CN106957227A - A kind of method for producing tung oil polyalcohol and by-product glycerol - Google Patents
A kind of method for producing tung oil polyalcohol and by-product glycerol Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- 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
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Abstract
The invention discloses a kind of method for producing tung oil polyalcohol and by-product glycerol,（1）It is added to after tung oil, methanol and base catalyst are mixed in proportion in autoclave, carries out tung oil methyl ester reaction, lower floor's glycerine is isolated after reaction, tung oil methyl ester is obtained；（2）Tung oil methyl ester and carboxylic acid, acid catalyst, hydroxylating agent, deionized water are mixed in proportion, 35-45 DEG C is warming up to；Stirring is lower to be added dropwise hydrogenperoxide steam generator, and control rate of addition makes reaction maintain after 40-65 DEG C, completion of dropping, maintenance reaction temperature 3-5h；（3）Reaction terminates rear stratification, isolates aqueous phase, oil phase is neutralized, washing, vacuum distillation, obtain tung oil polyalcohol.The present invention can improve epoxide group reactivity feature using the conjugated double bond of tung oil, tung oil methyl ester is carried out first, isolate glycerine, tung oil polyalcohol is prepared by raw material of tung oil methyl ester again, hydroxylating agent is added in epoxidation simultaneously, crosslinking side reaction can be prevented effectively from, the economy of whole technique is greatly improved.
Description
Technical field
The invention belongs to polyurethane material field, and in particular to a kind of method for producing tung oil polyalcohol and by-product glycerol.
Background technology
With petering out for Global Oil fossil resource, the development and utilization of biomass resource receives much concern.Vegetable oil is the triglycerides of the Long carbon chain acid containing double bond, and it is widely distributed in nature, and species is various, wherein common includes tung oil, soybean oil, linseed oil, corn oil, rapeseed oil, peanut oil, olive oil, palm oil, castor oil etc..Special construction and degradability, polymer therefrom not only low cost, and environmentally friendly that vegetable oil has by it, are widely used in the multiple fields such as polyurethane, biodiesel, coating, bio-medical.
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, by the polyunsaturated vegetable oils such as soybean oil or rapeseed oil and organic acid and hydroperoxidation, epoxidized vegetable oil is formed, 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, the invention provides a kind of method for producing tung oil polyalcohol and by-product glycerol.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, tung oil methyl ester is carried out first, isolate glycerine, then tung oil polyalcohol is prepared by raw material of tung oil methyl ester, epoxidised while adding hydroxylating agent, the generation of crosslinking side reaction can be effectively prevented from, and forms tung oil polyol product, the economy of whole production technology is significantly improved.
The method of present invention production tung oil polyalcohol and by-product glycerol, including following content：（1）It is added to after tung oil, methanol and base catalyst are mixed in proportion in autoclave, carries out tung oil methyl ester reaction, product isolates lower floor's glycerine after reaction, then through washing, vacuum distillation, obtains tung oil methyl ester；（2）Tung oil methyl ester and carboxylic acid, acid catalyst, hydroxylating agent, deionized water are mixed in proportion, 35-45 DEG C is warming up to；Lower dropwise addition hydrogenperoxide steam generator is stirred vigorously, control rate of addition makes reaction maintain after 40-65 DEG C, completion of dropping, maintenance reaction temperature 3-5h；（3）Reaction terminates rear stratification, isolates aqueous phase, oil phase is neutralized, washing, vacuum distillation, obtain tung oil polyol product.
Step（1）Described methanol and the alcohol oil quality ratio of tung oil are 0.1:1-0.3:1.Described base catalyst is the one or more in potassium hydroxide, NaOH, lithium hydroxide, calcium hydroxide etc., preferably potassium hydroxide；The consumption of base catalyst is the 0.5%-1.5% of tung oil quality.
Step（1）Described tung oil methyl esterization reaction is 55-65 DEG C of progress under agitation, and the reaction time is 15-30min.
Step（1）Described washing temperature is 40-60 DEG C；Vacuum distillation is the residual methanol and moisture in removing system under the conditions of pressure 1000-3000Pa, 50-80 DEG C of temperature.
Step（2）Described acid catalyst is the one or more in sulfuric acid, phosphoric acid, hydrochloric acid, sulfonic acid ion exchange resin etc., preferably sulfuric acid；Consumption is the 0.01%-1.0% of tung oil methyl ester quality.
Step（2）Described carboxylic acid can be the one or more in formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, phenylacetic acid etc., preferably formic acid.Carboxylic acid can be with hydrogenperoxide steam generator reaction generation peroxycarboxylic acid, peroxycarboxylic acid makes the conjugated double bond in tung oil methyl ester be converted into epoxy bond, discharge carboxylic acid simultaneously, therefore while epoxy bond is generated, carboxylic acid is not consumed, but very few carboxylic acid content will cause system reaction rate slack-off, so it is 0.05 to control carboxylic acid and the mass ratio of tung oil methyl ester:1-0.5:1.
Step（2）Described hydroxylating agent can be alcohols or alcamines, and consumption is 0.5-2 times of tung oil methyl ester quality.One or more of the wherein described 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.
Step（2）The consumption of the deionized water is 0.01-0.2 times of tung oil methyl ester quality, and the addition of deionized water can prevent the esterification of initial reaction stage carboxylic acid and hydroxylating agent, it is to avoid the consumption of carboxylic acid, increases double bond conversion rate.
Step（2）The hydrogenperoxide steam generator plays a part of oxidant, carboxylic acid is oxidized to peroxy acid.The concentration of hydrogen peroxide is higher, reacts more violent, system heat release is serious, easily occurs side reaction, so selection hydrogenperoxide steam generator concentration is 20wt%-60wt%, consumption is 0.6-1.2 times of tung oil methyl ester quality.
Step（3）The neutralization reaction can use ammoniacal liquor, sodium carbonate or sodium acid carbonate, preferably use the sodium bicarbonate aqueous solution that concentration is 5wt%-20wt% and neutralize.Described washing temperature 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%.
What tung oil polyalcohol of the present invention was prepared by the invention described above method.Prepared tung oil polyol 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.
Tung oil is carbon carbon conjugated triene key due in molecule more than 85% unsaturated bond, makes 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.It is direct using vegetable oil as raw material compared in traditional plant oil polyalcohol preparation technology, the present invention carries out esterification first by raw material of tung oil, glycerine in tung oil is cemented out, isolate the glycerin by-products of high added value, then vegetable oil polyol is prepared by raw material of tung oil methyl ester, because the conjugated double bond of tung oil methyl ester still has the characteristics of improving epoxide group reactivity（The conjugated double bond structures that tung oil methyl esterization reaction will not be destroyed in tung oil）, the generation of crosslinking side reaction can be avoided, therefore epoxidised while addition hydroxylating agent, can be effectively prevented from the generation of crosslinking side reaction, formation meets desired tung oil polyol product, it is adaptable to the preparation of polyurethane material.In addition, in system add 1 ton of methanol about it is replaceable go out 0.4-0.5 tons of glycerol products, and excessive methanol can be recycled and reused by distillation technique, the market price of glycerine is 7500-8000 yuan/ton, and methanol is about 3000 yuan/ton, so present invention process can greatly improve the economy of whole technique.
Tung oil polyalcohol prepared by the present invention has the advantages that raw material is renewable, non-toxic and biological degradability is good, belongs to environment-friendly biopolyol compared with petroleum-based polyols.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of tung oil polyalcohol prepared by the present invention.
Embodiment
The inventive method is described further with reference to embodiment.In the present invention, wt% represents mass fraction.
The hydroxyl value of tung oil polyol product prepared by the present invention is determined according to the phthalic anhydride esterification method in GB/T12008.3-2009, and viscosity is determined according to the rotation viscometer method in GB/T 12008.7-2010.
Embodiment 1
800g tung oil, 160g methanol, 8g potassium hydroxide are added in 2L autoclaves, it is stirred reaction, reaction temperature is 60 DEG C, reaction time is 20min, reaction terminates rear stratification, isolates lower floor glycerol product 76.2g, then with 50 DEG C of hot wash upper strata products 3 times, and the product after washing is distilled into 2h under the conditions of 2000Pa, 60 DEG C, obtain tung oil methyl ester.
Tung oil methyl ester, the 125g formic acid of the above-mentioned preparations of 500g are added in 2000mL there-necked flasks（85wt% solution）, the 0.5g concentrated sulfuric acids, 300g butanol, 50g deionized waters, be warming up to 40 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 450g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 50 DEG C or so, after completion of dropping, and the constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced.After testing, hydroxyl value is 249mgKOH/g, viscosity 7700mPas, acid number 0.78mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.2%, available for preparing hard polyurethane foam product.
Embodiment 2
800g tung oil, 100g methanol, 4g NaOH are added in 2L autoclaves, it is stirred reaction, reaction temperature is 55 DEG C, reaction time is 30min, reaction terminates rear stratification, isolates lower floor glycerol product 70.8g, then with 40 DEG C of hot wash upper strata products 4 times, and the product after washing is distilled into 2h under the conditions of 3000Pa, 50 DEG C, obtain tung oil methyl ester.
Tung oil methyl ester, the 125g formic acid of the above-mentioned preparations of 500g are added in 2000mL there-necked flasks（85wt% solution）, the 0.5g concentrated sulfuric acids, 300g butanol, 50g deionized waters, be warming up to 35 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 450g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 40 DEG C or so, after completion of dropping, and the constant temperature 5h at 40 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced.After testing, hydroxyl value is 162mgKOH/g, viscosity 2850mPas, acid number 0.63mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.9%, available for preparing polyurethane products.
Embodiment 3
800g tung oil, 220g methanol, 12g calcium hydroxides are added in 2L autoclaves, it is stirred reaction, reaction temperature is 65 DEG C, reaction time is 15min, reaction terminates rear stratification, isolates lower floor glycerol product 79.4g, then with 50 DEG C of hot wash upper strata products 3 times, and the product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, obtain tung oil methyl ester.
Tung oil methyl ester, the 125g formic acid of the above-mentioned preparations of 500g are added in 2000mL there-necked flasks（85wt% solution）, the 0.5g concentrated sulfuric acids, 300g butanol, 50g deionized waters, be warming up to 45 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 450g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 65 DEG C or so, after completion of dropping, and the constant temperature 3h at 65 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced.After testing, hydroxyl value is 232mgKOH/g, viscosity 9700mPas, acid number 0.88mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.0%, available for preparing hard polyurethane foam product.
Embodiment 4
800g tung oil, 120g methanol, 10g lithium hydroxides are added in 2L autoclaves, it is stirred reaction, reaction temperature is 60 DEG C, reaction time is 20min, reaction terminates rear stratification, isolates lower floor glycerol product 70.8g, then with 50 DEG C of hot wash upper strata products 3 times, and the product after washing is distilled into 2h under the conditions of 2000Pa, 60 DEG C, obtain tung oil methyl ester.
Tung oil methyl ester, the 80g formic acid of the above-mentioned preparations of 500g are added in 2000mL there-necked flasks（85wt% solution）, the 4g concentrated sulfuric acids, 250g butanol, 50g deionized waters, be warming up to 40 DEG C and stir.Then 40wt% hydrogenperoxide steam generator 350g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 50 DEG C or so, after completion of dropping, and the constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced.After testing, hydroxyl value is 187mgKOH/g, viscosity 14200mPas, acid number 0.91mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.3%, available for preparing hard polyurethane foam product.
Embodiment 5
800g tung oil, 180g methanol, 10g potassium hydroxide are added in 2L autoclaves, it is stirred reaction, reaction temperature is 60 DEG C, reaction time is 20min, reaction terminates stratification, isolates lower floor glycerol product 78.6g, then with 50 DEG C of hot wash upper strata products 3 times, and the product after washing is distilled into 2h under the conditions of 2000Pa, 60 DEG C, obtain tung oil methyl ester.
Tung oil methyl ester, the 150g formic acid of the above-mentioned preparations of 500g are added in 2000mL there-necked flasks（85wt% solution）, the 0.5g concentrated sulfuric acids, 500g butanol, 50g deionized waters, be warming up to 40 DEG C and stir.Then 20wt% hydrogenperoxide steam generator 500g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 50 DEG C or so, after completion of dropping, and the constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced.After testing, hydroxyl value is 227mgKOH/g, viscosity 6840mPas, acid number 0.71mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.0%, available for preparing hard polyurethane foam product.
Embodiment 6
With treatment process condition same as Example 1, difference is that the hydroxylating agent added in step 2 is 300g ethanol, and tung oil polyol product is made.After testing, hydroxyl value is 220mgKOH/g, viscosity 11800mPas, acid number 0.86mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.6%, available for preparing hard polyurethane foam product.
Embodiment 7
Using treatment process condition same as Example 1, difference is that the hydroxylating agent added is 300g triethanolamines, and tung oil polyol product is made.After testing, hydroxyl value is 223mgKOH/g, viscosity 12100mPas, acid number 0.87mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.5%, available for preparing hard polyurethane foam product.
Embodiment 8
Using treatment process condition same as Example 1, difference is that carboxylic acid uses 125g glacial acetic acids in step 2.After testing, hydroxyl value is 132mgKOH/g, viscosity 2100mPas, and moisture is less than 0.1wt%, and yield is 92.1%, available for preparing polyurethane products.
Embodiment 9
Using treatment process condition same as Example 1, difference is that acid catalyst uses 0.5g phosphoric acid in step 2.After testing, hydroxyl value is 231mgKOH/g, viscosity 7340mPas, and moisture is less than 0.1wt%, and yield is 92.7%, available for preparing hard polyurethane foam product.
Comparative example 1
Using treatment process condition same as Example 1, difference is to be added without hydroxylating agent in step 2.The viscosity 415000mPas of product, because product viscosity is excessive and can not dissolve, it is impossible to further carry out hydroxylating, therefore product is not used to prepare hard polyurethane foam product.
Comparative example 2
Using treatment process condition same as Example 1, difference is to prepare polyalcohol using soybean oil as raw material.After testing, hydroxyl value is 6.4mgKOH/g, and due to soybean oil methyl esters, not occur hydroxylating, hydroxyl value in step 2 too low, 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 Jatropha curcas oil as raw material.After testing, hydroxyl value is 4.8mgKOH/g, and due to soybean oil methyl esters, not occur hydroxylating, hydroxyl value in step 2 too low, therefore product is not used to prepare polyurethane products.
Claims (12)
1. a kind of method for producing tung oil polyalcohol and by-product glycerol, it is characterised in that including following content：（1）It is added to after tung oil, methanol and base catalyst are mixed in proportion in autoclave, carries out tung oil methyl ester reaction, lower floor's glycerine is isolated after reaction, then through washing, vacuum distillation, obtains tung oil methyl ester；（2）Tung oil methyl ester and carboxylic acid, acid catalyst, hydroxylating agent, deionized water are mixed in proportion, 35-45 DEG C is warming up to；Lower dropwise addition hydrogenperoxide steam generator is stirred vigorously, control rate of addition makes reaction maintain after 40-65 DEG C, completion of dropping, maintenance reaction temperature 3-5h；（3）Reaction terminates rear stratification, isolates aqueous phase, oil phase is neutralized, washing, vacuum distillation, obtain tung oil polyol product.
2. according to the method described in claim 1, it is characterised in that：Step（1）Described methanol and the alcohol oil quality ratio of tung oil are 0.1:1-0.3:1.
3. according to the method described in claim 1, it is characterised in that：Step（1）Described base catalyst is the one or more in potassium hydroxide, NaOH, lithium hydroxide, calcium hydroxide, and consumption is the 0.5%-1.5% of tung oil quality.
4. according to the method described in claim 1, it is characterised in that：Step（1）Described tung oil methyl esterization reaction is 55-65 DEG C of progress under agitation, and the reaction time is 15-30min.
5. according to the method described in claim 1, it is characterised in that：Step（1）Described washing temperature is 40-60 DEG C；Vacuum distillation is the residual methanol and moisture in removing system under the conditions of pressure 1000-3000Pa, 50-80 DEG C of temperature.
6. according to the method described in claim 1, it is characterised in that：Step（2）Described acid catalyst is the one or more in sulfuric acid, phosphoric acid, hydrochloric acid, sulfonic acid ion exchange resin, and consumption is the 0.01%-1.0% of tung oil methyl ester quality.
7. according to the method described in claim 1, it is characterised in that：Step（2）Described carboxylic acid is the one or more in formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, phenylacetic acid etc., and it is 0.05 to control carboxylic acid and the mass ratio of tung oil methyl ester:1-0.5:1.
8. according to the method described in claim 1, it is characterised in that：Step（2）Described hydroxylating agent is alcohols or alcamines, and consumption is 0.5-2 times of tung oil methyl ester quality.
9. method according to claim 8, 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；One or more of the alcamines hydroxylating agent in monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, monoethanolamine, diethanol amine, triethanolamine.
10. according to the method described in claim 1, it is characterised in that：Step（2）The consumption of the deionized water is 0.01-0.2 times of tung oil methyl ester quality；The hydrogenperoxide steam generator concentration is 20wt%-60wt%, and consumption is 0.6-1.2 times of tung oil methyl ester quality.
11. according to the method described in claim 1, it is characterised in that：Step（3）The neutralization reaction concentration neutralizes for 5wt%-20wt% sodium bicarbonate aqueous solution；The washing temperature is 50-80 DEG C；The 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%.
12. tung oil polyalcohol prepared by any methods describeds of claim 1-11, it is characterised in that：The product 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 92%, available for preparing polyurethane material.
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