CN105712880A - Tung oil polyol and synthesis method thereof - Google Patents
Tung oil polyol and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses tung oil polyol and a synthesis method thereof. The synthesis method comprises the following steps: mixing tung oil, carboxylic acid, urea, a hydroxylation reagent, and deionized water according to a certain ratio, heating the mixture to a temperature of 35 to 45 DEG C; dropwise adding a hydrogen peroxide solution under violent stirring, controlling the addition speed to maintain the temperature in a range of 40 to 65 DEG C, after addition, maintaining the reaction temperature for 3 to 5 hours, stopping the reactions; allowing the reaction system to stand still to carry out layering, separating water phase from the reaction system, neutralizing the oil phase, washing the oil phase by water, and subjecting the oil phase to reduced pressure distillation to obtain tung oil polyol. The yield of the prepared tung oil polyol is more than 92%, the hydroxyl value of the product is 120 to 270 mgKOH/g, the acid value is less than 1.0 mgKOH/g, the water content is less than 0.1 wt%, and the tung oil polyol can be used to prepare a polyurethane material.
Description
Technical field
The invention belongs to polyurethane material field, be specifically related to a kind of Oleum Verniciae fordii polyhydric alcohol and manufacture method thereof.
Background technology
Polyurethane material, owing to having good mechanical performance and being prone to molding, has been widely used in industry and daily life.Main raw material(s) for producing polyurethane includes isocyanates, polyhydric alcohol and other additives, and wherein the ratio of polyhydric alcohol account for more than 50%.In industrial processes, polyhydric alcohol is mainly used in polyurethane field, and therefore the influence factor of polyurethane industries among others is also the major influence factors in polyhydric alcohol market.Polyhydric alcohol can be divided into polyether polyol and PEPA by molecular structure, and wherein, polyether polyol is occupied an leading position in the market, occupies more than the 70% of whole polyhydric alcohol demand.
Generally, polyhydric alcohol extracts preparation from oil.And oil is as non-renewable resources, scarcity causes the continuous rise of its price, and cause the price continuous rise of primary raw material that the polyhydric alcohol such as downstream product expoxy propane, oxirane produces, and according to current depletion rate, petroleum resources want approach exhaustion eventually.Therefore, from the angle of sustainable development and enterprise competitiveness, new material and the new technology of finding energy petroleum replacing base polyethers become strategic development task.
The U.S. is the major country of production of soybean oil in the world, and except edible, the various chemical products that it is raw material with soybean oil that the scientific research institution of the U.S. is also actively working to develop, with petroleum replacing base chemicals.Concentrating on the unsaturated bond utilized in soybean oil subchain recently, by modifiying double bond, making the oxidation of vegetable oil initial ring, hydroxylating, thus preparing soybean oil polyol.The advantage of the method is reaction temperature relatively low (40-70 DEG C), and product qualities, color and luster are good, so the concern widely obtained.
The peroxy acid such as the Z.S.Petrovic in kansas, u.s.a (Kansas) polymer research center reacts with soybean oil, is prepared for epoxy soybean oil, and double bond is changed into epoxy radicals；Then epoxy soybean oil under the catalytic action of effective catalyst Tetrafluoroboric acid with water and alcohol generation ring-opening reaction, prepare the vegetable oil polyol containing hydroxyl, the hydroxyl value of polyhydric alcohol is 110 ~ 213mgKOH/g, and viscosity is 1000 ~ 7000mPa s, and conversion ratio is up to 85% ~ 95%.
US20070123725 provides a kind of method preparing soybean oil polyol, including epoxidation and the hydroxylation procedures of polyunsaturated vegetable oil, forms vegetable oil-based polyether polyol.First, by soybean oil or Semen Allii Tuberosi wet goods polyunsaturated vegetable oil and organic acid and hydroperoxidation, form epoxidized vegetable oil, then the mixed solution of epoxidized vegetable oil Yu first alcohol and water is carried out ring-opening reaction generation vegetable oil polyol.
US20060041157 describes the method for preparation soybean oil polyol, react with Ring Opening Reagent under catalysts conditions including the vegetable oil making PART EPOXY, forming oligomeric vegetable oil polylol, Ring Opening Reagent includes small molecule polyol, vegetable oil polyol or other polyols.The degree of functionality of oligomeric vegetable oil polyhydric alcohol is 1 ~ 6, and hydroxyl value is 20 ~ 300mgKOH/g.
Oleum Verniciae fordii is the special product of China, is also the important raw material of industry and traditional exporting.At present, China's Oleum Verniciae fordii annual production reaches more than 100,000 tons, accounts for about the 35% of world's Oleum Verniciae fordii yield.Therefore, China studies Oleum Verniciae fordii and makes more Product industrialization relevant with Oleum Verniciae fordii have special significance.But, utilize Oleum Verniciae fordii to prepare high-quality vegetable oil polyol, owing to Oleum Verniciae fordii degree of unsaturation is higher, and be the polyunsaturated vegetable oil uniquely in nature with conjugated double bond, iodine number reaches more than 170, wherein the unsaturated bond of more than 85% is carbon carbon conjugated triene key, so Oleum Verniciae fordii in preparing the epoxidised process of polyhydric alcohol owing to the existence of conjugated double bond makes epoxide group reactivity higher, poor selectivity, easily there is side reaction, thus generating macromolecules cross-linking product, cause that viscosity sharply increases, at room temperature normally solid, further synthesis of polyurethane material cannot be used for.Research Literature is (such as EpoxidationofNaturalTriglycerideswithEthylmethyldioxiran e, " JournaloftheAmericanOilChemists'Society ", 1996,73:461-464) investigate different vegetable oil, epoxidation process such as polyunsaturated vegetable oils such as Semen Maydis oil, soybean oil, Oleum Helianthi, Oleum Gossypii semen, Oleum Verniciae fordii, it is again seen that the Oleum Verniciae fordii only with conjugated double bond there occurs cross-linking reaction in epoxidised process, cause that viscosity sharply increases.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of Oleum Verniciae fordii polyhydric alcohol and synthetic method thereof.The present invention utilizes the conjugated double bond of Oleum Verniciae fordii can improve the feature of epoxide group reactivity, is simultaneously introduced hydroxylating agent epoxidised, it is possible to is effectively prevented from the generation of crosslinking side reaction, and forms Oleum Verniciae fordii polyol product.
The synthetic method of Oleum Verniciae fordii polyhydric alcohol of the present invention, including following content: Oleum Verniciae fordii, carboxylic acid, carbamide, hydroxylating agent, deionized water are mixed in proportion, and is warming up to 35 ~ 45 DEG C；Under intense agitation, drip hydrogenperoxide steam generator, control rate of addition and make reaction temperature maintain 40 ~ 65 DEG C, after dropwising, maintain reaction temperature 3 ~ 5 hours, terminate reaction；Reaction system sequentially passes through stratification, isolates aqueous phase, neutralizes, washing, decompression distillation, obtains Oleum Verniciae fordii polyhydric alcohol.
Described carboxylic acid can be one or more in formic acid, acetic acid, propanoic acid, butanoic acid, valeric acid, benzoic acid, phenylacetic acid etc., it is preferred to formic acid.Carboxylic acid can react generation peroxycarboxylic acid with hydrogenperoxide steam generator, peroxycarboxylic acid makes the conjugated double bond in Oleum Verniciae fordii be converted into epoxy bond, discharge carboxylic acid simultaneously, therefore while generating epoxy bond, carboxylic acid does not consume, but very few carboxylic acid content will cause that system reaction rate is slack-off, so the mass ratio controlling carboxylic acid and Oleum Verniciae fordii is 0.05:1 ~ 0.5:1.
Described carbamide is as catalyst, and consumption is the 0.1% ~ 2.0% of Oleum Verniciae fordii quality.It is to be noted, owing to strong acid can catalytic esterification, therefore the present invention does not use inorganic acid as catalyst, the degree that can be effectively reduced in reaction system organic carboxyl acid and hydroxylating agent generation esterification, improve the utilization ratio of carboxylic acid, the consumption of carboxylic acid can be reduced when preparing polyhydric alcohol；Do not use inorganic acid and reduction carboxylic acid content to make system acid concentration reduce simultaneously, desirably prevent product and crosslinking side reaction occurs, it is possible to decrease the viscosity of product.It addition, use urea seeding agent that environment is more friendly.
Described hydroxylating agent can be alcohols or alcamines, and consumption is 0.5 ~ 2 times of Oleum Verniciae fordii quality.Wherein one or more in methanol, ethanol, ethylene glycol, propanol, isopropanol, glycerol, butanol, BDO, tetramethylolmethane, xylitol, sorbitol etc. of alcohols hydroxylating agent, it is preferred to butanol；One or more in monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, ethanolamine, diethanolamine, triethanolamine etc. of alcamines hydroxylating agent, it is preferred to triethanolamine.
The consumption of described deionized water is 0.01 ~ 0.2 times of Oleum Verniciae fordii quality, and the addition of deionized water is possible to prevent the esterification of initial reaction stage carboxylic acid and hydroxylating agent, it is to avoid the consumption of carboxylic acid, increases double bond conversion rate.
Described hydrogenperoxide steam generator plays the effect of oxidant, makes carboxylic acid be oxidized to peroxy acid.The concentration of hydrogen peroxide is more high, reacts more violent, and system heat release is serious, and side reaction easily occurs, so the concentration selecting hydrogenperoxide steam generator is 20wt% ~ 60wt%, the consumption of hydrogenperoxide steam generator is Oleum Verniciae fordii quality 0.6 ~ 1.2 times.
Described neutralization reaction can use ammonia, sodium carbonate or sodium bicarbonate, it is preferred to use the sodium bicarbonate solution that concentration is 5wt% ~ 20wt% neutralizes.Described washing temperature is 50 ~ 80 DEG C, to prevent system from emulsion occur.Described decompression distillation is at pressure 1000 ~ 3000Pa, and under 60 ~ 120 DEG C of conditions of temperature, the hydroxylating agent in removing system and residual moisture, make product moisture content less than 0.1wt%.
Oleum Verniciae fordii polyhydric alcohol of the present invention is synthesized by the invention described above method.Synthesized Oleum Verniciae fordii polyhydric alcohol productivity is higher than 92%, and product hydroxyl value is 120 ~ 270mgKOH/g, and acid number is lower than 1.0mgKOH/g, and moisture, lower than 0.1wt%, can be used for preparing polyurethane material.
China is country of origin and the big producing country of Oleum Verniciae fordii in the world, raw material rich reserves, studies and is of great significance for raw material chemical products tool with Oleum Verniciae fordii, the polyol product that especially industrial consumption amount is huge.But owing in Oleum Verniciae fordii molecule, the unsaturated bond of more than 85% is carbon carbon conjugated triene key, owing to the existence of conjugated double bond makes epoxide group reactivity higher in preparing polyhydric alcohol process, poor selectivity, easily there is side reaction, thus generating macromolecules cross-linking product, cause that viscosity sharply increases, it is impossible to for further synthesis of polyurethane material.
The present invention utilizes the conjugated double bond of Oleum Verniciae fordii can improve the feature of epoxide group reactivity, is simultaneously introduced hydroxylating agent epoxidised, it is possible to be effectively prevented from the generation of crosslinking side reaction, it is thus achieved that Oleum Verniciae fordii polyol product be applicable to polyurethane material preparation.Prepared Oleum Verniciae fordii polyhydric alcohol is compared with petroleum-based polyols, has that raw material is renewable, avirulence and a good advantage of biological degradability, belongs to eco-friendly biopolyol.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.In the present invention, wt% represents mass fraction.The hydroxyl value of prepared polyol product all measures according to the phthalic anhydride esterification method in GB/T12008.3-2009, and acid number all measures according to GB/T12008.5-2010 method, and viscosity all measures according to the rotating cylinder viscometer method in GB/T12008.7-2010.
Embodiment 1
2000mL there-necked flask adds 500g Oleum Verniciae fordii, 110g formic acid (85wt% solution), 5g carbamide, 300g butanol, 50g deionized water, is warming up to 40 DEG C and stirs.Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 450g under intense agitation, control drop rate and make reaction temperature maintain about 50 DEG C, after dropwising, constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, remove aqueous phase, by oil phase with the washing of 10wt% sodium bicarbonate aqueous solution to neutral, then with 70 DEG C of hot wash products 3 times.Product after washing being distilled 2h under 2000Pa, 80 DEG C of conditions, obtains Oleum Verniciae fordii polyol product, productivity is 93.9%, product hydroxyl value is 254mgKOH/g, viscosity 7710mPa s, acid number 0.79mgKOH/g, moisture, lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 2
2000mL there-necked flask adds 500g Oleum Verniciae fordii, 110g formic acid (85wt% solution), 5g carbamide, 300g butanol, 50g deionized water, is warming up to 45 DEG C and stirs.Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 450g under intense agitation, control drop rate and make reaction temperature maintain about 65 DEG C, after dropwising, constant temperature 5h at 65 DEG C, reaction terminates.After question response system layering, remove aqueous phase, by oil phase with the washing of 10wt% sodium bicarbonate aqueous solution to neutral, then with 70 DEG C of hot wash products 3 times.Product after washing being distilled 2h under 2000Pa, 80 DEG C of conditions, obtains Oleum Verniciae fordii polyol product, productivity is 93.5%, product hydroxyl value is 241mgKOH/g, viscosity 9900mPa s, acid number 0.88mgKOH/g, moisture, lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 3
2000mL there-necked flask adds 500g Oleum Verniciae fordii, 110g formic acid (85wt% solution), 5g carbamide, 300g butanol, 50g deionized water, is warming up to 35 DEG C and stirs.Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 450g under intense agitation, control drop rate and make reaction temperature maintain about 40 DEG C, after dropwising, constant temperature 4h at 40 DEG C, reaction terminates.After question response system layering, remove aqueous phase, by oil phase with the washing of 10wt% sodium bicarbonate aqueous solution to neutral, then with 70 DEG C of hot wash products 3 times.Product after washing being distilled 2h under 2000Pa, 80 DEG C of conditions, obtains Oleum Verniciae fordii polyol product, productivity is 92.4%, and product hydroxyl value is 151mgKOH/g, viscosity 3050mPa s, acid number 0.63mgKOH/g, and moisture, lower than 0.1wt%, can be used for preparing polyurethane products.
Embodiment 4
2000mL there-necked flask adds 500g Oleum Verniciae fordii, 110g formic acid (85wt% solution), 5g carbamide, 300g ethanol, 50g deionized water, is warming up to 40 DEG C and stirs.Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 450g under intense agitation, control drop rate and make reaction temperature maintain about 50 DEG C, after dropwising, constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, remove aqueous phase, by oil phase with the washing of 10wt% sodium bicarbonate aqueous solution to neutral, then with 70 DEG C of hot wash products 3 times.Product after washing being distilled 2h under 2000Pa, 80 DEG C of conditions, obtains Oleum Verniciae fordii polyol product, productivity is 93.2%, product hydroxyl value is 227mgKOH/g, viscosity 11500mPa s, acid number 0.86mgKOH/g, moisture, lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 5
2000mL there-necked flask adds 500g Oleum Verniciae fordii, 110g formic acid (85wt% solution), 5g carbamide, 300g triethanolamine, 50g deionized water, is warming up to 40 DEG C and stirs.Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 450g under intense agitation, control drop rate and make reaction temperature maintain about 50 DEG C, after dropwising, constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, remove aqueous phase, by oil phase with the washing of 10wt% sodium bicarbonate aqueous solution to neutral, then with 70 DEG C of hot wash products 3 times.Product after washing being distilled 2h under 2000Pa, 80 DEG C of conditions, obtains Oleum Verniciae fordii polyol product, productivity is 93.2%, product hydroxyl value is 223mgKOH/g, viscosity 11700mPa s, acid number 0.86mgKOH/g, moisture, lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 6
2000mL there-necked flask adds 500g Oleum Verniciae fordii, 110g glacial acetic acid, 5g carbamide, 300g butanol, 50g deionized water, is warming up to 40 DEG C and stirs.Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 450g under intense agitation, control drop rate and make reaction temperature maintain about 50 DEG C, after dropwising, constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, remove aqueous phase, by oil phase with the washing of 10wt% sodium bicarbonate aqueous solution to neutral, then with 70 DEG C of hot wash products 3 times.Product after washing being distilled 2h under 2000Pa, 80 DEG C of conditions, obtains Oleum Verniciae fordii polyol product, productivity is 92.2%, and product hydroxyl value is 125mgKOH/g, viscosity 2540mPa s, acid number 0.63mgKOH/g, and moisture, lower than 0.1wt%, can be used for preparing polyurethane products.
Embodiment 7
2000mL there-necked flask adds 500g Oleum Verniciae fordii, 100g formic acid (85wt% solution), 2.5g carbamide, 300g butanol, 50g deionized water, is warming up to 40 DEG C and stirs.Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 350g under intense agitation, control drop rate and make reaction temperature maintain about 50 DEG C, after dropwising, constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, remove aqueous phase, by oil phase with the washing of 10wt% sodium bicarbonate aqueous solution to neutral, then with 60 DEG C of hot wash products 3 times.Product after washing being distilled 2h under 2000Pa, 90 DEG C of conditions, obtains Oleum Verniciae fordii polyol product, productivity is 92.9%, product hydroxyl value is 168mgKOH/g, viscosity 3750mPa s, acid number 0.57mgKOH/g, moisture, lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 8
2000mL there-necked flask adds 500g Oleum Verniciae fordii, 150g formic acid (85wt% solution), 8g carbamide, 300g butanol, 50g deionized water, is warming up to 40 DEG C and stirs.Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 700g under intense agitation, control drop rate and make reaction temperature maintain about 50 DEG C, after dropwising, constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, remove aqueous phase, by oil phase with the washing of 15wt% sodium bicarbonate aqueous solution to neutral, then with 70 DEG C of hot wash products 3 times.Product after washing being distilled 2h under 1500Pa, 100 DEG C of conditions, obtains Oleum Verniciae fordii polyol product, productivity is 93.8%, product hydroxyl value is 268mgKOH/g, viscosity 10400mPa s, acid number 0.83mgKOH/g, moisture, lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Comparative example 1
Adopt the treatment process condition identical with embodiment 1, be different in that and be added without hydroxylating agent.The viscosity 417000mPa s of product, owing to product viscosity is excessive and cannot dissolve, it is impossible to carry out hydroxylating further, therefore product is not used to and prepares hard polyurethane foam product.
Comparative example 2
Adopt the treatment process condition identical with embodiment 1, be different in that and be added without hydroxylating agent, add petroleum ether 300g(and play diluent effect).Product viscosity 410200mPa s, owing to product viscosity is excessive and cannot dissolve, it is impossible to carry out hydroxylating further, therefore product is not used to and prepares hard polyurethane foam product.
Comparative example 3
Adopt the treatment process condition identical with embodiment 1, be different in that polyhydric alcohol prepared by use soybean oil.Product hydroxyl value is 4.8mgKOH/g, does not occur due to product hydroxylating, hydroxyl value too low, therefore product is not used to and prepares polyurethane products.
Claims (11)
1. an Oleum Verniciae fordii polyhydric alcohol and synthetic method thereof, it is characterised in that include following content: Oleum Verniciae fordii, carboxylic acid, carbamide, hydroxylating agent, deionized water are mixed in proportion, and be warming up to 35 ~ 45 DEG C；Under intense agitation, drip hydrogenperoxide steam generator, control rate of addition and make reaction temperature maintain 40 ~ 65 DEG C, after dropwising, maintain reaction temperature 3 ~ 5 hours, terminate reaction；Reaction system sequentially passes through stratification, isolates aqueous phase, neutralized, washing, decompression distillation, obtains Oleum Verniciae fordii polyhydric alcohol.
2. in accordance with the method for claim 1, it is characterised in that: described carboxylic acid is one or more in formic acid, acetic acid, propanoic acid, butanoic acid, valeric acid, benzoic acid, phenylacetic acid, it is preferred to formic acid.
3. the method described in claim 1 or 2, it is characterised in that: the mass ratio controlling carboxylic acid and Oleum Verniciae fordii is 0.05:1 ~ 0.5:1.
4. in accordance with the method for claim 1, it is characterised in that: the consumption of carbamide is the 0.1% ~ 2.0% of Oleum Verniciae fordii quality.
5. in accordance with the method for claim 1, it is characterised in that: described hydroxylating agent is alcohols or alcamines, and consumption is 0.5 ~ 2 times of Oleum Verniciae fordii quality.
6. in accordance with the method for claim 5, it is characterised in that: one or more in methanol, ethanol, ethylene glycol, propanol, isopropanol, glycerol, butanol, BDO, tetramethylolmethane, xylitol, sorbitol of described alcohols hydroxylating agent；One or more in monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, ethanolamine, diethanolamine, triethanolamine of described alcamines hydroxylating agent.
7. the method described in claim 1 or 6, it is characterised in that: described hydroxylating agent is butanol.
8. in accordance with the method for claim 1, it is characterised in that: the consumption of described deionized water is 0.01 ~ 0.2 times of Oleum Verniciae fordii quality.
9. in accordance with the method for claim 1, it is characterised in that: the concentration of described hydrogenperoxide steam generator is 20wt% ~ 60wt%, and consumption is Oleum Verniciae fordii quality 0.6 ~ 1.2 times.
10. in accordance with the method for claim 1, it is characterised in that: the described reaction working concentration that neutralizes is the sodium bicarbonate solution of 5wt% ~ 20wt%；Washing temperature is 50 ~ 80 DEG C；Decompression distillation is at pressure 1000 ~ 3000Pa, and under 60 ~ 120 DEG C of conditions of temperature, the hydroxylating agent in removing system and residual moisture, make product moisture content less than 0.1wt%.
11. Oleum Verniciae fordii polyhydric alcohol prepared by the arbitrary described method of claim 1～10, it is characterised in that: Oleum Verniciae fordii polyhydric alcohol productivity is higher than 92%, and product hydroxyl value is 120 ~ 270mgKOH/g, and acid number is lower than 1.0mgKOH/g, and moisture, lower than 0.1wt%, can be used for preparing polyurethane material.
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