CN107151212A - A kind of low hydroxyl value tung oil polyalcohol and preparation method thereof - Google Patents
A kind of low hydroxyl value tung oil polyalcohol and preparation method thereof Download PDFInfo
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- CN107151212A CN107151212A CN201610119888.XA CN201610119888A CN107151212A CN 107151212 A CN107151212 A CN 107151212A CN 201610119888 A CN201610119888 A CN 201610119888A CN 107151212 A CN107151212 A CN 107151212A
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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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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Abstract
The invention discloses a kind of preparation method of low hydroxyl value tung oil polyalcohol, including（1）Tung oil, carboxylic acid, catalyst, hydroxylating agent are mixed in proportion, and are warming up to 35 45 DEG C；Hydrogenperoxide steam generator is added dropwise under intense agitation, reaction temperature is maintained 40 65 DEG C, after completion of dropping, maintenance reaction temperature 35 hours；Reaction terminates rear stratification, isolates aqueous phase, then neutralized, and washing, vacuum distillation obtains tung oil polyalcohol；（2）By step（1）Obtained tung oil polyalcohol is mixed in proportion with base catalyst, is warming up to after 90 140 DEG C, is added epoxides and is carried out polymerisation, is reacted after terminating through acid neutralization, washing, vacuum distillation, is obtained low hydroxyl value tung oil polyalcohol.The hydroxyl value of low hydroxyl value tung oil polyalcohol prepared by the present invention is 30 100mgKOH/g, and acid number is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 90%, it is adaptable to prepare flexible polyurethane foam material, polyurethane elastomer etc..
Description
Technical field
The invention belongs to polyurethane material field, and in particular to a kind of low hydroxyl value tung oil polyalcohol and preparation method thereof.
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, 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.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of low 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, efficiently synthesize tung oil polyalcohol；Then by the tung oil polyalcohol of preparation further with epoxide polymerization, obtain low hydroxyl value tung oil polyol product.
The preparation method of the low hydroxyl value tung oil polyalcohol of the present invention, including following content：（1）Tung oil, carboxylic acid, catalyst, hydroxylating agent are mixed in proportion, and are warming up to 35-45 DEG C；Hydrogenperoxide steam generator is added dropwise under intense agitation, control rate of addition makes reaction temperature maintain after 40-65 DEG C, completion of dropping, maintenance reaction temperature 3-5 hours；Reaction terminates rear stratification, isolates aqueous phase, then neutralized, and washing, vacuum distillation obtains tung oil polyalcohol；（2）By step（1）Obtained tung oil polyalcohol is mixed in proportion with base catalyst, is warming up to after 90-140 DEG C, is added epoxides and is carried out polymerisation, is reacted after terminating through acid neutralization, washing, vacuum distillation, is obtained low hydroxyl value tung oil polyalcohol.
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）Described catalyst is inorganic acid, urea or metal ion support type cation exchange resin catalyst etc..Inorganic acid catalyst 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.During using urea seeding agent, consumption is the 0.1%-2.0% of tung oil quality.In the metal ion support type cation exchange resin catalyst of use, matrix cationic ion-exchange resin is macroporous type strongly acidic styrene type cation exchange resin, and the metal ion of load is selected from Al3+、Fe3+、Fe2+、Cu2+、Zn2+、Sn4+、Ni2+、Co3+One or more in, preferably Al3+, metal ion load capacity accounts for the 0.5%-3% of catalyst quality；Catalyst amount is the 5%-15% 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.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 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）Described neutralization reaction 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%.
Step of the present invention（2）The course of reaction specially mixes tung oil polyalcohol with base catalyst in proportion, is progressively warming up under nitrogen protection after 90-140 DEG C, and epoxides is added in 5-10h, and isothermal reaction 2-6h terminates reaction.
Step of the present invention（2）The base catalyst is alkali metal（Such as lithium, sodium, potassium, rubidium, caesium, francium）Oxide or hydroxide, the one or more in such as lithia, sodium oxide molybdena, potassium oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide；Catalyst amount is the 0.1%-1.0% of tung oil polyol quality.
Step of the present invention（2）The epoxides is the one or more in the epoxides such as expoxy propane, oxirane, epoxy butane；Epoxides consumption is 2.0-5.0 times of tung oil polyol quality.
Step of the present invention（2）The sour neutralization reaction concentration neutralizes for 5wt%-20wt% phosphate aqueous solution.Described washing temperature is 50-80 DEG C, and described vacuum distillation is the 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%.
Low hydroxyl value tung oil polyalcohol of the present invention is prepared by the invention described above method.The hydroxyl value of prepared tung oil polyalcohol is 30-100mgKOH/g, and acid number is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 90%, it is adaptable to prepare flexible polyurethane foam material, polyurethane elastomer etc..
The application of the tung oil polyalcohol of preparation of the present 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 flexible polyurethane foam material, polyurethane elastomer etc..
More than 85% unsaturated bond is carbon carbon conjugated triene key in tung oil molecule, because the presence of conjugated double bond makes epoxide group reactivity higher during polyalcohol is prepared, poor selectivity, easily occurs side reaction, so as to generate macromolecules cross-linking product, viscosity is caused to sharply increase, it is impossible to for further synthesis of polyurethane material.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；By the tung oil polyalcohol of acquisition further with epoxide polymerization, the low hydroxyl value tung oil polyol product of high-quality, the preparation available for flexible polyurethane foam material, polyurethane elastomer can be obtained.Compared with petroleum-based polyols, low hydroxyl value tung oil polyalcohol prepared by the present invention has the advantages that raw material is renewable, non-toxic and biological degradability is good, belongs to environment-friendly biopolyol.
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, 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 process units construction cost.The present invention substitutes small molecule alcohol reagent 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
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 determined according to the phthalic anhydride esterification method in GB/T 12008.3-2009, 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, 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.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.
Take the tung oil polyalcohol 250g of above-mentioned preparation, sodium hydroxide 1.25g to be added in reactor to be well mixed, be progressively warming up to after 120 DEG C under nitrogen protection, 760g expoxy propane is added in 7.5h, then proceed to react 4h, terminate reaction.Reaction system is washed with 10wt% phosphate 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, low hydroxyl value tung oil polyalcohol is obtained.After testing, hydroxyl value is 68.3mgKOH/g, viscosity 7300mPas, acid number 0.42mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.4%, available for preparing the products such as flexible polyurethane foam material, polyurethane elastomer.
Embodiment 2
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 45 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 380g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 65 DEG C or so, after completion of dropping, and the constant temperature 3h at 65 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyalcohol is produced.
Take the tung oil polyalcohol 250g of above-mentioned preparation, potassium hydroxide 1.25g to be added in reactor to be well mixed, be progressively warming up to after 140 DEG C under nitrogen protection, 760g oxirane is added in 7.5h, then proceed to react 3h, terminate reaction.Reaction system is washed with 10wt% phosphate 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, low hydroxyl value tung oil polyalcohol is obtained.After testing, hydroxyl value is 72.4mgKOH/g, viscosity 7220mPas, acid number 0.42mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.5%, available for preparing the products such as flexible polyurethane foam material, polyurethane elastomer.
Embodiment 3
500g tung oil, 55g formic acid are added in 2000mL three-necked flasks（85wt% solution）, the 4g concentrated sulfuric acids, 100g n-caproic acids, be warming up to 35 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 285g 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 1000-3000Pa, 80 DEG C, tung oil polyalcohol is produced.
Take the tung oil polyalcohol 250g of above-mentioned preparation, lithium hydroxide 1.25g to be added in reactor to be well mixed, be progressively warming up to after 90 DEG C under nitrogen protection, 510g epoxy butanes are added in 5h, then proceed to react 6h, terminate reaction.Reaction system is washed with 10wt% phosphate 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, low hydroxyl value tung oil polyalcohol is obtained.After testing, hydroxyl value is 95.6mgKOH/g, viscosity 7750mPas, acid number 0.46mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.9%, available for preparing the products such as flexible polyurethane foam material, polyurethane elastomer.
Embodiment 4
Using handling process and operating condition same as Example 1, difference is step（1）Middle catalyst uses 5g urea.The hydroxyl value of obtained tung oil polyalcohol is 72.2mgKOH/g, viscosity 7250mPas, acid number 0.41mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.6%, available for preparing the products such as flexible polyurethane foam material, polyurethane elastomer.
Embodiment 5
Using handling process and operating condition same as Example 1, difference is step（1）Middle catalyst uses 50g Al3+Support type cation exchange resin catalyst, wherein Al3+Load capacity account for the 1.0% of catalyst quality.The hydroxyl value of obtained tung oil polyalcohol is 75.4mgKOH/g, viscosity 7180mPas, acid number 0.40mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.8%, available for preparing the products such as flexible polyurethane foam material, polyurethane elastomer.
Embodiment 6
Using handling process and operating condition same as Example 1, difference is step（1）Middle carboxylic acid uses acetic acid.The hydroxyl value of obtained tung oil polyalcohol is 46.4mgKOH/g, viscosity 7080mPas, acid number 0.40mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.2%, available for preparing the products such as flexible polyurethane foam material, polyurethane elastomer.
Embodiment 7
Using handling process and operating condition same as Example 1, difference is step（1）Middle hydroxylating agent uses positive enanthic acid.The hydroxyl value of obtained tung oil polyalcohol is 56.3mgKOH/g, viscosity 8800mPas, acid number 0.44mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.3%, available for preparing the products such as flexible polyurethane foam material, polyurethane elastomer.
Embodiment 8
Using handling process and operating condition same as Example 1, difference is step（1）Middle hydroxylating agent uses isooctyl acid.The hydroxyl value of obtained tung oil polyalcohol is 52.4mgKOH/g, viscosity 9400mPas, acid number 0.47mgKOH/g, and moisture is less than 0.1wt%, and yield is 91.9%, available for preparing the products such as flexible polyurethane foam material, polyurethane elastomer.
Embodiment 9
Using handling process and operating condition same as Example 1, difference is step（2）Neutral and alkali catalyst uses sodium oxide molybdena.The hydroxyl value of obtained tung oil polyalcohol is 73.6mgKOH/g, viscosity 6940mPas, acid number 0.40mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.7%, available for preparing the products such as flexible polyurethane foam material, polyurethane elastomer.
Comparative example 1
Using handling process and operating condition same as Example 1, difference is step（1）In be added without hydroxylating agent.Product viscosity is 470000mPas, 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 handling process and operating condition same as Example 1, difference is to use butanol as hydroxylating agent.The hydroxyl value of obtained tung oil polyalcohol is 42.5mgKOH/g, viscosity 57200mPas, because in reaction system easily with formic acid esterification occurs for butanol, cause actual concentrations of the butanol 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 3
Using treatment process condition same as Example 1, difference is to prepare polyalcohol using soybean oil.Product hydroxyl value is 6.2mgKOH/g, and due to product, no generation hydroxylating, hydroxyl value are too low in first step reaction, therefore can not occur polymerisation with epoxides, it is impossible to for preparing Contents In Polyether Polyol.
Comparative example 4
Using treatment process condition same as Example 1, difference is directly to use tung oil to be reacted with base catalyst.Because epoxidation and hydroxylating do not occur for tung oil, so product does not have reactive hydroxyl, it is impossible to for preparing Contents In Polyether Polyol.
Claims (15)
1. a kind of preparation method of low hydroxyl value tung oil polyalcohol, it is characterised in that including following content：（1）Tung oil, carboxylic acid, catalyst, hydroxylating agent are mixed in proportion, and are warming up to 35-45 DEG C；Hydrogenperoxide steam generator is added dropwise under intense agitation, control rate of addition makes reaction temperature maintain after 40-65 DEG C, completion of dropping, maintenance reaction temperature 3-5 hours；Reaction terminates rear stratification, isolates aqueous phase, then neutralized, and washing, vacuum distillation obtains tung oil polyalcohol；（2）By step（1）Obtained tung oil polyalcohol is mixed in proportion with base catalyst, is warming up to after 90-140 DEG C, is added epoxides and is carried out polymerisation, is reacted after terminating through acid neutralization, washing, vacuum distillation, is obtained low hydroxyl value tung oil polyalcohol.
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）Described catalyst is inorganic acid, urea or metal ion support type cation exchange resin catalyst.
4. in accordance with the method for claim 3, 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；During using urea seeding agent, consumption is the 0.1%-2.0% of tung oil quality；Using in metal ion support type cation exchange resin catalyst, matrix cationic ion-exchange resin is macroporous type strongly acidic styrene type cation exchange resin, and the metal ion of load is selected from Al3+、Fe3+、Fe2+、Cu2+、Zn2+、Sn4+、Ni2+、Co3+In one or more, metal ion load capacity accounts for the 0.5%-3% of catalyst quality, and catalyst amount is the 5%-15% of tung oil quality.
5. 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.
6. in accordance with the method for claim 5, it is characterised in that：Described oil-soluble aliphatic acid is selected from C6-C12Straight or branched saturated fatty acid in one or more.
7. in accordance with the method for claim 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. 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.
9. in accordance with the method for claim 1, it is characterised in that：Step（1）The neutralization reaction concentration is 5wt%-20wt% sodium bicarbonate 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%.
10. in accordance with the method for claim 1, it is characterised in that：Step（2）Described course of reaction is that after being progressively warming up to 90-140 DEG C under nitrogen protection, epoxides is added in 5-10h, and isothermal reaction 2-6h terminates reaction.
11. according to the method described in claim 1 or 10, it is characterised in that：Step（2）The base catalyst is the oxide or hydroxide of alkali metal, and the alkali metal is lithium, sodium, potassium, rubidium, caesium or francium.
12. in accordance with the method for claim 11, it is characterised in that：The base catalyst is the one or more in lithia, sodium oxide molybdena, potassium oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, and catalyst amount is the 0.1%-1.0% of tung oil polyol quality.
13. according to the method described in claim 1 or 10, it is characterised in that：Step（2）The epoxides is the one or more in expoxy propane, oxirane, epoxy butane, and consumption is 2.0-5.0 times of tung oil polyol quality.
14. according to the method described in claim 1 or 10, it is characterised in that：Step（2）The acid neutralizes concentration and neutralized for 5wt%-20wt% phosphate aqueous solution；Washing temperature is 50-80 DEG C；Vacuum distillation is the 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%.
15. low hydroxyl value tung oil polyalcohol prepared by any methods described of claim 1~14, it is characterised in that：The hydroxyl value of prepared low hydroxyl value tung oil polyalcohol is 30-100mgKOH/g, and acid number is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 90%, it is adaptable to prepare flexible polyurethane foam material, polyurethane elastomer.
Priority Applications (1)
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| CN108329284A (en) * | 2017-12-29 | 2018-07-27 | 安庆北化大科技园有限公司 | A kind of vegetable oil-based polyols and its preparation method and application |
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| WO2006012344A1 (en) * | 2004-06-25 | 2006-02-02 | Pittsburg State University | Modified vegetable oil-based polyols |
| WO2008130646A1 (en) * | 2007-04-18 | 2008-10-30 | Biobased Technologies, Llc | A process for the manufacture of natural oil hydroxylates |
| CN101386563A (en) * | 2008-10-24 | 2009-03-18 | 江苏钟山化工有限公司 | Method for preparing plant oil-based polyol |
| CN102206154A (en) * | 2011-03-11 | 2011-10-05 | 清华大学 | Vegetable oil polyol and preparation method thereof |
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| WO2006012344A1 (en) * | 2004-06-25 | 2006-02-02 | Pittsburg State University | Modified vegetable oil-based polyols |
| WO2008130646A1 (en) * | 2007-04-18 | 2008-10-30 | Biobased Technologies, Llc | A process for the manufacture of natural oil hydroxylates |
| CN101386563A (en) * | 2008-10-24 | 2009-03-18 | 江苏钟山化工有限公司 | Method for preparing plant oil-based polyol |
| CN102206154A (en) * | 2011-03-11 | 2011-10-05 | 清华大学 | Vegetable oil polyol and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108329284A (en) * | 2017-12-29 | 2018-07-27 | 安庆北化大科技园有限公司 | A kind of vegetable oil-based polyols and its preparation method and application |
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