oil, be warming up to 220 ℃ of reactions 3 hours.Cooling, namely get approximately 2400g of product.The product hydroxyl value is about 460mgKOH/g.
Embodiment 3
Epoxy oleum lini 1600g
Four Polyglycerine 532g
KOH 1.3g
Above-mentioned each component is fed intake, under nitrogen protection, be warming up to 220 ℃ the reaction 3 hours (.Close nitrogen, vacuumize, be warming up to 230 ℃ of reactions 3 hours (water outlet and oil material approximately 13 grams) again.Cooling, namely get approximately 2120g of product.The product hydroxyl value is about 230mgKOH/g.
Embodiment 4
Said components (except epoxy plam oil and Uniphat A60) is fed intake, and logical nitrogen is warming up to 8 hours (water outlet is 550 grams approximately) of 270 ℃ of reactions.Slightly cooling, close nitrogen, vacuumize, add epoxy palm oil, be warming up to 230 ℃ of reactions 2 hours.Add again Uniphat A60, be warming up to 260 ℃ and react 5 hours (going out approximately 50 grams of methyl alcohol).Cooling, get approximately 2900g of product.The product hydroxyl value is about 430mgKOH/g.
Embodiment 5
Glycerine and potassium hydroxide are fed intake, and logical nitrogen is warming up to 3.5 hours (water outlet is 55 grams approximately) of 260 ℃ of reactions.Slightly cooling, close nitrogen, vacuumize, add epoxy soybean oil, be warming up to 210 ℃ of reactions 3 hours.Add again methyl soyate, be warming up to 270 ℃ and react 4 hours (going out approximately 100 grams of methyl alcohol).Cooling, get approximately 2700g of product.The product hydroxyl value is about 360mgKOH/g.
Embodiment 6
Epoxy oleum lini 1400g
Glycerine 1000g
Triethylene diamine 24g
Said components (except the epoxy oleum lini) is fed intake, under nitrogen protection, be warming up to 5 hours (water outlet is 100 grams approximately) of 265 ℃ of reactions.Slightly cooling, close nitrogen, vacuumize, add the epoxy oleum lini, be warming up to 210 ℃ of reactions 4 hours.Cooling, namely get approximately 2300g of product.The product hydroxyl value is about 520mgKOH/g.
Embodiment 7
Said components (except Uniphat A60) is fed intake, and logical nitrogen is warming up to 220 ℃ of reactions 3 hours.Close nitrogen, vacuumize, add Uniphat A60, be warming up to 260 ℃ and react 4 hours (going out approximately 30 grams of methyl alcohol).Cooling, get approximately 2470g of product.The product hydroxyl value is about 210mgKOH/g.
Being only preferred embodiment of the present invention in sum, is not to limit practical range of the present invention.Be that all equivalences of doing according to the content of the present patent application the scope of the claims change and modify, all should be technology category of the present invention.
Claims (9)
1. pure vegetable oil-based polyols, it is characterized in that: its hydroxyl value is 200-700mgKOH/g.
2. the preparation method of a pure vegetable oil-based polyols as claimed in claim 1; it is characterized in that: main raw material comprises vegetables oil, glycerine, lipid acid or corresponding derived material; at first above-mentioned raw materials reacts under protection of inert gas; and then react under vacuum; cooling, namely get product.
3. the preparation method of pure vegetable oil-based polyols according to claim 1 is characterized in that: it is to be participated in reaction and prepared by a, b, c, four kinds of components of d; Wherein:
A, vegetables oil and/or epoxidized vegetable oil;
B, glycerine and/or Polyglycerine;
C, alkaline oxidiser;
The small molecules alcohol ester of d, lipid acid and/or lipid acid;
With the total reactant weighing scale, the preferred weight of each component is: vegetables oil and/or epoxidized vegetable oil account for 10 ~ 75% weight; Glycerine and/or Polyglycerine account for 20 ~ 75% weight; Basic catalyst (water is not counted in) accounts for 0.06 ~ 1% weight; Lipid acid and/or lipid acid small molecules alcohol ester account for 0 ~ 35% weight;
At first four kinds of components react under protection of inert gas according to the above ratio, and then react under vacuum, cooling, namely get product.
4. the preparation method of according to claim 2 or 3 described pure vegetable oil-based polyols, it is characterized in that: described vegetables oil is selected from one or more in soybean oil, Semen Maydis oil, sesame oil, peanut oil, sweet oil, Oleum Gossypii semen, rubber seed oil, sunflower seed oil, Thistle oil, tung oil, linseed oil, seed of Papaver somniferum L. powder, Rice pollard oil, Viscotrol C, rape seed oil, plam oil, palm kernel oil; The derivative of vegetables oil after oxidation, i.e. epoxidized vegetable oil, epoxidized vegetable oil are selected from one or more of epoxidized vegetable oil corresponding in above-mentioned vegetables oil.
5. the preparation method of according to claim 2 or 3 described pure vegetable oil-based polyols, it is characterized in that: described glycerine and derivative thereof comprise: glycerine and Polyglycerine; Glycerine is one of product after the vegetables oil hydrolysis, and Polyglycerine is obtained after dehydrating condensation by glycerine.
6. the preparation method of according to claim 2 or 3 described pure vegetable oil-based polyols, it is characterized in that: described lipid acid and derivative thereof comprise: corresponding product lipid acid after the vegetables oil hydrolysis, and the small molecules alcohol ester of the derivative of this lipid acid.
7. the preparation method of according to claim 2 or 3 described pure vegetable oil-based polyols, it is characterized in that: described alkaline oxidiser comprises that sodium hydroxide, potassium hydroxide, sodium carbonate, two encircle [4.3.0]-1, the mixture of one or more in 5-phenodiazine-5-hendecene (DBU), triethylene diamine, N-methylmorpholine, sodium methylate, sodium ethylate, or its aqueous solution.
8. the preparation method of according to claim 2 or 3 described pure vegetable oil-based polyols, it is characterized in that: described rare gas element comprises nitrogen or helium.
9. the preparation method of according to claim 2 or 3 described pure vegetable oil-based polyols, is characterized in that: preferred 2-12 hour described reaction times in rare gas element; The preferred 180-300 of temperature of reaction ℃; Preferred 2-15 of reaction times under vacuum condition hour; The preferred 160-320 of temperature of reaction ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449328A (en) * | 2013-09-23 | 2015-03-25 | 丹阳恒安化学科技研究所有限公司 | Production technology for low-VOC polyurethane home decoration paint |
| CN106748767A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of low hydroxyl value plant oil polylol and preparation method thereof |
| CN106947073A (en) * | 2016-01-07 | 2017-07-14 | 万华化学集团股份有限公司 | A kind of polyglycereol polyether natural oil polyols and preparation method thereof and a kind of polyurethane elastomer and preparation method thereof |
| CN107151214A (en) * | 2016-03-03 | 2017-09-12 | 中国石油化工股份有限公司 | The method and device of tung oil polyalcohol is prepared under the conditions of a kind of hypergravity |
| CN107151210A (en) * | 2016-03-03 | 2017-09-12 | 中国石油化工股份有限公司 | A kind of method that tung oil polyalcohol is prepared under Ultrasonic Conditions |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1869184A (en) * | 2006-04-13 | 2006-11-29 | 上海中科合臣股份有限公司 | Preparation method of plant oil polyalcohol |
| EP1790678A1 (en) * | 2005-11-26 | 2007-05-30 | Bayer MaterialScience AG | Process for manufacturing polyols based on natural oils |
| CN101016225A (en) * | 2007-02-07 | 2007-08-15 | 上海中科合臣股份有限公司 | Preparing method for high hydroxyl value plant oil polyhydric alcohol |
| CN101085943A (en) * | 2006-06-07 | 2007-12-12 | 上海桑迪精细化工研究所有限公司 | Method for preparing vegetable oil based polyatomic alcohol for hard bubble polyurethane |
| CN101397250A (en) * | 2007-09-28 | 2009-04-01 | 上海爱默金山药业有限公司 | Preparation method of aliphatic ester polyol |
| US20100222541A1 (en) * | 2009-03-02 | 2010-09-02 | Joseph James Zupancic | Bio-based polyol |
-
2013
- 2013-01-30 CN CN201310036253XA patent/CN103113553A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1790678A1 (en) * | 2005-11-26 | 2007-05-30 | Bayer MaterialScience AG | Process for manufacturing polyols based on natural oils |
| CN1869184A (en) * | 2006-04-13 | 2006-11-29 | 上海中科合臣股份有限公司 | Preparation method of plant oil polyalcohol |
| CN101085943A (en) * | 2006-06-07 | 2007-12-12 | 上海桑迪精细化工研究所有限公司 | Method for preparing vegetable oil based polyatomic alcohol for hard bubble polyurethane |
| CN101016225A (en) * | 2007-02-07 | 2007-08-15 | 上海中科合臣股份有限公司 | Preparing method for high hydroxyl value plant oil polyhydric alcohol |
| CN101397250A (en) * | 2007-09-28 | 2009-04-01 | 上海爱默金山药业有限公司 | Preparation method of aliphatic ester polyol |
| US20100222541A1 (en) * | 2009-03-02 | 2010-09-02 | Joseph James Zupancic | Bio-based polyol |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449328A (en) * | 2013-09-23 | 2015-03-25 | 丹阳恒安化学科技研究所有限公司 | Production technology for low-VOC polyurethane home decoration paint |
| CN106748767A (en) * | 2015-11-19 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of low hydroxyl value plant oil polylol and preparation method thereof |
| CN106748767B (en) * | 2015-11-19 | 2020-03-17 | 中国石油化工股份有限公司 | Low-hydroxyl-value vegetable oil-based polyol and preparation method thereof |
| CN106947073A (en) * | 2016-01-07 | 2017-07-14 | 万华化学集团股份有限公司 | A kind of polyglycereol polyether natural oil polyols and preparation method thereof and a kind of polyurethane elastomer and preparation method thereof |
| CN106947073B (en) * | 2016-01-07 | 2019-02-05 | 万华化学集团股份有限公司 | A kind of polyglycereol polyether natural oil polyols and preparation method thereof and a kind of polyurethane elastomer and preparation method thereof |
| CN107151214A (en) * | 2016-03-03 | 2017-09-12 | 中国石油化工股份有限公司 | The method and device of tung oil polyalcohol is prepared under the conditions of a kind of hypergravity |
| CN107151210A (en) * | 2016-03-03 | 2017-09-12 | 中国石油化工股份有限公司 | A kind of method that tung oil polyalcohol is prepared under Ultrasonic Conditions |
| CN107151214B (en) * | 2016-03-03 | 2020-07-07 | 中国石油化工股份有限公司 | Method and device for preparing tung oil polyol under hypergravity condition |
| CN107151210B (en) * | 2016-03-03 | 2020-07-07 | 中国石油化工股份有限公司 | Method for preparing tung oil polyol under ultrasonic condition |
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Application publication date: 20130522 |