CN107151211A - A kind of high hydroxyl value tung oil polyalcohol and preparation method thereof - Google Patents
A kind of high hydroxyl value tung oil polyalcohol and preparation method thereof 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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- C—CHEMISTRY; METALLURGY
- 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 preparation method of high hydroxyl value tung oil polyalcohol, including（1）Tung oil, carboxylic acid, acid catalyst, hydroxylating agent are mixed in proportion, and are warming up to 35 45 DEG C；Hydrogenperoxide steam generator is added dropwise with vigorous stirring, control rate of addition makes reaction temperature maintain 40 65 DEG C, after completion of dropping, the 5h of maintenance reaction temperature 3；Reaction terminates rear stratification, isolates aqueous phase, then it is neutralized, wash, be dried under reduced pressure, obtain tung oil polyalcohol；（2）By step（1）Tung oil polyalcohol and aminolysis agent mix in proportion, carry out aminolysis reaction under base catalyst effect, high hydroxyl value tung oil polyalcohol be made.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, hydroxylating agent is added in epoxidation simultaneously, synthesizes tung oil polyalcohol；Then high hydroxyl value tung oil polyalcohol is made by aminolysis reaction.The hydroxyl value of obtained tung oil polyalcohol is 250 450mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 92%, it is adaptable to prepare polyurethane material.
Description
Technical field
The invention belongs to polyurethane material field, and in particular to a kind of high hydroxyl value tung oil polyalcohol and preparation method thereof.
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 that vegetable oil has by it, not only cost is low for polymer therefrom, and environmentally friendly, is 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, 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.
Tung oil can also prepare tung oil polyalcohol by ester bond alcoholysis method.CN103360246A discloses a kind of method that eleostearic acid monoglyceride is prepared by tung oil, is after tung oil is hydrolyzed in the basic conditions, then is acidified isolated eleostearic acid；Glycerine and acetone react under solid acid catalysis obtains isopropylidene glycerol-4-methanol；With isopropylidene glycerol-4-methanol esterification occurs under solid acid catalysis for last eleostearic acid, then hydrolyzes deprotection and obtain eleostearic acid monoglyceride.But in this method, the carbon carbon conjugated triene key of tung oil is not effectively transformed utilization, causes product stability poor, the side reactions such as solidification are easily crosslinked in storing process.In addition, ester bond alcoholysis method is also present, conversion ratio is low, reaction temperature is too high（220-260℃）The shortcomings of, the energy is not only wasted, and react easily increase accessory substance at high temperature for a long time.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of high hydroxyl value tung oil polyalcohol and preparation method thereof.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, epoxidised while addition hydroxylating agent, can be effectively prevented from the generation of crosslinking side reaction, synthesis tung oil polyalcohol；Then by aminolysis reaction, the hydroxyl value of tung oil polyalcohol is improved, high hydroxyl value tung oil polyol product is made.
The preparation method of high hydroxyl value tung oil polyalcohol of the present invention, including following content：
（1）Tung oil, carboxylic acid, acid catalyst, hydroxylating agent are mixed in proportion, and are warming up to 35-45 DEG C；Hydrogenperoxide steam generator is added dropwise with vigorous stirring, control rate of addition makes reaction temperature maintain after 40-65 DEG C, completion of dropping, maintenance reaction temperature 3-5h；Reaction terminates rear stratification, isolates aqueous phase, then it is neutralized, wash, be dried under reduced pressure, obtain tung oil polyalcohol；
（2）By step（1）Obtained tung oil polyalcohol and aminolysis agent are mixed in proportion, carry out aminolysis reaction under base catalyst effect, high hydroxyl value tung oil polyalcohol is made.
Step of the present invention（1）The carboxylic acid 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 0.05:1-0.3:1.
Step of the present invention（1）The acid catalyst can be the one or more in sulfuric acid, phosphoric acid, hydrochloric acid or sulfonic acid ion exchange resin etc., preferably sulfuric acid；Acid catalyst levels are the 0.01%-1.0% of tung oil quality.
Step of the present invention（1）Described hydroxylating agent is oil-soluble aliphatic acid, and consumption is 0.1-0.5 times of tung oil quality.C can be selected from6-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）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, the crosslinking side reaction of vegetable oil molecule interchain is avoided, and forms alcoholic extract hydroxyl group, reaction temperature window is wider；（2）Selected aliphatic acid can be dissolved in the oil phase in reaction system, it is to avoid cause the problem of reaction rate 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 and 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.
Step of the present invention（1）The hydrogenperoxide steam generator plays a part of oxidant, carboxylic acid is oxidized to peroxy 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%, the consumption of hydrogenperoxide steam generator is 0.4-0.8 times of tung oil quality.
Step of the present invention（1）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 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%.
Step of the present invention（2）The detailed process of described aminolysis reaction is：By step（1）Obtained tung oil polyalcohol and aminolysis agent are mixed in proportion, 80-100 DEG C are progressively warming up under nitrogen protection, and add base catalyst；Then 110-150 DEG C is warming up to vigorous stirring, and maintenance reaction temperature 4-8h terminates reaction, obtains high hydroxyl value tung oil polyalcohol.Compared with alcoholysis reaction, the aminolysis reaction temperature of vegetable oil is relatively low, and side reaction is few, is a kind of method for being more suitable for preparing tung oil polyalcohol.
Step of the present invention（2）Described aminolysis agent is that agent is the Organic Alcohol aminated compounds with-NH structures, preferably diethanol amine, and consumption is step（1）0.05-0.2 times of obtained tung oil polyol quality.
Step of the present invention（2）The base catalyst is the one or more in sodium methoxide, caustic alcohol, sodium hydroxide, lithium hydroxide etc., and base catalyst consumption is step（1）The 0.05%-0.5% of obtained tung oil polyol quality.
High hydroxyl value tung oil polyalcohol of the present invention is prepared by the invention described above method.The hydroxyl value of prepared high hydroxyl value tung oil polyalcohol is 250-450mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 92%, it is adaptable to prepare polyurethane material.
The application of prepared high hydroxyl value tung oil polyalcohol of the invention, the raw material based on tung oil polyalcohol, PPG, it is aided with auxiliary agent and is configured to combination material, the auxiliary agent includes but is not limited to catalyst, foam stabiliser, water, fire retardant, combination material is well mixed with foaming agent, foamed again with isocyanates reaction, you can prepare RPUF etc..
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 addition hydroxylating agent, can be effectively prevented from the generation of crosslinking side reaction；Obtained tung oil polyalcohol and aminolysis agent are subjected to aminolysis reaction, so that high hydroxyl value tung oil polyol product is made.Prepared high hydroxyl value tung oil polyol product is compared with petroleum-based polyols, with hydroxyl value is high, stability is good, and raw material is renewable, non-toxic and the good advantage of biological degradability, belongs to environment-friendly biopolyol.
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 polyalcohol.But in epoxidization reaction process, easily and with oxygen agent formic acid esterification occurs for small molecule alcohol reagent, causing the concentration of reaction system small molecular alcohol reagent and formic acid substantially reduces, and epoxidation and ring-opening reaction speed in situ are slow, it is to avoid the problems such as crosslinking side reaction effect is not good.Therefore, reaction system must avoid above mentioned problem by increasing the inventory of small molecule alcohol reagent, formic acid and hydrogen peroxide, increase considerably raw materials for production cost and the treating capacity of industrial wastewater.In addition, 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.The present invention substitutes small molecule alcohol using oil-soluble aliphatic acid and is used as hydroxylating agent, make epoxy bond ring-opening reaction in situ that there is higher selectivity, reaction temperature window is wider, 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, the inventory of hydroxylating agent, formic acid and hydrogen peroxide is effectively reduced, production cost has been saved.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of high hydroxyl value 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 polyalcohol prepared by the present invention is determined according to the phthalic anhydride esterification method in GB/T 12008.3-2009, and viscosity is determined according to the rotation viscometer method in GB/T 12008.7-2010.
Embodiment 1
500g tung oil, 80g formic acid are added in 2000mL three-necked flasks（85wt% solution）, the 0.5g concentrated sulfuric acids, 150g n-caproic acids, be warming up to 40 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 325g 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.Stand after question response system layering, remove aqueous phase, 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 made.
The tung oil polyalcohol 80g of above-mentioned preparation is well mixed with 11g diethanol amine, 90 DEG C are progressively warming up under nitrogen protection, and add catalyst sodium methoxide 0.16g; 130 DEG C are warming up under intense agitation; isothermal reaction 6h, terminates reaction, obtains high hydroxyl value tung oil polyalcohol.After testing, hydroxyl value is 427mgKOH/g, viscosity 9100mPas, and moisture is less than 0.1wt%, and yield is 92.8%, available for preparing hard polyurethane foam product.
Embodiment 2
500g tung oil, 55g formic acid are added in 2000mL three-necked flasks（85wt% solution）, the 4g concentrated sulfuric acids, 130g n-caproic acids, be warming up to 45 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 285g 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.Stand after question response system layering, remove aqueous phase, 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 made.
The tung oil polyalcohol 80g of above-mentioned preparation is well mixed with 11g diethanol amine, 100 DEG C are progressively warming up under nitrogen protection, and add catalyst sodium methoxide 0.16g; 150 DEG C are warming up under intense agitation; isothermal reaction 4h, terminates reaction, obtains high hydroxyl value tung oil polyalcohol.After testing, hydroxyl value is 282mgKOH/g, viscosity 8800mPas, and moisture is less than 0.1wt%, and yield is 92.1%, available for preparing hard polyurethane foam product.
Embodiment 3
500g tung oil, 100g formic acid are added in 2000mL three-necked flasks（85wt% solution）, the 0.25g concentrated sulfuric acids, 250g n-caproic acids, be warming up to 35 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 380g 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 polyalcohol is made.
The tung oil polyalcohol 80g of above-mentioned preparation is well mixed with 11g diethanol amine, 80 DEG C are progressively warming up under nitrogen protection, and add catalyst sodium methoxide 0.16g; 110 DEG C are warming up under intense agitation; isothermal reaction 8h, terminates reaction, obtains high hydroxyl value tung oil polyalcohol.After testing, hydroxyl value is 447mgKOH/g, viscosity 9050mPas, and moisture is less than 0.1wt%, and yield is 93.1%, available for preparing hard polyurethane foam product.
Embodiment 4
Using handling process and operating condition same as Example 1, difference is that the carboxylic acid added is acetic acid.The hydroxyl value of obtained high hydroxyl value tung oil polyalcohol is 288mgKOH/g, and viscosity 4200mPas, moisture is less than 0.1wt%, and yield can be used for preparing hard polyurethane foam product for 92.0%.
Embodiment 5
Using handling process and operating condition same as Example 1, difference is that the acid catalyst added is phosphoric acid.The hydroxyl value of obtained high hydroxyl value tung oil polyalcohol is 408mgKOH/g, and viscosity 8600mPas, moisture is less than 0.1wt%, and yield is 92.5%, available for preparing hard polyurethane foam product.
Embodiment 6
Using handling process and operating condition same as Example 1, difference is that the hydroxylating agent added is positive enanthic acid.The hydroxyl value of obtained high hydroxyl value tung oil polyalcohol is 420mgKOH/g, and viscosity 9140mPas, moisture is less than 0.1wt%, and yield is 92.4%, available for preparing hard polyurethane foam product.
Embodiment 7
Using handling process and operating condition same as Example 1, difference is that the hydroxylating agent added is caprylic acid.The hydroxyl value of obtained high hydroxyl value tung oil polyalcohol is 416mgKOH/g, and viscosity 9210mPas, moisture is less than 0.1wt%, and yield is 92.3%, available for preparing hard polyurethane foam product.
Embodiment 8
Using handling process and operating condition same as Example 1, difference is that the hydroxylating agent added is isooctyl acid.The hydroxyl value of obtained high hydroxyl value tung oil polyalcohol is 405mgKOH/g, and viscosity 9420mPas, moisture is less than 0.1wt%, and yield is 92.2%, available for preparing hard polyurethane foam product.
Embodiment 9
Using handling process and operating condition same as Example 1, difference is that the base catalyst added is sodium hydroxide.The hydroxyl value of obtained high hydroxyl value tung oil polyalcohol is 422mgKOH/g, and viscosity 9050mPas, moisture is less than 0.1wt%, and yield is 92.7%, available for preparing hard polyurethane foam product.
Comparative example 1
Using handling process and operating condition same as Example 1, difference is to be added without hydroxylating agent.The viscosity of product is 470000mPas, because product viscosity is excessive and can not dissolve, it is impossible to further carry out aminolysis reaction, therefore is not used to prepare hard polyurethane foam product.
Comparative example 2
Using handling process and operating condition same as Example 1, difference is to prepare polyalcohol using soybean oil.Product hydroxyl value is 138mgKOH/g, viscosity 3400mPas.Due to product, soybean oil does not have hydroxylating in situ in first step reaction, so unsaturated double-bond utilization ratio is low, product hydroxyl value is low, it is impossible to for preparing hard polyurethane foam product.
Comparative example 3
Using handling process and operating condition same as Example 1, difference is to use methanol as hydroxylating agent.The hydroxyl value of obtained tung oil polyalcohol is 245.5mgKOH/g, viscosity is 83200mPas, because in reaction system easily with formic acid esterification occurs for methanol, cause actual concentrations of the methanol in reaction system relatively low, the crosslinking of tung oil in the epoxidation can not be avoided completely, so viscosity is excessive, it is impossible to for preparing Contents In Polyether Polyol.
Comparative example 4
Using handling process and operating condition same as Example 1, difference is directly to use tung oil to be reacted with aminolysis agent and base catalyst.The hydroxyl value of obtained tung oil polyalcohol is 182mgKOH/g, because the carbon carbon conjugated double bond of tung oil is not used effectively, causes product hydroxyl value relatively low.Further, since carbon carbon conjugated double bond reactivity is higher, easily occur the reaction such as polymerization or diene synthesis, it is unstable during preservation or use, so product is also not used to synthesis of polyurethane product.
Claims (13)
1. a kind of preparation method of high hydroxyl value tung oil polyalcohol, it is characterised in that including following content：
（1）Tung oil, carboxylic acid, acid catalyst, hydroxylating agent are mixed in proportion, and are warming up to 35-45 DEG C；Hydrogenperoxide steam generator is added dropwise with vigorous stirring, control rate of addition makes reaction temperature maintain after 40-65 DEG C, completion of dropping, maintenance reaction temperature 3-5h；Reaction terminates rear stratification, isolates aqueous phase, then it is neutralized, wash, be dried under reduced pressure, obtain tung oil polyalcohol；（2）By step（1）Obtained tung oil polyalcohol and aminolysis agent are mixed in proportion, carry out aminolysis reaction under base catalyst effect, high hydroxyl value tung oil polyalcohol is made.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described carboxylic acid is formic acid or acetic acid, and the mass ratio for controlling carboxylic acid and tung oil is 0.05:1-0.3:1.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）The 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 quality.
4. in accordance with the method for claim 1, it is characterised in that：Step（1）Described hydroxylating agent is oil-soluble aliphatic acid, and consumption is 0.1-0.5 times of tung oil quality.
5. in accordance with the method for claim 4, it is characterised in that：Described oil-soluble aliphatic acid is selected from C6-C12Straight or branched saturated fatty acid in one or more.
6. according to the method described in claim 4 or 5, 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.
7. in accordance with the method for claim 1, it is characterised in that：Step（1）The concentration of the hydrogenperoxide steam generator is 20wt %-60wt%, and consumption is 0.4-0.8 times of tung oil quality.
8. in accordance with the method for claim 1, it is characterised in that：Step（1）The neutralization reaction concentration neutralizes for 5wt%-20wt% sodium bicarbonate aqueous solution；Washing temperature is 50-80 DEG C；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%.
9. in accordance with the method for claim 1, it is characterised in that：Step（2）The detailed process of described aminolysis reaction is：By step（1）Obtained tung oil polyalcohol and aminolysis agent are mixed in proportion, 80-100 DEG C are progressively warming up under nitrogen protection, and add base catalyst；Then 110-150 DEG C is warming up to vigorous stirring, and maintenance reaction temperature 4-8h terminates reaction, obtains high hydroxyl value tung oil polyalcohol.
10. according to the method described in claim 1 or 9, it is characterised in that：Step（2）Described aminolysis agent is the Organic Alcohol aminated compounds with-NH structures, and consumption is step（1）0.05-0.2 times of tung oil polyol quality.
11. in accordance with the method for claim 10, it is characterised in that：Step（2）Described aminolysis agent is diethanol amine.
12. according to the method described in claim 1 or 9, it is characterised in that：Step（2）The base catalyst is one kind in sodium methoxide, caustic alcohol, sodium hydroxide, lithium hydroxide, and base catalyst consumption is step（1）The 0.05%-0.5% of tung oil polyol quality.
13. the high hydroxyl value tung oil polyalcohol prepared using any methods described of claim 1~12, it is characterised in that：The hydroxyl value of obtained high hydroxyl value tung oil polyalcohol is 250-450mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 92%, it is adaptable to prepare polyurethane material.
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| CN103274930A (en) * | 2013-06-20 | 2013-09-04 | 南京工业大学 | Method for preparing vegetable oil polyalcohol by adopting continuous method |
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| CN103274930A (en) * | 2013-06-20 | 2013-09-04 | 南京工业大学 | Method for preparing vegetable oil polyalcohol by adopting continuous method |
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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等: "Polyurethanes From Tung Oil: Polymer Characterization and Composites", 《POLYMER ENGINEERING AND SCIENCE》 * |
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