CN101805258B - Preparation method of novel vegetable oil polyol for polyurethane rigid foam - Google Patents
Preparation method of novel vegetable oil polyol for polyurethane rigid foam Download PDFInfo
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Abstract
The invention relates to a method for preparing polyol for polyurethane rigid foam from vegetable oil. Raw materials used in the method mainly comprise the following components: 100 parts by mass of vegetable oil, 5-85 parts by mass of modifier, 10-200 parts by mass of small molecular polyol and/or polyamine compounds, and 0-5000ppm of base catalyst based on the total mass of the vegetable oil, the modifier and the small molecular polyol or the polyamine compounds. The method mainly comprises the following reaction steps: (1) under the protection of inert gases, carrying out modification reaction on the vegetable oil by using the modifier; and (2) under the protection of inert gases, adding the small molecular polyol or the polyamine compounds and the base catalyst for carrying out reaction to prepare vegetable oil based polyol. The polyol prepared by the method of the invention has the advantages of good storage stability, high functionality and the like and can be widely applied to production of polyurethane rigid foam.
Description
Technical field
The present invention relates to a kind of preparation method of use for hard bubble of polyurethane polyvalent alcohol, more particularly, the present invention relates to a kind of method of using vegetables oil to prepare the use for hard bubble of polyurethane polyvalent alcohol.
Background technology
Hard polyurethane foam is widely used in the building energy conservation heat insulation field, and because of the advantage of the aspects such as environmental protection, regeneration and price, Chinese scholars constantly substitutes traditional petroleum base polyvalent alcohol take vegetables oil as the development of raw materials vegetable oil polyol.Except the Viscotrol C hydroxyl, other all hydroxyls not so the exploitation vegetable oil polyol mainly is that the vegetables oil structure is carried out modification, are introduced great amount of hydroxy group at the molecular chain of vegetables oil in the middle of present as can be known vegetables oil.
Chief component is fatty acid triglyceride in the vegetables oil, in its molecular structure, contain two keys and ester group isoreactivity group, at present all are to mainly being to introduce stronger functional group or the hydroxyl of polymerizing power in these active groups in the research of vegetable oil polyol, thereby obtain the vegetable oil-based polyols of suitable hydroxyl value and functionality.In the middle of present available document, mainly prepare vegetable oil polyol by alcoholysis, alkoxylate, ozone oxidation, epoxidation and the Lung biopsies such as hydroxylation, hydroformylation.
It mainly is the ester bond structure of utilizing in the vegetables oil that alcoholysis method prepares vegetable oil polyol.(the Journal of Applied Polymer Science such as K.H.BADRI, 2001,81,384-389) adopt plam oil as reaction raw materials, take potassium octanoate as catalyzer, adopting sorbyl alcohol and diethanolamine is that the alcoholysis agent is carried out alcoholysis to plam oil and prepared the high functionality vegetable oil polyol, product functionality 4.0-4.5, hydroxyl value 450-470mgKOH/g.(the Proc.Estonian Acad.Sci.Chem. such as Uldis Stirnaa, 2006,55 (2), 101-110.) take rapeseed oil as raw material, adopting trolamine or glycerine is the alcoholysis agent, has prepared the vegetable oil polyol of hydroxyl value at 290-310mgKOH/g under catalyst action.CN 1869184, CN 101016225 and CN 101029112A disclose and have selected respectively vegetables oil, vegetables oil and Epoxy oil mixture and refiltered oil as raw material, take aliphatic amide and Fatty Alcohol(C12-C14 and C12-C18) as the alcoholysis agent, in the presence of basic catalyst, prepare vegetable oil polyol, the hydroxyl value of product is used for hard polyurethane foam at 200-700mgKOH/g.By the synthetic vegetable oil polyol of the method, little because of the structural modification to lipid acid, can there be the problem of vegetable oil polyol product stock stability; From analysis of the molecular structure, the fatty acid carbon chain of product is suspension chain, and the consumption in hard bubbling is less, and foamy body is lower.
Alkoxylation process prepares vegetable oil polyol.(Utech Europe2009,31/3-2/4) such as Wouter Van Biesen take Viscotrol C as initiator, employing DMC is catalyzer, the castor oil polyhydric alcohol of the low VOC of the low smell of preparation.CN 101121784 discloses a kind of preparation method of the castor oil group polyether glycol for flexible PU foam, its technique mainly be by Viscotrol C under bimetallic catalyst (the sour zinc of six cyanogen cobalts (III)) effect, under 0-0.6MPa pressure, carry out alkoxylate at 100-200 ℃ with epoxy compounds and prepare the castor oil-base polyvalent alcohol.(Utech Europe 2009 31/3-2/4) uses vegetables oil and high functionality small molecular alcohol (sorbyl alcohol, sucrose) as initiator to K.Lorenz etc., prepares the vegetable oil polyol of high functionality under catalyst action with propylene oxide reaction.Though adopt the vegetable oil polyol of the method preparation to have sufficiently high functionality and hydroxyl value, but a large amount of petroleum derivatives such as propylene oxide and oxyethane that use in the integral system, renewable component concentration is low, petroleum derivative is relied on large, need simultaneously to adopt distinctive DMC catalysis system, the industrialization cost is higher.
Ozone oxidation prepares vegetable oil polyol.(CPI-Polyurethanes 2009 Technical Conference, 5/10-7/10.) such as Herman P.Benecke have developed vegetable oil polyol by the ozone oxidation mode.At first, under an acidic catalyst effect, by small molecular alcohol and ozone oxidation vegetables oil, animal tallow and the derivative thereof that contains primary hydroxyl; Then with small molecular alcohol the carboxylic acid of fatty acid derived is carried out esterification, thereby obtain the vegetable oil polyol of various functionality and hydroxyl value.Zoran S.Petrovic etc. (Biomacromolecules, 2005,6,713-719.) prepare the vegetable oil polyol that contains primary hydroxyl by ozone oxidation, the functionality of polyvalent alcohol is relevant with the content of the unsaturated link(age) that adopts vegetables oil.The functionality of the vegetable oil polyol that this legal system is standby is lower, and the at normal temperatures easy crystallization of product, and stability in storage is relatively poor, and needs the equipment such as ozone generator, and the industrialization cost is higher.
Epoxidation and hydroxylation prepare vegetable oil polyol.Method for hydroxylation prepared the method for vegetable oil polyol after US P 6433121 and US P 6107433 disclosed and adopted vegetables oil by first epoxidation.First peroxy acid is joined and form epoxidized vegetable oil in the vegetables oil, the epoxidation transformation efficiency is 91-94%, then adopts water or small molecular alcohol to form vegetable oil-based polyols under the fluoroboric acid katalysis.Yan Hong Hu etc. (Journal of Applied Polymer Science, 2002,84,591-597.) explored the technique for preparing vegetable oil polyol take rapeseed oil as raw material.Its synthesis technique mainly was divided into for two steps, at first adopted Peracetic Acid that two keys of Fatty Acid in Rapeseed Oil are carried out hydroxylation, then, adopted trolamine that hydroxylated rapeseed oil alcoholysis is increased hydroxyl value.Adopt the vegetable oil polyol hydroxyl value of this technique preparation can reach 360mgKOH/g, can be used as the raw material of hard polyurethane foam, but the stability in storage of this polyvalent alcohol is relatively poor, after storing one month, product becomes solid.The ester bond of CN1907944 comprehensive utilization vegetables oil and two key have prepared the high vegetable oil polyol product of functionality and hydroxyl value.Its select epoxy rapeseed oil under catalyst action with the nucleophilic reagent generation epoxy ring-opening reaction that contains reactive hydrogen, generate the tri-glyceride with hydroxyl, then add polyvalent alcohol or hydramine and carry out alcoholysis reaction, the preparation vegetable oil polyol.This operational path can take full advantage of two keys of vegetables oil, and temperature of reaction and pressure also can both be fit to large-scale explained hereafter, but and epoxy soybean oil suitability for industrialized production.But commonly used to solvent toluene in the epoxidised production process of vegetables oil, increase environmental pollution, the catalyzer that uses simultaneously all is an acidic catalyst, and is serious to equipment contaminate.Although functionality is enough high in theory, the product functionality of actual preparation is lower.
The standby vegetable oil polyol of hydroformylation legal system.WO 2004/096744A2 discloses and has adopted hydroformylation to prepare the method for vegetable oil polyol.Its preparation method is: introduce methylol at the unsaturated fatty acids position of double bond, this synthetic route need to be under the synthetic gas pressure of 3000-4000psig, and under about 100-150 ℃ temperature realization hydrogenation formyloxy.Then be about 1000-2000psig at hydrogen pressure, the hydrogenation temperature is about 150-180 ℃ of lower realization hydrogenation.This technique can be used the same catalyzer in the process of hydroformylation and catalytic hydrogenation; and can pass through the filtered and recycled Reusability; also avoided the waste discharge in the production process; be conducive to environment protection; methyl alcohol can repeat to be conducive to reduce industrial cost utilizing in this technological process simultaneously.Vegetable oil polyol functionality and hydroxyl value that this technique obtains are controlled, and product application is extensive.But reaction process is long, and is high to equipment requirements, needs special catalyst, and the industrialization cost is high.Because need very high pressure, present technical qualification also can't reach, thereby the large-scale application that has hindered it is in industry.
In view of the shortcoming of above-mentioned preparation vegetable oil polyol, the operational path that develops new synthetic vegetable oil polyol is significant.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of method of using vegetables oil to prepare the use for hard bubble of polyurethane polyvalent alcohol.
The present invention uses vegetables oil to prepare the raw material that uses in the method for use for hard bubble of polyurethane polyvalent alcohol mainly to comprise:
The vegetables oil of 100 mass parts;
The properties-correcting agent of 5～85 mass parts;
The small molecules polyvalent alcohol of 10～200 mass parts and/or polyamine compound; And
The alkaline catalysts based on vegetables oil, properties-correcting agent, small molecules polyvalent alcohol or polyamine compound quality summation of 0～5000ppm;
Wherein, reactions steps mainly comprises:
1) under the protection of rare gas element, use described properties-correcting agent that described vegetables oil is carried out modified-reaction; Then
2) under the protection of rare gas element, add described small molecules polyvalent alcohol and/or polyamine compound and described alkaline catalysts and react, make vegetable oil-based polyols.
In a preferred embodiment, the mass parts of described properties-correcting agent is 5～65, and the mass parts of described small molecules polyvalent alcohol and/or polyamine compound is 20～145, and the mass parts of described alkaline catalysts is 10-2000ppm.
In a preferred embodiment, described vegetables oil is selected from soybean oil, Rice pollard oil, Semen Maydis oil, peanut oil, sesame oil, sweet oil, plam oil, Thistle oil, sunflower seed oil, rapeseed oil, rapeseed oil, jatropha curcas oil, coptis wood oil or shinyleaf yellowhorn oil, or two kinds, two or more combination in them.
In a further preferred embodiment, described vegetables oil is selected from soybean oil, peanut oil, plam oil, rapeseed oil, jatropha curcas oil or coptis wood oil, or two kinds, two or more combination in them.
In preferred embodiment further, described vegetables oil is selected from soybean oil, plam oil or jatropha curcas oil, or two kinds, two or more combination in them.
In a preferred embodiment, described properties-correcting agent is the compound of double bond containing hydroxyl, carboxyl, acid anhydrides and the ester bonds such as maleic anhydride, maleic anhydride methyl esters, maleic anhydride ethyl ester, maleic anhydride butyl ester or fumaric acid.
In a further preferred embodiment, described properties-correcting agent is maleic anhydride.
In a preferred embodiment, described small molecules polyvalent alcohol and/or polyamine compound are functionality 2～6, the polyvalent alcohol of molecular weight 62～400 and/or polyamine compound, as include but not limited to ethylene glycol, glycol ether, propylene glycol, butyleneglycol, hexylene glycol, glycerine, TriMethylolPropane(TMP), thanomin, diethanolamine, trolamine, tetramethylolmethane, methylglucoside, Xylitol, sorbyl alcohol or sucrose, or two kinds, two or more combination in them.
In a preferred embodiment, described alkaline catalysts is potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, yellow soda ash, triethylene diamine, N-methylmorpholine, sodium methylate, sodium ethylate, potassium methylate, potassium ethylate, triethylamine or dimethylamine, or two kinds, two or more combination in them, or in the aqueous solution of above-claimed cpd one or more.
In a further preferred embodiment, described alkaline catalysts is the aqueous solution of potassium hydroxide or potassium hydroxide.
In a preferred embodiment, described rare gas element is nitrogen.
In a preferred embodiment, described step 1) temperature of reaction is 120-250 ℃, and the reaction times is 0.5-10 hour.
In a further preferred embodiment, described step 1) temperature of reaction is 160-240 ℃, and the reaction times is 2-6 hour.
In a preferred embodiment, step 2) temperature of reaction is 80-280 ℃, and the reaction times is 1-20 hour.
In a further preferred embodiment, step 2) temperature of reaction is 150-250 ℃, and the reaction times is 4-15 hour.
Reaction process of the present invention is:
1) under protection of inert gas, vegetables oil and properties-correcting agent are heated to certain temperature, under this temperature, keep for some time, obtain modified vegetable oil.Preferred reaction conditions is in rare gas element such as nitrogen, and temperature of reaction is 120-250 ℃, and the reaction times is 0.5-10 hour.
2) under protection of inert gas, add small molecules polyvalent alcohol and/or polyamine and alkaline catalysts, be heated to certain temperature reaction for some time namely to get product.Preferred reaction conditions is: temperature of reaction 80-280 ℃, reaction is 1-20 hour under this temperature, obtains the vegetable oil-based polyols product.
The present invention can obtain the polyvalent alcohol product of different hydroxyl values, different functionality, different viscosity by regulating different reaction raw materials and proportioning, is fit to the requirement of variant production.
The advantage of the inventive method is that technique is simple, and the products material wide material sources are renewable, and the hydroxyl value functionality of product is controlled, and aftertreatment is easy, is fit to large-scale industrialization production.
The vegetable oil-based polyols that makes by the inventive method has following advantage: the functionality of product and hydroxyl value are high, viscosity is controlled, molecular structure is reasonable.And the functionality of product, hydroxyl value, viscosity, molecular structure can be adjusted by selecting different raw materials, the proportioning between the feed change, change reaction times, adjustment temperature of reaction.
The high functionality of preparation method's gained of the present invention, high hydroxyl value plant oil polylol, the consumption in hard polyurethane foam can reach 100%, improves simultaneously the hydrophobic performance of polyurethane products, is adapted at widespread use in the hard polyurethane foam.
Polyvalent alcohol prepared by this method has stable storing, and functionality is high, the hydroxyl value advantages of higher, can be widely used in hard polyurethane foam production.
Embodiment
Following embodiment is used for further specifying the present invention, but does not limit the present invention.Except as otherwise noted, all umbers and per-cent is all in mass in an embodiment.
Embodiment 1
Soybean oil 100g
Maleic anhydride 30g
Glycerine 60g
Sorbyl alcohol 40g
Trolamine 30g
KOH 0.5g
Soybean oil and maleic anhydride are put in the reactor; under nitrogen protection; be warming up to 210 ℃ of reactions 180 minutes; drop to room temperature, add glycerine, sorbyl alcohol, trolamine and KOH, be warming up to 230 ℃ of insulations 6 hours; cooling namely gets product; product hydroxyl value 500mgKOH/g, viscosity 20000mPas stores 6 months under the product normal temperature precipitation and layering does not occur.
Embodiment 2
Peanut oil 100g
Maleic anhydride 50g
Glycol ether 40g
TriMethylolPropane(TMP) 60g
KOH 0.3g
Peanut oil and maleic anhydride are put in the reactor; under nitrogen protection; be warming up to 180 ℃ of reactions 360 minutes, drop to room temperature, add glycol ether, TriMethylolPropane(TMP) and KOH; be warming up to 220 ℃ of insulations 12 hours; cooling namely gets product, product hydroxyl value 480mgKOH/g; viscosity 12000mPas stores 6 months under the product normal temperature precipitation and layering does not occur.
Embodiment 3
Plam oil 100g
Maleic anhydride 20g
Glycerine 60g
KOH 0.2g
Plam oil and maleic anhydride are put in the reactor; under nitrogen protection; be warming up to 240 ℃ of reactions 540 minutes, drop to room temperature, add glycerine and KOH; be warming up to 240 ℃ of insulations 8 hours; cooling namely gets product, product hydroxyl value 400mgKOH/g; viscosity 2000mPas stores 6 months under the product normal temperature precipitation and layering does not occur.
Embodiment 4
Sunflower seed oil 100g
Maleic anhydride ethyl ester 40g
Ethylene glycol 40g
Tetramethylolmethane 20g
KOH 0.1g
Sunflower seed oil and maleic anhydride ethyl ester are put in the reactor; under nitrogen protection; be warming up to 190 ℃ of reactions 300 minutes, drop to room temperature, add ethylene glycol and KOH; be warming up to 160 ℃ of insulations 15 hours; cooling namely gets product, product hydroxyl value 420mgKOH/g; viscosity 10000mPas stores 6 months under the product normal temperature precipitation and layering does not occur.
Embodiment 5
Sweet oil 100g
Maleic anhydride 60g
Butyleneglycol 10g
Propylene glycol 20g
Diethanolamine 20g
Glycerine 40g
KOH 0.6g
Sweet oil and maleic anhydride are put in the reactor; under nitrogen protection; be warming up to 220 ℃ of reactions 150 minutes, drop to room temperature, add propylene glycol, butyleneglycol, diethanolamine, glycerine and KOH; be warming up to 210 ℃ of insulations 6 hours; cooling namely gets product, product hydroxyl value 520mgKOH/g; viscosity 15000mPas stores 6 months under the product normal temperature precipitation and layering does not occur.
Embodiment 6
Jatropha curcas oil 100g
Maleic anhydride 10g
Glycol ether 10g
Sorbyl alcohol 40g
KOH 0.8g
Jatropha curcas oil and maleic anhydride are put in the reactor; under nitrogen protection; be warming up to 230 ℃ of reactions 120 minutes, drop to room temperature, add glycol ether, sorbyl alcohol and KOH; be warming up to 250 ℃ of insulations 4 hours; cooling namely gets product, product hydroxyl value 620mgKOH/g; viscosity 30000mPas stores 6 months under the product normal temperature precipitation and layering does not occur.
The comparative example 7
Plam oil 100g
Glycerine 30g
KOH 0.2g
With plam oil, glycerine and KOH, be warming up to 240 ℃ of insulations 8 hours, cooling namely gets product, product hydroxyl value 240mgKOH/g, viscosity 2000mPas stores 1 month under the product normal temperature precipitation and layering occurs.
The comparative example 8
Jatropha curcas oil 100g
Glycol ether 10g
Sorbyl alcohol 25g
KOH 0.8g
With jatropha curcas oil, glycol ether, sorbyl alcohol and KOH, be warming up to 240 ℃ of insulations 6 hours, cooling namely gets product, product hydroxyl value 400mgKOH/g, viscosity 10000mPas.
Above-mentioned comparative example 7 and 8 is the vegetable oil polyols that adopt traditional alcoholysis method preparation.
Comparing embodiment 3 and comparative example 7 have been introduced the properties-correcting agent maleic anhydride because of the embodiment of the invention 3, the consumption of the small molecules polyol compound glycerine that can react is increased, and then the hydroxyl value degree of the finished product is increased.The product parameters of two embodiment of contrast can find out, the vegetable oil polyol product hydroxyl value by the embodiment of the invention 3 preparation is apparently higher than comparative example 7 vegetable oil polyol product hydroxyl value; In addition, the vegetable oil polyol product of the embodiment of the invention 3 preparations is compared comparative example 7 vegetable oil polyol product, and stability in storage improves.
Comparing embodiment 6 and comparative example 8 equally because embodiment 6 has introduced the properties-correcting agent maleic anhydride, increase the small molecules polyol compound glycol ether that can react and the consumption of sorbyl alcohol, and the hydroxyl value degree of the finished product are increased.The product parameters that contrasts these two embodiment can find out, the vegetable oil polyol product hydroxyl value by the embodiment of the invention 6 preparations is apparently higher than comparative example 8 vegetable oil polyol product hydroxyl value.
To sum up, it is good that the polyvalent alcohol of the inventive method preparation has stability in storage, and functionality is high, the hydroxyl value advantages of higher, can be widely used in hard polyurethane foam production.
Although above-described embodiment describes in detail technical scheme of the present invention, but technical scheme of the present invention is not limited to above embodiment, in the situation that does not break away from thought of the present invention and aim, any change that technical scheme of the present invention is done all will fall into claims limited range of the present invention.
Claims (15)
1. a method of using vegetables oil to prepare the use for hard bubble of polyurethane polyvalent alcohol is characterized in that, described method comprises:
The vegetables oil of 100 mass parts;
The properties-correcting agent of 5～85 mass parts;
The small molecules polyvalent alcohol of 10～200 mass parts and/or polyamine compound; And
The alkaline catalysts based on vegetables oil, properties-correcting agent, small molecules polyvalent alcohol and/or polyamine compound quality summation of 0～5000ppm;
Wherein, reactions steps is:
1) under the protection of rare gas element, use described properties-correcting agent that described vegetables oil is carried out modified-reaction; Then
2) under the protection of rare gas element, add described small molecules polyvalent alcohol and/or polyamine compound and described alkaline catalysts and react, namely make vegetable oil-based polyols;
Wherein, described properties-correcting agent is maleic anhydride, maleic anhydride methyl esters, maleic anhydride ethyl ester, maleic anhydride butyl ester or fumaric acid, or two kinds, two or more combination in them.
2. method according to claim 1 is characterized in that, described properties-correcting agent is maleic anhydride.
3. method according to claim 1, it is characterized in that, described properties-correcting agent is 5～65 mass parts, described small molecules polyvalent alcohol and/or polyamine compound are 20～145 mass parts, and described alkaline catalysts based on vegetables oil, properties-correcting agent, small molecules polyvalent alcohol and/or polyamine compound quality summation is 10-2000ppm.
4. method according to claim 1, it is characterized in that, described vegetables oil is selected from soybean oil, Rice pollard oil, Semen Maydis oil, peanut oil, sesame oil, sweet oil, plam oil, Thistle oil, sunflower seed oil, rapeseed oil, rapeseed oil, jatropha curcas oil, coptis wood oil or shinyleaf yellowhorn oil, or two kinds, two or more combination in them.
5. method according to claim 4 is characterized in that, described vegetables oil is selected from soybean oil, peanut oil, plam oil, rapeseed oil, jatropha curcas oil or coptis wood oil, or two kinds, two or more combination in them.
6. method according to claim 5 is characterized in that, described vegetables oil is selected from soybean oil, plam oil or jatropha curcas oil, or two kinds, two or more combination in them.
7. method according to claim 1 is characterized in that, described small molecules polyvalent alcohol and/or polyamine compound are polyvalent alcohol and/or the polyamine of functionality 2～6, molecular weight 62～400.
8. method according to claim 7, it is characterized in that, described small molecules polyvalent alcohol and/or polyamine compound are ethylene glycol, glycol ether, propylene glycol, butyleneglycol, hexylene glycol, glycerine, TriMethylolPropane(TMP), thanomin, diethanolamine, trolamine, tetramethylolmethane, methylglucoside, Xylitol, sorbyl alcohol or sucrose, or two kinds, two or more combination in them.
9. method according to claim 1, it is characterized in that, described alkaline catalysts is potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, yellow soda ash, triethylene diamine, N-methylmorpholine, sodium methylate, sodium ethylate, potassium methylate, potassium ethylate, triethylamine or dimethylamine, or two kinds, two or more combination in them, or their aqueous solution.
10. method according to claim 9 is characterized in that, described alkaline catalysts is the aqueous solution of potassium hydroxide or potassium hydroxide.
11. method according to claim 1 is characterized in that, described rare gas element is nitrogen.
12. each described method is characterized in that according to claim 1-11, the temperature of reaction of modified-reaction is 120-250 ℃ in the described step 1), and the reaction times is 0.5-10 hour.
13. method according to claim 12 is characterized in that, the temperature of reaction of modified-reaction is 160-240 ℃ in the described step 1), and the reaction times is 2-6 hour.
14. each described method is characterized in that step 2 according to claim 1-11) temperature of reaction be 80-280 ℃, the reaction times is 1-20 hour.
15. method according to claim 14 is characterized in that step 2) temperature of reaction be 150-250 ℃, the reaction times is 4-15 hour.
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| CN102167808A (en) * | 2011-03-08 | 2011-08-31 | 江苏绿源新材料有限公司 | Method for preparing bio-based polyether glycol from jatropha curcas oil |
| CN102167809B (en) * | 2011-03-08 | 2012-08-01 | 江苏绿源新材料有限公司 | Method for preparing biobased polyether polylol from vegetable oil |
| CN103360596A (en) * | 2012-03-28 | 2013-10-23 | 江苏卡特新能源有限公司 | Method for producing plant polyalcohol by utilizing waste oil |
| CN103087304B (en) * | 2013-01-18 | 2015-02-11 | 张家港南光化工有限公司 | Production method of polyester polyol |
| CN103421162B (en) * | 2013-08-12 | 2015-04-08 | 江西科技师范大学 | Preparation method for pure rapeseed oil-based waterborne polyurethane resin |
| CN108164677A (en) * | 2018-01-23 | 2018-06-15 | 广州市聚科聚氨酯有限公司 | Soybean oil polyol prepares and its application in polyurethane foam |
| CN111269759B (en) * | 2018-12-04 | 2022-04-19 | 北京化工大学 | Method for preparing castor oil-based polyols with different hydroxyl values |
| CN113060992B (en) * | 2019-05-21 | 2022-03-22 | 烟台大学 | Foam concrete preparation method based on utilization of tanning chrome-containing leather scraps and coal gangue |
| CN110982414B (en) * | 2019-12-18 | 2021-07-23 | 万华化学集团股份有限公司 | Food contact water-based wood coating and preparation method thereof |
| CN112011038A (en) * | 2020-08-25 | 2020-12-01 | 江苏德励达新材料有限公司 | Process for preparing aromatic polyester polyol with good pentane compatibility |
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| 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 |
| CN101195577A (en) * | 2007-12-13 | 2008-06-11 | 天津工业大学 | Method for preparing polylol with soybean oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN101195577A (en) * | 2007-12-13 | 2008-06-11 | 天津工业大学 | Method for preparing polylol with soybean oil |
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