CN107151304A - A kind of preparation method of tung oil polyalcohol - Google Patents
A kind of preparation method of tung oil polyalcohol Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
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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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- 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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Abstract
The present invention relates to a kind of preparation method of tung oil polyalcohol, tung oil, hydroxylating agent, deionized water, pro-oxidant aldehyde compound, radical initiator are proportionally added into autoclave, and nitrogen is passed through into autoclave, replace air in kettle, after the completion of displacement, oxygen/nitrogen mixed gas is filled with into kettle, until pressure reaches 6.0 8.5MPa in kettle；Stirring is opened, controlling reaction temperature is 65 80 DEG C, reacts 2.5 4.5h, terminates reaction；Reaction system pressure is down to normal pressure, temperature is down to normal temperature, then through 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, utilize molecular oxygen/aldehyde system catalytic epoxidation, and hydroxylating agent is added simultaneously in epoxidation, crosslinking side reaction can be prevented effectively from, tung oil polyol product is synthesized.The hydroxyl value of obtained 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%, it is adaptable to prepare polyurethane material.
Description
Technical field
The invention belongs to polyurethane material field, and in particular to a kind of preparation method of tung oil polyalcohol.
Background technology
The characteristics of polyurethane material is due to good mechanical performance with shaping is easy to, has been widely used in industry and daily life.Main raw material(s) for producing polyurethane includes isocyanates, polyalcohol and other additives, and the ratio of wherein polyalcohol account for more than 50%.In industrial processes, polyalcohol is mainly used in polyurethane field, thus polyurethane industries among others influence factor be also polyalcohol market major influence factors.Polyalcohol can be divided into PPG and PEPA by molecular structure, wherein, PPG is occupied an leading position in the market, occupies more than the 70% of whole polyalcohol demand.
Generally, polyalcohol is to extract to prepare from oil.And oil is used as non-renewable resources, scarcity causes the continuous rise of its price, and cause the price continuous rise of the primary raw material of the polynary alcohol production such as downstream product expoxy propane, oxirane, and according to current depletion rate, petroleum resources are depleted eventually.Therefore, from sustainable development and the angle of enterprise competitiveness, the new material and new technology that can substitute petroleum base polyethers are found as strategic development task.
The U.S. is the major producing country of soybean oil in the world, and in addition to edible, the scientific research institution in the U.S. is also actively working to develop the various chemical products by raw material of soybean oil, to substitute petroleum-based chemicals.Concentrate on recently using the unsaturated bond in soybean oil strand, by the modification to double bond, vegetable oil is occurred epoxidation, hydroxylating, so as to prepare soybean oil polyol.The advantage of the method is that reaction temperature is relatively low（40-70℃）, product qualities, color and luster are good, so obtained extensive concern.
The Z.S. in kansas, U.S.A (Kansas) polymer research center
Petrovic etc. is reacted with peroxy acid with soybean oil, is prepared for epoxidized soybean oil, double bond is changed into epoxy radicals；Then under the catalytic action of effective catalyst tetrafluoro boric acid with water and alcohol ring-opening reaction occurs for epoxidized soybean oil, prepare the vegetable oil polyol containing hydroxyl, the hydroxyl value of polyalcohol is 110-213mgKOH/g, and viscosity is 1000-7000mPas, and conversion ratio is up to 85%-95%.
US20070123725 provides a kind of method for preparing soybean oil polyol, includes the epoxidation and hydroxylation procedures of polyunsaturated vegetable oil, forms vegetable oil-based polyether polyol.First, the polyunsaturated vegetable oils such as soybean oil or rapeseed oil and organic acid and hydrogenperoxide steam generator are reacted, forms epoxidized vegetable oil, the mixed solution of epoxidized vegetable oil and first alcohol and water is then subjected to ring-opening reaction generation vegetable oil polyol.
US20060041157 describes the method for preparing soybean oil polyol, 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 study hotspot that epoxidized vegetable oil is always vegetable oil field of deep is prepared using molecular oxygen/aldehyde system catalysis oxidation vegetable oil, because traditional epoxidized vegetable technique needs to use substantial amounts of carboxylic acid and hydrogenperoxide steam generator, and hydrogenperoxide steam generator produces the danger of blast as easily being decomposed during oxidant in industrial production, and big quantity carboxylic acid is needed to use, the selection to reactor proposes strict requirements.And from the aspect of economical and environmentally friendly two, molecular oxygen is optimal oxidant.Blumenstein etc.（Blumenstein M. Epoxidation of Methyl Oleate With
Molecular Oxygen in Presence of Aldehydes,《European
journal of lipid science and technology》, volume 110, the 6th phase, the 581-586 pages）Using molecular oxygen/aldehyde system catalysis oxidation synthesizing epoxy methyl oleate, double bond conversion rate reaches more than 95%, achieves in good result, and reaction and does not need a large amount of hydrogenperoxide steam generators and formic acid, makes production process safer and environmental protection.
But, using molecular oxygen/aldehyde catalytic oxidation system, vegetable oil is set to reach that the reaction temperature of preferable epoxidation effect is usually more than 65 DEG C, and under conditions of using small molecule alcohol reagent as hydroxylating agent, because reaction selectivity is not high under high temperature, so easily crosslinking side reaction, the reduction of product hydroxyl value, viscosity increase, therefore molecular oxygen/aldehyde catalytic oxidation system is caused to be difficult to use in catalysis oxidation synthesis tung oil polyalcohol.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of preparation method of tung oil polyalcohol.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, utilize molecular oxygen/aldehyde system catalytic epoxidation, and epoxidised while addition oil-soluble aliphatic acid, can be effectively prevented from the generation of crosslinking side reaction, efficiently synthesize tung oil polyol product.
The preparation method of tung oil polyalcohol of the present invention, including following content：Tung oil, hydroxylating agent, deionized water, pro-oxidant aldehyde compound, radical initiator are proportionally added into autoclave, and nitrogen is passed through into autoclave, replace air in kettle, after the completion of displacement, oxygen/nitrogen mixed gas is filled with into kettle, until pressure reaches 6.0-8.5MPa in kettle；Stirring is opened, controlling reaction temperature is 65-80 DEG C, reacts 2.5-4.5h, terminates reaction；Reaction system pressure is down to normal pressure, temperature is down to normal temperature, then through washing, vacuum distillation, obtains tung oil polyalcohol.
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）The hydrogen of oil-soluble 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, and alcoholic extract hydroxyl group is formed, reaction temperature window is wider, it is adaptable to the characteristics of molecular oxygen/aldehyde compound system can be only achieved preferable epoxidation effect at relatively high temperatures；（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）Oil-soluble aliphatic acid and the carboxylic acid of reaction generation will not chemically react in system, cause the decline of reaction substrate concentration, influence epoxidation and ring-opening reaction effect in situ, and significantly reduce the consumption of hydroxylating agent, reduce raw materials for production cost.
The consumption of deionized water of the present invention is 0.01-0.2 times of tung oil quality, and deionized water is the green solvent of reaction.
Pro-oxidant aldehyde compound of the present invention is the one or more in acetaldehyde, propionic aldehyde, hutanal, isobutylaldehyde, valeraldehyde, benzaldehyde, phenylacetaldehyde etc., preferably acetaldehyde, and consumption is 0.05-0.3 times of tung oil quality.Pro-oxidant aldehyde compound（RCHO）First in radical initiator（initiator）Induction under form acyl group free radical（RCO）, then acyl group free radical is in oxygen（O2）Peroxy radical can be generated under effect（RCOOO）, the peroxy radical formed is again by radical transfer to aldehyde compound, formation peroxy acid（RCOOOH）With acyl group free radical（RCO）, react the progress that goes round and begins again.Wherein, the peroxy acid of generation can make the conjugated double bond in tung oil be converted into epoxy bond, and epoxy bond further reacts to form tung oil polyalcohol with hydroxylating agent.
Radical initiator of the present invention is selected from azo-initiator, such as azodiisobutyronitrile, ABVN, or selected from organic peroxide, such as cyclohexanone peroxide, dibenzoyl peroxide, consumption is 0.001-0.01 times of tung oil quality.
It is of the present invention that nitrogen displacement air is passed through into autoclave, after the completion of displacement, the oxygen/nitrogen mixed gas that volume ratio is 1/99-10/90 is filled with into autoclave, pressure in kettle is reached 6.0-8.5MPa.
Washing temperature of the present invention 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 92%, 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, using molecular oxygen/aldehyde system catalytic epoxidation, and epoxidised while addition oil-soluble aliphatic acid, can effectively prevent the generation of crosslinking side reaction, efficiently synthesize tung oil polyol product.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, 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, the methods such as the inventory that reaction system must be by increasing small molecule alcohol reagent, formic acid, hydrogenperoxide steam generator avoid above mentioned problem, have increased considerably raw materials for production cost and the treating capacity of industrial wastewater.The problem of small molecule alcohol reagent has pyroreaction poor selectivity is additionally, since, the deficiencies such as the reduction of product hydroxyl value, viscosity increase occurs compared with Gao Shiyi in reaction temperature, so must strictly be controlled reaction temperature, adds the construction cost of process units.The present invention, as hydroxylating agent, makes epoxy bond ring-opening reaction in situ have higher selectivity, reaction temperature window is wider, can meet the use requirement of molecular oxygen/oxidation of aldehydes system using oil-soluble aliphatic acid.And avoid in epoxidization reaction process, esterification occurs for formic acid of the small molecule alcohol reagent easily with reaction generation, causing the concentration of reaction system small molecular alcohol reagent substantially reduces, prevent the problems such as crosslinking side reaction effect is not good, the consumption of hydroxylating agent is effectively reduced, raw materials for production cost is reduced.
In addition, using molecular oxygen/aldehyde catalytic oxidation system, avoid the danger easily decomposed, exploded using a large amount of hydrogenperoxide steam generators in traditional plant oil ring oxidation technology, big quantity carboxylic acid is needed to use as band oxygen agent with traditional handicraft, reactor choice requirement harshness is compared, equipment construction cost is significantly reduced.
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 polyalcohol prepared by the present invention is determined according to the phthalic anhydride esterification method in GB/T 12008.3-2009, and acid number is determined according to GB/T 12008.5-2010 methods, and viscosity is determined according to the rotation viscometer method in GB/T 12008.7-2010.
Embodiment 1
500g tung oil, 70g acetaldehyde, 2.5g azodiisobutyronitriles, 150g n-caproic acids, 50g deionized waters are added in autoclave, and is stirred.Then air 3 times in nitrogen, displacement kettle are passed through into autoclave, after the completion of displacement, the oxygen/nitrogen mixed gas that volume ratio is 5/95 are filled with into kettle, until pressure reaches 7.5MPa in kettle.Stirring is opened, controlling reaction temperature is 70 DEG C, reacts 3.5h, terminates reaction.Opening vent valve makes system pressure be down to normal pressure, and is cooled to after normal temperature, question response system layering, removes aqueous phase, and 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.After testing, hydroxyl value is 246mgKOH/g, viscosity 7350mPas, acid number 0.71mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.4%, available for preparing hard polyurethane foam product.
Embodiment 2
500g tung oil, 90g propionic aldehyde, 2.5g azodiisobutyronitriles, 100g n-caproic acids, 50g deionized waters are added in autoclave, and is stirred.Then air 3 times in nitrogen, displacement kettle are passed through into autoclave, after the completion of displacement, the oxygen/nitrogen mixed gas that volume ratio is 5/95 are filled with into kettle, until pressure reaches 6.5MPa in kettle.Stirring is opened, controlling reaction temperature is 80 DEG C, reacts 2.5h, terminates reaction.Opening vent valve makes system pressure be down to normal pressure, and is cooled to normal temperature, then reaction system 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 234mgKOH/g, viscosity 7210mPas, acid number 0.70mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.2%, available for preparing hard polyurethane foam product.
Embodiment 3
500g tung oil, 115g hutanals, 3.8g ABVNs, 200g n-caproic acids, 50g deionized waters are added in autoclave, and is stirred.Then air 3 times in nitrogen, displacement kettle are passed through into autoclave, after the completion of displacement, the oxygen/nitrogen mixed gas that volume ratio is 5/95 are filled with into kettle, until pressure reaches 8.5MPa in kettle.Stirring is opened, controlling reaction temperature is 65 DEG C, reacts 4h, terminates reaction.Opening vent valve makes system pressure be down to normal pressure, and is cooled to normal temperature, then reaction system 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 208mgKOH/g, viscosity 7040mPas, acid number 0.68mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.9%, available for preparing hard polyurethane foam product.
Embodiment 4
Using treatment process condition same as Example 1, difference is that the pro-oxidant aldehyde added is isobutylaldehyde.The hydroxyl value of obtained tung oil polyalcohol is 174mgKOH/g, viscosity 6200mPas, acid number 0.63mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.5%, available for preparing hard polyurethane foam product.
Embodiment 5
Using treatment process condition same as Example 1, difference is that the pro-oxidant aldehyde added is valeraldehyde.The hydroxyl value of obtained tung oil polyalcohol is 228mgKOH/g, viscosity 7290mPas, acid number 0.68mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.1%, available for preparing hard polyurethane foam product.
Embodiment 6
Using treatment process condition same as Example 1, difference is that the pro-oxidant aldehyde added is benzaldehyde.The hydroxyl value of obtained tung oil polyalcohol is 166mgKOH/g, viscosity 5600mPas, acid number 0.55mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.3%, available for preparing polyurethane products.
Embodiment 7
Using treatment process condition same as Example 1, difference is that the radical initiator added is ABVN.The hydroxyl value of obtained tung oil polyalcohol is 232mgKOH/g, viscosity 7140mPas, acid number 0.69mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 93.3%, available for preparing hard polyurethane foam product.
Embodiment 8
Using treatment process condition same as Example 1, difference is that the radical initiator added is cyclohexanone peroxide.The hydroxyl value of obtained tung oil polyalcohol is 228mgKOH/g, viscosity 7050mPas, acid number 0.67mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 93.2%, available for preparing hard polyurethane foam product.
Embodiment 9
Using treatment process condition same as Example 1, difference is that the radical initiator added is dibenzoyl peroxide.The hydroxyl value of obtained tung oil polyalcohol is 230mgKOH/g, viscosity 7110mPas, acid number 0.68mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 93.3%, available for preparing hard polyurethane foam product.
Embodiment 10
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 238mgKOH/g, viscosity 7640mPas, acid number 0.73mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 93.2%, available for preparing hard polyurethane foam product.
Embodiment 11
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 211mgKOH/g, viscosity 8450mPas, acid number 0.78mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 92.9%, available for preparing hard polyurethane foam product.
Embodiment 12
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 8030mPas, acid number 0.75mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 93.1%, available for preparing hard polyurethane foam product.
Embodiment 13
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 202mgKOH/g, viscosity 8820mPas, acid number 0.81mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 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.The viscosity of product is 383000mPas, 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 use methanol as hydroxylating agent.Product hydroxyl value is 125mgKOH/g, viscosity 69600mPas, esterification occurs for the formic acid due to methanol easily with generation in reaction system, cause actual concentrations of the methanol in reaction system relatively low, 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, causes product viscosity to sharply increase, it is impossible to further synthesis of polyurethane product.
Comparative example 3
Using treatment process condition same as Example 1, difference is to prepare polyalcohol using soybean oil.Product hydroxyl value is 4.1mgKOH/g, and due to product, not occur hydroxylating, hydroxyl value too low, therefore is not used to prepare polyurethane products.
Claims (11)
1. a kind of preparation method of tung oil polyalcohol, it is characterised in that including following content：Tung oil, hydroxylating agent, deionized water, pro-oxidant aldehyde compound, radical initiator are proportionally added into autoclave, and nitrogen is passed through into autoclave, replace air in kettle, after the completion of displacement, oxygen/nitrogen mixed gas is filled with into kettle, until pressure reaches 6.0-8.5MPa in kettle；Stirring is opened, controlling reaction temperature is 65-80 DEG C, reacts 2.5-4.5h, terminates reaction；Reaction system pressure is down to normal pressure, temperature is down to normal temperature, then through washing, vacuum distillation, obtains tung oil polyalcohol.
2. 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.
3. method according to claim 2, it is characterised in that：Described oil-soluble aliphatic acid is selected from C6-C12Straight or branched saturated fatty acid in one or more.
4. according to the method in claim 2 or 3, 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.
5. according to the method described in claim 1, it is characterised in that：The consumption of the deionized water is 0.01-0.2 times of tung oil quality.
6. according to the method described in claim 1, it is characterised in that：Described pro-oxidant aldehyde compound is the one or more in acetaldehyde, propionic aldehyde, hutanal, isobutylaldehyde, valeraldehyde, benzaldehyde, phenylacetaldehyde, and consumption is 0.05-0.3 times of tung oil quality.
7. according to the method described in claim 1, it is characterised in that：Described radical initiator is selected from azo-initiator or organic peroxide, and consumption is 0.001-0.01 times of tung oil quality.
8. method according to claim 7, it is characterised in that：Described azo-initiator is azodiisobutyronitrile or ABVN；Described organic peroxide is cyclohexanone peroxide or dibenzoyl peroxide.
9. according to the method described in claim 1, it is characterised in that：The volume ratio of the described oxygen/nitrogen mixed gas being filled with into autoclave is 1/99-10/90.
10. according to the method described in claim 1, it is characterised in that：Described washing temperature is 50-80 DEG C；Described vacuum distillation is the hydroxylating agent and residual moisture in removing system under the conditions of pressure 1000-3000Pa, 60-120 DEG C of temperature, product moisture content is less than 0.1wt%.
11. tung oil polyalcohol prepared by any methods describeds of claim 1-10, 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 92%, it is adaptable to prepare polyurethane material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103274930A (en) * | 2013-06-20 | 2013-09-04 | 南京工业大学 | Vegetable oil polyol preparation method by using continuous method |
Non-Patent Citations (3)
| Title |
|---|
| JUMAT SALIMON,ET AL.: "Chemically modified biolubricant basestocks from epoxidized oleic acid: Improved low temperature properties and oxidative stability", 《JOURNAL OF SAUDI CHEMICAL SOCIETY》 * |
| M.A.MOSIEWICKI,ET AL.: "Polyurethanes From Tung Oil: Polymer Characterization and Composites", 《POLYMER ENGINEERING AND SCIENCE》 * |
| 蔡双飞等: "环氧植物油增塑剂的合成工艺进展", 《塑料助剂》 * |
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