CN107151210A - A kind of method that tung oil polyalcohol is prepared under Ultrasonic Conditions - Google Patents
A kind of method that tung oil polyalcohol is prepared under Ultrasonic Conditions Download PDFInfo
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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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- 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
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
- C07D301/16—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof formed in situ, e.g. from carboxylic acids and hydrogen peroxide
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- 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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- 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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- 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
- C08G2110/00—Foam properties
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Abstract
The invention discloses a kind of method that utilization ultrasonic wave prepares tung oil polyalcohol, tung oil, carboxylic acid, inorganic acid catalyst, hydroxylating agent are proportionally added into ultrasound reactor, are warming up to after 35 45 DEG C, starts ultrasound reactor；Then under intense agitation, hydrogen peroxide is added dropwise, it is 45 65 DEG C to control temperature of reactor, after completion of dropping, continues to react 1 3h, terminate reaction；Reaction system isolates aqueous phase through stratification, then neutralized, and washing, vacuum distillation obtains tung oil polyalcohol.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, epoxidised while adding oil-soluble aliphatic acid, the generation of crosslinking side reaction can be effectively prevented from, and use intensified by ultrasonic wave course of reaction, significantly improve reaction rate, the usage amount of the decomposition of peroxycarboxylic acid, reduction hydrogen peroxide and carboxylic acid is reduced, tung oil polyol product is efficiently synthesized.
Description
Technical field
The invention belongs to polyurethane material field, and in particular to a kind of method that tung oil polyalcohol is prepared under Ultrasonic Conditions.
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 peroxycarboxylic 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, including making the vegetable oil of PART EPOXY be reacted 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 that tung oil polyalcohol is prepared under Ultrasonic Conditions.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, epoxidised while adding oil-soluble aliphatic acid, and utilize intensified by ultrasonic wave course of reaction, the generation of crosslinking side reaction can be effectively prevented from, two phase reaction speed is improved, shortens the reaction time, and the decomposition of peroxycarboxylic acid can be reduced, the usage amount of hydrogen peroxide and carboxylic acid is reduced, production cost is saved.
The preparation method of tung oil polyalcohol of the present invention, including following content：Tung oil, carboxylic acid, inorganic acid catalyst, hydroxylating agent are proportionally added into ultrasound reactor, are warming up to after 35-45 DEG C, starts ultrasound reactor；Then hydrogenperoxide steam generator is added dropwise with vigorous stirring, control rate of addition makes reaction temperature maintain after 45-65 DEG C, completion of dropping, continues to react 1-3h, terminates reaction；Reaction system isolates aqueous phase, then neutralized, washing, vacuum distillation, obtains tung oil polyalcohol through stratification.
Ultrasound reactor of the present invention can be such that course of reaction is efficiently carried out under Ultrasonic Conditions, and ultrasonic power is 30-200W.The present invention uses ultrasound reactor, reaction system is set to be under the conditions of ultrasonic radiation, the cavitation of ultrasound can make to form substantial amounts of cavitation bubble in reaction system, cavitation bubble is rapidly formed, grows, collapses and cavitation bubble surrounding liquid is poured cavitation bubble center at a high speed, disturb boundary, the reaction rate of two phase reaction with efficient hardening two-phase mass transfer, can be improved, shortens the reaction time；And the usage amount of the decomposition of peroxycarboxylic acid, reduction hydrogen peroxide and carboxylic acid can be reduced, save production cost.
Carboxylic acid of the present invention can be formic acid or acetic acid, 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 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 the mass ratio for controlling carboxylic acid and tung oil is 0.03:1-0.3:1.
Inorganic acid catalyst of the present invention can be the one or more in sulfuric acid, phosphoric acid or hydrochloric acid etc., preferably sulfuric acid；Inorganic acid catalyst consumption is the 0.01%-1.0% of tung oil quality.
Hydroxylating agent of the present invention is oil-soluble aliphatic acid, and consumption is 0.1-0.5 times of tung oil quality.Oil-soluble aliphatic acid can be selected from C6-C12Straight or branched saturated fatty acid in one or more, such as n-caproic acid, positive enanthic acid, caprylic acid, isocaproic acid, isoamyl acetic acid, isooctyl acid.Compared to small molecule alcohol reagent, there is advantages below using oil-soluble aliphatic acid：（1）Because epoxidized vegetable reaction is very exothermic reaction, reaction accelerates reaction rate under Ultrasonic Conditions, it is more easy to occur temperature overshot, and reaction selectivity of the small molecule alcohol reagent as hydroxylating agent when temperature is higher is poor, crosslinking side reaction can not be avoided, causes product viscosity to sharply increase；And the hydrogen of aliphatic acid more easily ionizable, reactivity is significantly higher than the alcoholic extract hydroxyl group of neighbouring vegetable oil molecule chain formation, so when reaction temperature is higher, still there is good reaction selectivity, avoid the crosslinking side reaction of vegetable oil molecule interchain, reaction temperature window is wider, can preferably be applied to ultrasonic reactor；（2）Oil-soluble aliphatic acid can be dissolved in the oil phase in reaction system, it is to avoid cause the problem of hydroxylating ring-opening reaction speed declines in the alternate migration of oil, water two, improve the selectivity of reaction；（3）It oil-soluble aliphatic acid and will not be chemically reacted in system with oxygen agent formic acid, cause the decline of reaction substrate concentration, influence epoxidation and ring-opening reaction effect in situ；（4）The consumption of hydroxylating agent, formic acid, hydrogen peroxide is reduced, and reaction system initial stage is without adding deionized water, reduces raw materials for production cost and the treating capacity of industrial wastewater.
Hydrogenperoxide steam generator of the present invention plays a part of oxidant, carboxylic acid is oxidized to peroxycarboxylic acid.The concentration of hydrogen peroxide 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%, hydrogenperoxide steam generator consumption is 0.4-0.8 times of tung oil quality.
Neutralization reaction of the present invention can use ammoniacal liquor, sodium carbonate or sodium acid carbonate, preferably use the sodium bicarbonate solution that concentration is 5wt%-20wt% and neutralize.Described washing temperature is 50-80 DEG C, to prevent system from emulsion occur.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%, it is adaptable to prepare polyurethane material.
More than 85% unsaturated bond is carbon carbon conjugated triene key in tung oil molecule, 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.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, epoxidised while adding oil-soluble aliphatic acid, and tung oil polyalcohol is prepared under Ultrasonic Conditions, the generation of crosslinking side reaction can be effectively prevented from, the reaction rate of two phase reaction is improved, tung oil polyol product is efficiently synthesized.Prepared tung oil polyalcohol 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.
The crosslinking side reaction of tung oil molecule interchain can be avoided by being added in the epoxidization reaction process of tung oil under small molecule alcohol reagent, certain condition, synthesize tung oil polyol product.But in epoxidization reaction process, easily and with oxygen agent formic acid esterification occurs for small molecule alcohol reagent, causes the concentration of reaction system small molecular alcohol reagent and formic acid substantially to reduce, epoxidation and ring-opening reaction speed in situ are slow, avoid the problems such as crosslinking side reaction effect is not good.Therefore, reaction system must avoid above mentioned problem by increasing the method for small molecule alcohol reagent, formic acid, the inventory of hydrogen peroxide and addition deionized water, increase considerably raw materials for production cost and the treating capacity of industrial wastewater.And, because the problem of there is pyroreaction poor selectivity under the conditions of acidic catalyst in small molecule alcohol reagent, there are the deficiencies such as the reduction of product hydroxyl value, viscosity increase compared with Gao Shiyi in reaction temperature, so must strictly be controlled reaction temperature, add the construction cost of process units.In addition, in the epoxidization reaction process of tung oil, there is oil, water two-phase in system, the peroxycarboxylic acid of generation is in aqueous phase, and vegetable oil belongs to oil phase, epoxidation reaction is only carried out on oil, the boundary of water two-phase, causes reaction rate to reduce, and peroxycarboxylic acid is easily decomposed after being formed, consumption and the cost of material of oxidant are added.The present invention, as hydroxylating agent, makes epoxy bond ring-opening reaction in situ have higher selectivity, reaction temperature window is wider, the characteristics of preferably being applied to high reaction rate under Ultrasonic Conditions using oil-soluble aliphatic acid.And avoid in epoxidization reaction process, easily and with oxygen agent formic acid esterification occurs for small molecule alcohol reagent, the concentration of reaction system small molecular alcohol reagent and formic acid is caused substantially to reduce, epoxidation and ring-opening reaction speed in situ are slow, prevent the problems such as crosslinking side reaction effect is not good, effectively reduce the consumption of hydroxylating agent, formic acid, hydrogen peroxide, and reaction system initial stage is without adding deionized water, raw materials for production cost and the treating capacity of industrial wastewater are reduced.
In addition, in the preparation process of tung oil polyalcohol, due in epoxidization reaction process, there is oil, water two-phase in system, the peroxycarboxylic acid of generation is in aqueous phase, and tung oil causes reaction rate to reduce in oil phase, and peroxycarboxylic acid is easily decomposed, and adds consumption.The present invention uses ultrasound reactor, the microcosmic mixing and mass transport process for making two-phase reaction system are greatly strengthened, the reaction rate of two phase reaction can be effectively improved, shorten the reaction time, and the decomposition of peroxycarboxylic acid can be reduced, the usage amount of hydrogenperoxide steam generator and carboxylic acid is reduced, production cost is saved.
Embodiment
With reference to embodiment, the invention will be further described.In the present invention, wt% represents mass fraction.
The hydroxyl value of tung oil polyol product prepared by the present invention is according to GB/T
12008.3-2009 in phthalic anhydride esterification method determine, acid number is according to GB/T
12008.5-2010 methods are determined, and viscosity is determined according to the rotation viscometer method in GB/T 12008.7-2010.
Embodiment 1
By 500g tung oil, 80g formic acid（85wt% solution）, the 0.5g concentrated sulfuric acids, 150g n-caproic acids be added in ultrasound reactor, be warming up to after 40 DEG C, setting ultrasonic power is 120W；30wt% hydrogenperoxide steam generator 325g are added dropwise with vigorous stirring, controlling reaction temperature is 50 DEG C, after completion of dropping, continue to react 2h, terminate reaction；By reaction system stratification, 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.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyalcohol is produced.After testing, hydroxyl value is 241mgKOH/g, viscosity 8117mPas, acid number 0.75mgKOH/g, and moisture is less than 0.1wt%, and yield is 94.3%, available for preparing hard polyurethane foam product.
Embodiment 2
By 500g tung oil, 100g formic acid（85wt% solution）, the 0.25g concentrated sulfuric acids, 250g n-caproic acids be added in ultrasound reactor, be warming up to after 45 DEG C, setting ultrasonic power is 180W；30wt% hydrogenperoxide steam generator 380g are added dropwise with vigorous stirring, it is 65 DEG C to control temperature of reactor, after completion of dropping, continue to react 1.5h, terminate reaction；By reaction system stratification, 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 polyalcohol is produced.After testing, hydroxyl value is 255mgKOH/g, viscosity 8220mPas, acid number 0.76mgKOH/g, and moisture is less than 0.1wt%, and yield is 94.5%, available for preparing hard polyurethane foam product.
Embodiment 3
By 500g tung oil, 60g formic acid（85wt% solution）, the 4g concentrated sulfuric acids, 120g n-caproic acids be added in ultrasound reactor, be warming up to after 35 DEG C, setting ultrasonic power is 80W；30wt% hydrogenperoxide steam generator 280g are added dropwise with vigorous stirring, it is 45 DEG C to control temperature of reactor, after completion of dropping, continue to react 2.5h, terminate reaction；By reaction system stratification, 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 polyalcohol is produced.After testing, hydroxyl value is 177mgKOH/g, viscosity 12440mPas, acid number 0.88mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.0%, available for preparing polyurethane products.
Embodiment 4
Using treatment process condition same as Example 1, difference is that the carboxylic acid added is acetic acid.The hydroxyl value of obtained tung oil polyalcohol is 155mgKOH/g, viscosity 3130mPas, acid number 0.51mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.1%, available for preparing polyurethane products.
Embodiment 5
Using treatment process condition same as Example 1, difference is that the inorganic acid catalyst added is phosphoric acid.The hydroxyl value of obtained tung oil polyalcohol is 226mgKOH/g, viscosity 7820mPas, acid number 0.72mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.9%, available for preparing hard polyurethane foam product.
Embodiment 6
Using treatment process condition same as Example 1, difference is that the hydroxylating agent added is positive enanthic acid.The hydroxyl value of obtained tung oil polyalcohol is 233mgKOH/g, viscosity 8440mPas, acid number 0.77mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 94.1%, 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 isoamyl acetic acid.The hydroxyl value of obtained tung oil polyalcohol is 208mgKOH/g, viscosity 8950mPas, acid number 0.82mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 93.8%, available for preparing hard polyurethane foam product.
Embodiment 8
Using treatment process condition same as Example 1, difference is that the hydroxylating agent added is caprylic acid.The hydroxyl value of obtained tung oil polyalcohol is 224mgKOH/g, viscosity 8640mPas, acid number 0.79mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 94.0%, available for preparing hard polyurethane foam product.
Embodiment 9
Using treatment process condition same as Example 1, difference is that the hydroxylating agent added is isooctyl acid.The hydroxyl value of obtained tung oil polyalcohol is 201mgKOH/g, viscosity 9210mPas, acid number 0.85mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 93.5%, 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.The viscosity 452000mPas of product, because product viscosity is excessive and can not dissolve, it is impossible to further carry out hydroxylating, therefore be not used to prepare polyurethane products.
Comparative example 2
Using treatment process condition same as Example 1, difference is to prepare polyalcohol using soybean oil.Product hydroxyl value is 6.4mgKOH/g, and due to product, not occur hydroxylating, hydroxyl value too low, therefore is not used to prepare polyurethane products.
Comparative example 3
Using process conditions and raw material dosage same as Example 1, difference is to be reacted using common synthesis reaction vessel, prepares tung oil polyalcohol.Product hydroxyl value is 197mgKOH/g, hence it is evident that less than the hydroxyl value 241mgKOH/g of product in embodiment 1, illustrate using common synthesis reaction vessel, and the utilization rate of formic acid and hydrogenperoxide steam generator is relatively low, and high hydroxyl value product, increase production cost can not be prepared under the conditions of same amount.
Comparative example 4
Using treatment process condition same as Example 1, difference is to use methanol as hydroxylating agent.Product hydroxyl value is 108mgKOH/g, viscosity 94500mPas, because in reaction system easily with formic acid esterification occurs for methanol, cause actual concentrations of the methanol in reaction system relatively low, and due to using ultrasound reactor, epoxidation reaction speed is high, exothermic heat of reaction is caused to be aggravated, and reaction selectivity of the methanol as hydroxylating agent when temperature is higher is poor, factors above causes the alcohol reagents such as methanol can not avoid the epoxidised crosslinking side reaction of tung oil, product viscosity is caused to sharply increase, it is impossible to further synthesis of polyurethane product.
Claims (10)
1. a kind of method that utilization ultrasonic wave prepares tung oil polyalcohol, it is characterised in that including following content：Tung oil, carboxylic acid, inorganic acid catalyst, hydroxylating agent are proportionally added into ultrasound reactor, are warming up to after 35-45 DEG C, starts ultrasound reactor；Then hydrogenperoxide steam generator is added dropwise with vigorous stirring, control rate of addition makes reaction temperature maintain after 45-65 DEG C, completion of dropping, continues to react 1-3h, terminates reaction；Reaction system isolates aqueous phase, then neutralized, washing, vacuum distillation, obtains tung oil polyalcohol through stratification.
2. according to the method described in claim 1, it is characterised in that：The ultrasonic power of the ultrasound reactor is 30-200W.
3. according to the method described in claim 1, it is characterised in that：Described carboxylic acid is formic acid or acetic acid, and the mass ratio for controlling carboxylic acid and tung oil is 0.03:1-0.3:1.
4. according to the method described in claim 1, it is characterised in that：Described inorganic acid catalyst is the one or more in sulfuric acid, phosphoric acid or hydrochloric acid, and consumption is the 0.01%-1.0% of tung oil quality.
5. according to the method described in claim 1, it is characterised in that：Described hydroxylating agent is oil-soluble aliphatic acid, and consumption is 0.1-0.5 times of tung oil quality.
6. method according to claim 5, it is characterised in that：One or more in the saturated fatty acid of described straight or branched of the oil-soluble aliphatic acid selected from C6-C12.
7. the method according to claim 5 or 6, it is characterised in that：Described oil-soluble aliphatic acid is n-caproic acid, positive enanthic acid, caprylic acid, isocaproic acid, isoamyl acetic acid or isooctyl acid.
8. according to the method described in claim 1, it is characterised in that：The concentration of the hydrogenperoxide steam generator is 20wt%-60wt%, and consumption is 0.4-0.8 times of tung oil quality.
9. according to the method described in claim 1, it is characterised in that：Described neutralization reaction concentration neutralizes for 5wt%-20wt% sodium bicarbonate solution；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 described of claim 1~9, it is characterised in that：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.
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| CN102070433A (en) * | 2010-12-27 | 2011-05-25 | 桂林师范高等专科学校 | Preparation method for aryl acetic acid derivative |
| CN102206154A (en) * | 2011-03-11 | 2011-10-05 | 清华大学 | Vegetable oil polyol and preparation method thereof |
| CN103113553A (en) * | 2013-01-30 | 2013-05-22 | 上海市医药保健品进出口有限公司 | Pure vegetable oil based polyalcohol and preparation method thereof |
| CN103288642A (en) * | 2013-06-08 | 2013-09-11 | 南京工业大学 | Method for preparing vegetable oil polyalcohol by continuous process |
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| CN109574846A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | A method of Lubricity of Low-Sulfur Diesel Fuels modifier is prepared using ultrasonic wave |
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