CN106957230A - A kind of utilization supercritical CO 2 prepares the method and device of tung oil polyalcohol - Google Patents
A kind of utilization supercritical CO 2 prepares the method and device of tung oil polyalcohol Download PDFInfo
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- CN106957230A CN106957230A CN201610012120.2A CN201610012120A CN106957230A CN 106957230 A CN106957230 A CN 106957230A CN 201610012120 A CN201610012120 A CN 201610012120A CN 106957230 A CN106957230 A CN 106957230A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Supercritical CO is utilized the invention discloses one kind2The method and device of tung oil polyalcohol is prepared, tung oil, hydroxylating agent, hydrogenperoxide steam generator are proportionally added into high-pressure reactor, stirring is opened, and be passed through into high-pressure reactor CO2, make CO2In supercriticality, 8-12h is reacted at 30-50 DEG C；Reaction system is passed through in expansion separator by reaction after terminating, and CO is made at ambient pressure2Reclaimed and reused after gasification；Finally by remaining liq mixture by washing, vacuum distillation obtains tung oil polyol product.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, epoxidised while add hydroxylating agent, and utilizes supercritical CO2Tung oil polyalcohol is prepared, the generation of crosslinking side reaction can be effectively prevented from, the mass transfer rate of heterogeneous reaction is improved, it is not necessary to uses catalyst, and the consumption of hydrogen peroxide and hydroxylating agent can be reduced, save production cost.
Description
Technical field
The invention belongs to polyurethane material field, and in particular to one kind utilizes supercritical CO2Prepare the method and device of tung oil polyalcohol.
Background technology
The characteristics of polyurethane material is due to good mechanical performance with shaping is easy to, has been widely used in industry and daily life.Main raw material(s) for producing polyurethane includes isocyanates, polyalcohol and other additives, and the ratio of wherein polyalcohol account for more than 50%.In industrial processes, polyalcohol is mainly used in polyurethane field, thus polyurethane industries among others influence factor be also polyalcohol market major influence factors.Polyalcohol can be divided into PPG and PEPA by molecular structure, wherein, PPG is occupied an leading position in the market, occupies more than the 70% of whole polyalcohol demand.
Generally, polyalcohol is to extract to prepare from oil.And oil is used as non-renewable resources, scarcity causes the continuous rise of its price, and cause the price continuous rise of the primary raw material of the polynary alcohol production such as downstream product expoxy propane, oxirane, and according to current depletion rate, petroleum resources are depleted eventually.Therefore, from sustainable development and the angle of enterprise competitiveness, the new material and new technology that can substitute petroleum base polyethers are found as strategic development task.
The U.S. is the major producing country of soybean oil in the world, and in addition to edible, the scientific research institution in the U.S. is also actively working to develop the various chemical products by raw material of soybean oil, to substitute petroleum-based chemicals.Concentrate on recently using the unsaturated bond in soybean oil strand, by the modification to double bond, vegetable oil is occurred epoxidation, hydroxylating, so as to prepare soybean oil polyol.The advantage of the method is that reaction temperature is relatively low（40-70℃）, product qualities, color and luster are good, so obtained extensive concern.
The Z.S. in kansas, U.S.A (Kansas) polymer research center
Petrovic etc. is reacted with peroxy acid with soybean oil, is prepared for epoxidized soybean oil, double bond is changed into epoxy radicals；Then under the catalytic action of effective catalyst tetrafluoro boric acid with water and alcohol ring-opening reaction occurs for epoxidized soybean oil, prepare the vegetable oil polyol containing hydroxyl, the hydroxyl value of polyalcohol is 110-213mgKOH/g, and viscosity is 1000-7000mPas, and conversion ratio is up to 85%-95%.
US20070123725 provides a kind of method for preparing soybean oil polyol, includes the epoxidation and hydroxylation procedures of polyunsaturated vegetable oil, forms vegetable oil-based polyether polyol.First, the polyunsaturated vegetable oils such as soybean oil or rapeseed oil and organic acid and hydrogenperoxide steam generator are reacted, forms epoxidized vegetable oil, the mixed solution of epoxidized vegetable oil and first alcohol and water is then subjected to ring-opening reaction generation vegetable oil polyol.
US20060041157 describes the method for preparing soybean oil polyol, vegetable oil including making PART EPOXY reacts under catalysts conditions with Ring Opening Reagent, oligomeric vegetable oil polylol is formed, Ring Opening Reagent includes small molecule polyol, vegetable oil polyol or other polyols.The degree of functionality of oligomeric vegetable oil polyalcohol is 1-6, and hydroxyl value is 20-300mgKOH/g.
Tung oil is a kind of important raw material of industry and traditional exporting.At present, the annual production of China's tung oil accounts for 35% or so of world's tung oil yield up to more than 100,000 tons.Therefore, study tung oil and make more Product industrializations relevant with tung oil that there is special significance.But, high-quality vegetable oil polyol is prepared using tung oil, because tung oil degree of unsaturation is higher, and be unique polyunsaturated vegetable oil with conjugated double bond in nature, iodine number reaches more than 170, wherein more than 85% unsaturated bond is carbon carbon conjugated triene key, so tung oil prepare polyalcohol it is epoxidised during because the presence of conjugated double bond makes epoxide group reactivity higher, poor selectivity, easily occurs side reaction, so as to generate macromolecules cross-linking product, viscosity is caused to sharply increase, it is normally solid at room temperature, further synthesis of polyurethane material can not be used for.Research Literature（Such as Epoxidation of Natural
Triglycerides with Ethylmethyldioxirane,《Journal of the American Oil Chemists' Society》, 1996,73:461-464）Different vegetable oil are investigated, such as corn oil, soybean oil, sunflower oil, cottonseed oil, the epoxidation process of tung oil polyunsaturated vegetable oil, it is again seen that only the tung oil with conjugated double bond there occurs cross-linking reaction during epoxidised, viscosity is caused to increased dramatically, it is impossible to for preparing polyurethane material.
The content of the invention
In view of the shortcomings of the prior art, supercritical CO is utilized the invention provides one kind2Prepare the method and device of tung oil polyalcohol.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, epoxidised while add hydroxylating agent, and utilizes supercritical CO2Tung oil polyalcohol is prepared, the generation of crosslinking side reaction can be effectively prevented from, the mass transfer rate of heterogeneous reaction is improved, it is not necessary to uses catalyst, and the consumption of hydrogen peroxide and hydroxylating agent can be reduced, save production cost.
The present invention utilizes supercritical CO2The method for preparing tung oil polyalcohol, including following content：Tung oil, hydroxylating agent, hydrogenperoxide steam generator are proportionally added into high-pressure reactor, stirring is opened, and be passed through into high-pressure reactor CO2, make CO2In supercriticality, 8-12h is reacted at 30-50 DEG C；Reaction system is passed through in expansion separator by reaction after terminating, and CO is made at ambient pressure2Reclaimed and reused after gasification；Finally by remaining liq mixture by washing, tung oil polyol product is made in vacuum distillation.
In the present invention, before tung oil, hydroxylating agent, hydrogenperoxide steam generator are added into high-pressure reactor, first a certain amount of bicarbonate is put into high-pressure reactor, described bicarbonate can be the one or more in sodium acid carbonate, saleratus, lithium bicarbonate etc., preferably sodium acid carbonate, consumption is 0.01-0.05 times of tung oil quality.Bicarbonate plays stabilizer, and the decomposition of peroxycarbonic acid can be effectively prevented after adding in advance, improves the utilization rate of hydrogen peroxide.
Hydroxylating agent of the present invention can be alcohols or alcamines, and consumption is 0.2-0.8 times of tung oil quality.Wherein one or more of the alcohols hydroxylating agent in methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol, glycerine, butanol, BDO, pentaerythrite, xylitol, sorbierite etc., preferably butanol；One or more of the alcamines hydroxylating agent in monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, monoethanolamine, diethanol amine, triethanolamine etc., preferably triethanolamine.
Hydrogenperoxide steam generator of the present invention plays a part of oxidant, makes CO2It is oxidized to peroxycarbonic acid.The concentration of hydrogenperoxide steam generator is higher, reacts more violent, system heat release is serious, easily occurs side reaction, so the concentration of selection hydrogenperoxide steam generator is 20wt%-60wt%, consumption is 0.4-0.8 times of tung oil quality.
It is of the present invention to make CO2Condition as critical fluids is：It is 7.8-9.5MPa to make reaction system pressure, and is warming up to 30-50 DEG C.
Washing temperature of the present invention is 50-80 DEG C, to prevent that emulsion from occurring in system.Described vacuum distillation is the hydroxylating agent and residual moisture in removing system under the conditions of pressure 1000-3000Pa, 60-120 DEG C of temperature, product moisture content is less than 0.1wt%.
Tung oil polyalcohol of the present invention is prepared by the invention described above method.The hydroxyl value of prepared tung oil polyalcohol is 120-270mgKOH/g, and acid number is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 93%, available for preparing polyurethane material.
The present invention utilizes supercritical CO2Prepare the device of tung oil polyalcohol, including CO2Gas bomb, high-pressure reactor, tung oil storage tank, hydroxylating agent storage tank, hydrogenperoxide steam generator storage tank, expansion separator, washing kettle, distillation still and product storage tank.
Tung oil is carbon carbon conjugated triene key due in molecule more than 85% unsaturated bond, make epoxide group reactivity higher during polyalcohol is prepared, poor selectivity, easily occurs side reaction, so as to generate macromolecules cross-linking product, viscosity is caused to sharply increase, it is impossible to for further synthesis of polyurethane material.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, epoxidised while add hydroxylating agent, and utilizes supercritical CO2Tung oil polyalcohol is prepared, the generation of crosslinking side reaction can be effectively prevented from, prepared tung oil polyalcohol has the advantages that raw material is renewable, non-toxic and biological degradability is good, belong to environment-friendly biopolyol compared with petroleum-based polyols.
The present invention introduces supercritical fluid CO during the course of the reaction2, it is both reaction medium, is reactant again, it can be with hydrogen peroxide effect generation peroxycarbonic acid intermediate, and peroxycarbonic acid makes the conjugated double bond in tung oil be converted into epoxy bond, while discharging CO2, therefore while epoxy bond is generated, CO2Do not consume, recyclable after reaction, recycling.Supercritical CO2There is advantages below as reaction medium：The mass transfer rate of heterogeneous reaction is substantially improved, without using catalyst, and the consumption of hydrogen peroxide and hydroxylating agent can be reduced, save production cost；Realize the epoxidation under the conditions of no carboxylic acid, it is to avoid the etching problem of reactor, reduce the degree of crosslinking side reaction；With environment-friendly CO2Supercritical fluid replaces hazardous solvent, is a kind of reaction technology of environmental protection.
Brief description of the drawings
Fig. 1 is the Structure and Process schematic diagram of tung oil polyols preparation device of the present invention；
Wherein：1-CO2Gas bomb, 2- high-pressure reactors, 3- tung oil storage tanks, 4- hydroxylating agent storage tanks, 5- hydrogenperoxide steam generator storage tanks, 6- expansion separators, 7- washing kettles, 8- distillation stills, 9- product storage tanks.
Fig. 2 is the infrared spectrogram of tung oil polyalcohol prepared by the present invention.
Embodiment
The invention will be further described with reference to the accompanying drawings and examples.In the present invention, wt% represents mass fraction.
The present invention utilizes supercritical CO2The device of tung oil polyalcohol is prepared as shown in figure 1, including CO2Gas bomb 1, high-pressure reactor 2, tung oil storage tank 3, hydroxylating agent storage tank 4, hydrogenperoxide steam generator storage tank 5 expand separator 6, washing kettle 7, distillation still 8 and product storage tank 9.Tung oil, hydroxylating agent and hydrogenperoxide steam generator in tung oil storage tank 3, hydroxylating agent storage tank 4, hydrogenperoxide steam generator storage tank 5 is added sequentially in high-pressure reactor 2 in proportion.Then CO is passed through2Gas bomb 1 is passed through CO into high-pressure reactor2, make CO2In supercriticality；Stirring is opened, controlling reaction temperature is 30-50 DEG C, reacts 8-12h；Reaction system is passed through in expansion separator 6 by reaction after terminating, and CO is made at ambient pressure2Reclaimed and reused after gasification；Remaining liq mixture finally is passed through into washing kettle 7 to be washed, then through the vacuum distillation of distillation still 8, obtained in tung oil polyol product feeding product storage tank 9.
The hydroxyl value of tung oil polyalcohol prepared by the present invention is determined according to the phthalic anhydride esterification method in GB/T 12008.3-2009, and acid number is determined according to GB/T 12008.5-2010 methods, and viscosity is determined according to the rotation viscometer method in GB/T 12008.7-2010.
Embodiment 1
500g tung oil, 250g butanol, 300g concentration are proportionally added into autoclave for 30% hydrogenperoxide steam generator.CO is passed through into autoclave2, and 8.5MPa is pressurized to, 40 DEG C are warming up to, makes CO2In supercriticality.Stirring is opened, controlling reaction temperature is 40 DEG C, is stopped after reaction 10h.Reaction system is passed into expansion separator, pressure is down to normal pressure, supercritical CO2Phase is changed into conventional gas phase CO2, through collecting and reusing after discharge.Remaining liq mixture is passed through in washing kettle, through 70 DEG C of hot wash products 3 times；Then product after washing is squeezed into distillation still, distills 2h at 2000Pa, 80 DEG C, obtain tung oil polyol product.After testing, hydroxyl value is 244mgKOH/g, viscosity 7700mPas, acid number 0.24mgKOH/g, and moisture is less than 0.1wt%, and yield is 94.3%, available for preparing hard polyurethane foam product.
Embodiment 2
500g tung oil, 150g butanol, 200g concentration are proportionally added into autoclave for 40% hydrogenperoxide steam generator.CO is passed through into autoclave2, and 7.8MPa is pressurized to, 30 DEG C are warming up to, makes CO2In supercriticality.Stirring is opened, controlling reaction temperature is 30 DEG C, is stopped after reaction 12h.Reaction system is passed into expansion separator, pressure is down to normal pressure, supercritical CO2Phase is changed into conventional gas phase CO2, through collecting and reusing after discharge.Remaining liq mixture is passed through in washing kettle, through 50 DEG C of hot wash products 4 times；Then product after washing is squeezed into distillation still, distills 2h at 3000Pa, 60 DEG C, obtain tung oil polyol product.After testing, hydroxyl value is 187mgKOH/g, viscosity 6400mPas, acid number 0.24mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.4%, available for preparing hard polyurethane foam product.
Embodiment 3
500g tung oil, 350g butanol, 400g concentration are proportionally added into autoclave for 20% hydrogenperoxide steam generator.CO is passed through into autoclave2, and 9.5MPa is pressurized to, 50 DEG C are warming up to, makes CO2In supercriticality.Stirring is opened, controlling reaction temperature is 50 DEG C, is stopped after reaction 8h.Reaction system is passed into expansion separator, pressure is down to normal pressure, supercritical CO2Phase is changed into conventional gas phase CO2, through collecting and reusing after discharge.Remaining liq mixture is passed through in washing kettle, through 80 DEG C of hot wash products 3 times；Then product after washing is squeezed into distillation still, distills 2h at 1000Pa, 100 DEG C, obtain tung oil polyol product.After testing, hydroxyl value is 228mgKOH/g, viscosity 8100mPas, acid number 0.25mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.9%, available for preparing hard polyurethane foam product.
Embodiment 4
First 10g sodium acid carbonates are put into autoclave, are then driven into 500g tung oil, 250g butanol, 300g concentration in autoclave for 30% hydrogenperoxide steam generator, the other the same as in Example 2.After testing, hydroxyl value is 220mgKOH/g, viscosity 6100mPas, acid number 0.22mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.6%, available for preparing hard polyurethane foam product.
Embodiment 5
First 15g saleratus is put into autoclave, is then driven into 500g tung oil, 250g butanol, 300g concentration in autoclave for 30% hydrogenperoxide steam generator, the other the same as in Example 2.After testing, hydroxyl value is 226mgKOH/g, viscosity 6300mPas, acid number 0.23mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.8%, available for preparing hard polyurethane foam product.
Embodiment 6
Butanol is replaced with into ethanol, the other the same as in Example 2.After testing, hydroxyl value is 157mgKOH/g, viscosity 9800mPas, acid number 0.26mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.1%, available for preparing hard polyurethane foam product.
Embodiment 7
Butanol is replaced with into triethanolamine, the other the same as in Example 2.After testing, hydroxyl value is 162mgKOH/g, viscosity 10400mPas, acid number 0.23mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.2%, available for preparing polyurethane products.
Comparative example 1
Using treatment process condition same as Example 1, difference is to be added without hydroxylating agent.The viscosity 350000 of product
MPas, because product viscosity is excessive and can not dissolve, it is impossible to further carry out hydroxylating, therefore product is not used to prepare polyurethane products.
Comparative example 2
Using treatment process condition same as Example 1, difference is to be added without supercritical CO2And hydroxylating agent, and add petroleum ether 300g（Play diluent effect）.Due to epoxidation and hydroxylating not occurring, alcoholic extract hydroxyl group is not formed, therefore product is not used to prepare polyurethane products.
Comparative example 3
Using treatment process condition same as Example 1, difference is to prepare polyalcohol using soybean oil.After testing, hydroxyl value is 6.6mgKOH/g, and because no generation hydroxylating, hydroxyl value are too low, therefore product is not used to prepare polyurethane products.
Comparative example 4
Using treatment process condition same as Example 1, difference is to prepare polyalcohol using Jatropha curcas oil.After testing, hydroxyl value is 4.7mgKOH/g, and because no generation hydroxylating, hydroxyl value are too low, therefore product is not used to prepare polyurethane products.
Claims (11)
1. one kind utilizes supercritical CO2The method for preparing tung oil polyalcohol, it is characterised in that including following content：Tung oil, hydroxylating agent, hydrogenperoxide steam generator are proportionally added into high-pressure reactor, stirring is opened, and be passed through into high-pressure reactor CO2, make CO2In supercriticality, 8-12h is reacted at 30-50 DEG C；Reaction system is passed through in expansion separator by reaction after terminating, and CO is made at ambient pressure2Reclaimed and reused after gasification；Finally by remaining liq mixture by washing, vacuum distillation obtains tung oil polyol product.
2. according to the method described in claim 1, it is characterised in that：Before reaction mass is added into high-pressure reactor, first a certain amount of bicarbonate is put into high-pressure reactor.
3. method according to claim 2, it is characterised in that：One or more of the bicarbonate in sodium acid carbonate, saleratus, lithium bicarbonate, consumption is 0.01-0.05 times of tung oil quality.
4. according to the method described in claim 1, it is characterised in that：Described hydroxylating agent is alcohols or alcamines, and consumption is 0.2-0.8 times of tung oil quality.
5. method according to claim 4, it is characterised in that：One or more of the described alcohols hydroxylating agent in methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol, glycerine, butanol, 1,4- butanediols, pentaerythrite, xylitol, sorbierite etc..
6. method according to claim 4, it is characterised in that：One or more of the described alcamines hydroxylating agent in monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, monoethanolamine, diethanol amine, triethanolamine etc..
7. according to the method described in claim 1, it is characterised in that：The concentration of described hydrogenperoxide steam generator is 20wt%-60wt%, and consumption is 0.4-0.8 times of tung oil quality.
8. according to the method described in claim 1, it is characterised in that：It is described to make CO2Condition as critical fluids is：It is 7.8-9.5MPa to make reaction system pressure, and is warming up to 30-50 DEG C.
9. method according to claim 1, it is characterised in that：Described washing temperature is 50-80 DEG C；Described vacuum distillation is the hydroxylating agent and residual moisture in removing system under the conditions of pressure 1000-3000Pa, 60-120 DEG C of temperature, product moisture content is less than 0.1wt%.
10. tung oil polyalcohol prepared by any methods describeds of claim 1-9, it is characterised in that：Product hydroxyl value is 120-270mgKOH/g, and acid number is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 92%, available for preparing polyurethane material.
11. supercritical CO is utilized described in claim 12Prepare the device of tung oil polyalcohol, it is characterised in that：Including CO2Gas bomb, high-pressure reactor, tung oil storage tank, hydroxylating agent storage tank, hydrogenperoxide steam generator storage tank expand separator, washing kettle, distillation still and product storage tank.
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Citations (2)
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| CN101456849A (en) * | 2008-12-30 | 2009-06-17 | 清华大学 | Method and apparatus for preparing epoxypropane by catalyzing propone epoxidation at supercritical condition |
| CN103274930A (en) * | 2013-06-20 | 2013-09-04 | 南京工业大学 | Vegetable oil polyol preparation method by using continuous method |
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- 2016-01-11 CN CN201610012120.2A patent/CN106957230B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456849A (en) * | 2008-12-30 | 2009-06-17 | 清华大学 | Method and apparatus for preparing epoxypropane by catalyzing propone epoxidation at supercritical condition |
| CN103274930A (en) * | 2013-06-20 | 2013-09-04 | 南京工业大学 | Vegetable oil polyol preparation method by using continuous method |
Non-Patent Citations (2)
| Title |
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| JUMAT SALIMON,ET AL.: "Chemically modified biolubricant basestocks from epoxidized oleic acid: Improved low temperature properties and oxidative stability", 《JOURNAL OF SAUDI CHEMICAL SOCIETY》 * |
| M.A.MOSIEWICKI,ET AL.: "Polyurethanes From Tung Oil: Polymer Characterization and Composites", 《POLYMER ENGINEERING AND SCIENCE》 * |
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