CN105646225A - Tung oil-based polyol and preparation method thereof - Google Patents
Tung oil-based polyol and preparation method thereof Download PDFInfo
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- CN105646225A CN105646225A CN201410730986.8A CN201410730986A CN105646225A CN 105646225 A CN105646225 A CN 105646225A CN 201410730986 A CN201410730986 A CN 201410730986A CN 105646225 A CN105646225 A CN 105646225A
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Abstract
The invention discloses a tung oil-based polyol and a preparation method thereof. The preparation method comprises following steps: tung oil, an organic metal complex catalyst, and a hydroxylation reagent are mixed at a certain ratio, and are heated to 50 to 70 DEG C; under violent stirring, a hydrogen peroxide solution is added dropwise, adding speed is controlled so as to maintain the reaction temperature to be 70 to 90 DEG C, after adding of the hydrogen peroxide solution, reaction temperature is maintained for 3 to 5, and reaction is stopped; an obtained reaction system is subjected to filtering so as to separate the solid catalyst, is allowed to stand for layering so as to separate a water phase, and is subjected to reduced pressure distillation so as to obtain the tung oil-based polyol. The yield of the tung oil-based polyol is higher than 92%; product hydroxyl value ranges from 120 to 270mgKOH/g; acid value is lower than 1.0mgKOH/g; water content is lower than 0.1wt%; and the tung oil-based polyol can be used for preparing polyurethane materials.
Description
Technical field
The invention belongs to polyurethane material field, be specifically related to a kind of Oleum Verniciae fordii polylol and preparation method.
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 polylol and preparation method. 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 polylol product.
The preparation method of Oleum Verniciae fordii polylol of the present invention, including following content: Oleum Verniciae fordii, organometallic complex catalyst, hydroxylating agent are mixed in proportion, and are warming up to 50 ~ 70 DEG C; Under intense agitation, drip hydrogenperoxide steam generator, control rate of addition and make reaction temperature maintain 70 ~ 90 DEG C, after dropwising, maintain reaction temperature 3 ~ 5 hours, terminate reaction; Reaction system sequentially passes through and filters to isolate solid catalyst, stratification, isolates aqueous phase, decompression distillation, obtains Oleum Verniciae fordii polylol.
Described organometallic complex catalyst has below formula:
Wherein, M can be transition metal molybdenum, vanadium, titanium, manganese, cobalt, copper, nickel etc. Described transition metal source is in acetyl acetone, vanadium acetylacetonate, titanium acetylacetone, manganese acetylacetonate, acetylacetone cobalt, acetylacetone copper, nickel acetylacetonate, manganese acetate, cobalt acetate, copper acetate, nickel acetate, copper chloride or Nickel dichloride. etc. ?ip circle sends ? green pepper �� ticket Jiangxi, the cap nine fluffy Kuo Yan to thank to the ? fish hawk folds in a garment creek rank far or indistinct tip of polished ? to fulfill and send Meng Nan ? irstDioxomolybdenum (VI) ComplexesContainingChiralOxazolineLigands:Synthesis, CharacterizationandCatalyticActivity(" EuropeanJournalofInorganicChemistry ", 2001,4:1071-1076) described method prepares organometallic complex. Organometallic complex is utilized to have the advantage that epoxidation when achieving without carboxylic acid as catalyst, it is to avoid the etching problem of reactor; Product post processing is easy, it is not necessary to the steps such as washing, it is to avoid the problems such as discharge of wastewater; Anacidity reaction system can reduce the degree of crosslinking side reaction; Catalyst reclaims easy and can reuse, and is the novel solid organometallic complex catalyst of a kind of environmental protection. Described catalyst amount is the 0.01% ~ 2.0% of Oleum Verniciae fordii quality.
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.
Described hydrogenperoxide steam generator plays the effect of oxidant, under the effect of organometallic complex catalyst, it is possible to the unsaturated double-bond directly and in vegetable oil carries out epoxidation reaction. 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 1.0 ~ 2.0 times.
Described decompression distillation is at pressure 1000 ~ 3000Pa, hydroxylating agent and residual moisture in removing system under 60 ~ 120 DEG C of conditions of temperature, makes product moisture content less than 0.1wt%.
Oleum Verniciae fordii polylol of the present invention is prepared by the invention described above method. Prepared Oleum Verniciae fordii polylol productivity is higher than 92%, and product hydroxyl value is 120 ~ 270mgKOH/g, and acid number is lower than 1.0mgKOH/g, and moisture is lower than 0.1wt%, it is adaptable to prepare 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 polylol 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, 0.5g Organic Molybdenum Metal coordination compound, 300g butanol, is warming up to 60 DEG C and stirs. Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 750g under intense agitation, control drop rate and make reaction temperature maintain about 80 DEG C, after dropwising, constant temperature 4h at 80 DEG C, reaction terminates. By filtering to isolate SOLID ORGANIC molybdenum composition catalyst, then after question response system layering, remove aqueous phase, oil phase is distilled under 2000Pa, 80 DEG C of conditions 2h, obtains Oleum Verniciae fordii polylol product, productivity is 93.5%, product hydroxyl value is 241mgKOH/g, viscosity 7900mPa s, acid number 0.47mgKOH/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, 0.5g Organic Molybdenum Metal coordination compound, 300g butanol, is warming up to 70 DEG C and stirs. Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 750g under intense agitation, control drop rate and make reaction temperature maintain about 90 DEG C, after dropwising, constant temperature 5h at 90 DEG C, reaction terminates. By filtering to isolate SOLID ORGANIC molybdenum composition catalyst, then after question response system layering, remove aqueous phase, oil phase is distilled under 2000Pa, 80 DEG C of conditions 2h, obtains Oleum Verniciae fordii polylol product, productivity is 93.3%, product hydroxyl value is 232mgKOH/g, viscosity 8600mPa s, acid number 0.48mgKOH/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, 0.5g Organic Molybdenum Metal coordination compound, 300g butanol, is warming up to 50 DEG C and stirs. Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 750g under intense agitation, control drop rate and make reaction temperature maintain about 70 DEG C, after dropwising, constant temperature 4h at 70 DEG C, reaction terminates. By filtering to isolate SOLID ORGANIC molybdenum composition catalyst, then after question response system layering, remove aqueous phase, oil phase is distilled under 2000Pa, 80 DEG C of conditions 2h, obtains Oleum Verniciae fordii polylol product, productivity is 92.6%, product hydroxyl value is 176mgKOH/g, viscosity 6900mPa s, acid number 0.42mgKOH/g, moisture, lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 4
2000mL there-necked flask adds 500g Oleum Verniciae fordii, 0.5g Organic Molybdenum Metal coordination compound, 300g ethanol, is warming up to 60 DEG C and stirs. Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 750g under intense agitation, control drop rate and make reaction temperature maintain about 80 DEG C, after dropwising, constant temperature 4h at 80 DEG C, reaction terminates. By filtering to isolate SOLID ORGANIC molybdenum composition catalyst, then after question response system layering, remove aqueous phase, oil phase is distilled under 2000Pa, 80 DEG C of conditions 2h, obtains Oleum Verniciae fordii polylol product, productivity is 93.2%, product hydroxyl value is 227mgKOH/g, viscosity 11200mPa s, acid number 0.44mgKOH/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, 0.5g Organic Molybdenum Metal coordination compound, 300g triethanolamine, is warming up to 60 DEG C and stirs. Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 750g under intense agitation, control drop rate and make reaction temperature maintain about 80 DEG C, after dropwising, constant temperature 4h at 80 DEG C, reaction terminates. By filtering to isolate SOLID ORGANIC molybdenum composition catalyst, then after question response system layering, remove aqueous phase, oil phase is distilled under 2000Pa, 80 DEG C of conditions 2h, obtains Oleum Verniciae fordii polylol product, productivity is 93.2%, product hydroxyl value is 224mgKOH/g, viscosity 10900mPa s, acid number 0.44mgKOH/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, 4g Organic Molybdenum Metal coordination compound, 250g butanol, is warming up to 60 DEG C and stirs. Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 750g under intense agitation, control drop rate and make reaction temperature maintain about 80 DEG C, after dropwising, constant temperature 4h at 80 DEG C, reaction terminates. By filtering to isolate SOLID ORGANIC molybdenum composition catalyst, then after question response system layering, remove aqueous phase, oil phase is distilled under 2000Pa, 80 DEG C of conditions 2h, obtains Oleum Verniciae fordii polylol product, productivity is 93.3%, product hydroxyl value is 244mgKOH/g, viscosity 12200mPa s, acid number 0.49mgKOH/g, moisture, lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 7
2000mL there-necked flask adds 500g Oleum Verniciae fordii, 0.5g Organic Molybdenum Metal coordination compound, 500g butanol, is warming up to 60 DEG C and stirs. Then being slowly added dropwise 30wt% aqueous hydrogen peroxide solution 900g under intense agitation, control drop rate and make reaction temperature maintain about 80 DEG C, after dropwising, constant temperature 4h at 80 DEG C, reaction terminates. By filtering to isolate SOLID ORGANIC molybdenum composition catalyst, then after question response system layering, remove aqueous phase, oil phase is distilled under 2000Pa, 80 DEG C of conditions 2h, obtains Oleum Verniciae fordii polylol product, productivity is 93.8%, product hydroxyl value is 258mgKOH/g, viscosity 7450mPa s, acid number 0.45mgKOH/g, moisture, lower than 0.1wt%, can be used for preparing hard polyurethane foam product.
Embodiment 8
Adopt the treatment process condition identical with embodiment 1, be different in that addition 0.5g organic vanadium metal complex catalysts. The productivity of Oleum Verniciae fordii polylol is 93.4%, and product hydroxyl value is 224mgKOH/g, viscosity 7150mPa s, acid number 0.42mgKOH/g, and 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 195000mPa 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 polyurethane products.
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 173000mPa 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 polyurethane products.
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 5.9mgKOH/g, does not occur due to product hydroxylating, hydroxyl value too low, therefore product is not used to and prepares polyurethane products.
Claims (10)
1. the preparation method of an Oleum Verniciae fordii polylol, it is characterised in that include following content: Oleum Verniciae fordii, organometallic complex catalyst, hydroxylating agent are mixed in proportion, and are warming up to 50 ~ 70 DEG C; Under intense agitation, drip hydrogenperoxide steam generator, control rate of addition and make reaction temperature maintain 70 ~ 90 DEG C, after dropwising, maintain reaction temperature 3 ~ 5 hours, terminate reaction; Reaction system sequentially passes through and filters to isolate solid catalyst, stratification, isolates aqueous phase, decompression distillation, obtains Oleum Verniciae fordii polylol.
2. in accordance with the method for claim 1, it is characterised in that: described organometallic complex catalyst has below formula:
Wherein, M is transition metal molybdenum, vanadium, titanium, manganese, cobalt, copper or nickel.
3. in accordance with the method for claim 2, it is characterized in that, described transition metal source is in acetyl acetone, vanadium acetylacetonate, titanium acetylacetone, manganese acetylacetonate, acetylacetone cobalt, acetylacetone copper, nickel acetylacetonate, manganese acetate, cobalt acetate, copper acetate, nickel acetate, copper chloride or Nickel dichloride..
4. the method described in claim 1,2 or 3, it is characterised in that: catalyst amount is the 0.01% ~ 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 characterized 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 concentration of described hydrogenperoxide steam generator is 20wt% ~ 60wt%, and consumption is Oleum Verniciae fordii quality 1.0 ~ 2.0 times.
9. in accordance with the method for claim 1, it is characterised in that: 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%.
10. the Oleum Verniciae fordii polylol that prepared by the arbitrary described method of claim 1��9, it is characterized in that: Oleum Verniciae fordii polylol productivity is higher than 92%, and product hydroxyl value is 120 ~ 270mgKOH/g, and acid number is lower than 1.0mgKOH/g, moisture, lower than 0.1wt%, can be used for preparing polyurethane material.
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| CN106957227B (en) * | 2016-01-11 | 2020-01-10 | 中国石油化工股份有限公司 | Method for producing tung oil polyalcohol and byproduct glycerol |
| CN107151209A (en) * | 2016-03-03 | 2017-09-12 | 中国石油化工股份有限公司 | A kind of method that utilization ionic liquid synthesizes tung oil polyalcohol |
| CN107151209B (en) * | 2016-03-03 | 2020-01-10 | 中国石油化工股份有限公司 | Method for synthesizing tung oil polyol by using ionic liquid |
| CN106076424A (en) * | 2016-07-05 | 2016-11-09 | 南京林业大学 | A kind of preparation method and application of straight chain corn starch loaded catalyst |
| CN107602843A (en) * | 2017-09-08 | 2018-01-19 | 浙江皇马科技股份有限公司 | A kind of low-unsaturation-degree isomery alcohol polyoxyethylene poly-oxygen propylene aether and preparation method thereof |
| CN107602843B (en) * | 2017-09-08 | 2022-04-15 | 浙江皇马科技股份有限公司 | Low-unsaturation-degree isomeric alcohol polyoxyethylene polyoxypropylene ether and preparation method thereof |
| CN111905668A (en) * | 2020-09-04 | 2020-11-10 | 南京工业大学 | Reaction device and application thereof in continuous preparation of vegetable oil polyalcohol |
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