CN102850189A - Preparation method of high-purity saturated urushiol and its formal derivative - Google Patents
Preparation method of high-purity saturated urushiol and its formal derivative Download PDFInfo
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Abstract
The invention discloses a preparation method of high-purity saturated urushiol and its formal derivative. The preparation method comprises the following steps: modifying urushiol which is an acetone extract of raw lacquer through formalization to obtain an urushiol derivative having a new structure, wherein the formalization process enables the polarities of urushiol monomers having o-dihydroxybenzene structures to be substantially reduced; carrying out a hydrogenation reaction through adopting palladium carbon as a catalyst to obtain saturated formalized urushiol; carrying out normal-phase column separation to separate the urushiol monomers from polymerized urushiol and polar impurities in the extract; and removing formal groups from the saturated formal urushiol to obtain the high-purity saturated urushiol. The urushiol and its derivative have strong biological activities, and have a good market prospect.
Description
Technical field
This patent relates to the preparation method of a kind of high purity urushiol and formal derivatives thereof, is widely used in bio-pharmaceuticals, the fields such as makeup, fine chemistry industry.
Background technology
Raw lacquer is a kind of sumac(h)bark secretory product, is mainly used at present coating industry, and is corrosion-resistant because raw lacquer coating has high gloss, the characteristic of elegant and have the good reputation of " king of coating "; China's lacquer tree cultivated area is extensive, is distributed in the areas such as Yunnan, Guizhou, Sichuan, Chongqing, Gansu, Shaanxi, Hubei of China, and every annual output lacquer reaches 5000 tons.The main component of raw lacquer is laccol, mainly be the laccol compound that three types is arranged at present, China's laccol, Vietnam's laccol and thitsiol, the main difference of three kinds of laccols is the length of the residing position of side chain and side chain, is the catechol derivatives composition of 15 carbon atoms by a position (with respect to No. 1 hydroxyl, lower same) mainly in the Chinese laccol, Vietnam's laccol be between the position contain the laccol of 17 carbon atoms, thitsiol is that contraposition is the side chain of 17 carbon atoms.Laccol possesses good biological activity, and the record that is used as medicine is namely arranged from ancient times; The recent domestic researchist has carried out a large amount of research to the laccol biological activity: Korea S member of Imperial Academy university research person finds that laccol has the restraining effect of detailed row to Hp, studies show that best antibacterial pH is 6-9, is 0.064-0.256mg/mL to the minimum inhibitory concentration of bacterial strain; Taiwan's scholars is extracted from Rhus succedanea Rhus succedanea lacquer juice and is separated 2 hydroquinones new compounds, its side chain is C17 diene or three allylic alkylations, have good anti-oxidant and anticancer efficient, find that antithetical phrase epithelium of cervix uteri cancer HeLa, liver cancer Huh7, large bowel cancer HCT116 and adenocarcinoma of colon Lovo have obvious restraining effect; Patent CN101805246A has announced laccol and the serial laccol salt derivative such as acetylize, methyl-etherified thereof, and the biological activity of laccol inquired into, the result shows laccol and salt derivative thereof to breast cancer cell, and esophageal cancer cell etc. have splendid inhibition; YUN-RU CHEN etc. has studied in the raw lacquer laccol thereby the TYR Enzyme Regulation has been controlled melanic generation, and imagination laccol compound as whitening agent, substitutes the pyrocatechol that tradition is used in makeup; Itokawa etc. separate chain alkyl phenols (C13-17) from gingko episperm have good inhibition to tumour cell S180, HCT-15, MCF-7, A-549, HT-1197 and SKOV-3.The content of laccol is about about 70% in the hair dam lacquer of China, and abundant output provides sufficient raw material for extracting laccol, also be laccol at makeup, the bio-pharmaceuticals industry has been established solid basis.
Laccol is a kind of derivative of pyrocatechol, its oxidation activity is high, laccol just begins polymerization reaction take place from the raw lacquer collection, studies show that the raw lacquer of getting fresh collection adopts the alcoholic extraction laccol immediately, the content of polymkeric substance and reach 7% wherein, the long-time storage, even adopt deepfreeze raw lacquer also progressively to have oyster white to become dark brown, and polyurushiol and laccol monomer are difficult to separate after mixing, and the laccol that separates is easy to oxidative deformation and is difficult for preserving; Simultaneously, raw lacquer has strong sensitization, corresponding studies show that, and pyrocatechol structure and the two keys on the side chain alkyl structure of laccol are the major causes of sensitization.On structure, laccol is serial different saturation catechol derivatives, there is the close homologue of structure in identical saturation ratio simultaneously, the separation of laccol is very difficult like this, using the methanol-water system can separate the laccol of different saturation at the C18 post, use LC-MS and the analysis showed that laccol monomer and its dipolymer occur simultaneously, therefore the external gel chromatography that usually adopts carries out pre-separation to sample, the polymkeric substance of removing in the raw material obtains series monomers, then carries out follow-up Separation Research.
About the separation preparation of laccol, mainly be at present to use the method for preparing liquid phase, this method requires high to plant and instrument, and solvent consumption is large, and the output of laccol is extremely low simultaneously; Chen Lianxi etc. directly carry out the hydrogenation principle that laccol is discussed in hydrogenation with the raw lacquer acetone extract as raw material, and this method can make unsaturated laccol become urushiol; Be to find that composition is not single but use the liquid-phase chromatographic analysis hydrogenation products, preliminary deduction wherein may be mingled with for different chain length laccol and polyurushiol, thereby direct hydrogenation can not solve the difficult problem of separating of laccol; Foreign literature is reported in before the separation of laccol at first to laccol sample application gel chromatography separation, but because very easily oxidation of laccol, in crossing the process of gel column easily chemical bond and and cause dead absorption, large to the injury of column packing, even in experimentation, find directly to use simultaneously C
18The liquid phase post is analyzed the acetone extract of raw lacquer, and liquid-phase chromatographic column post effect also is to reduce rapidly, adopts the mode of directly separating laccol to increase undoubtedly the cost that separates; The pyrocatechol hydroxyl of laccol is its polar group, has identical retention time with polymkeric substance or the oxidation products of laccol, pyrocatechol reacts in the formal reaction process, phenolic hydroxyl group with polar character disappears, cause polarity to reduce significantly, on the other hand because the oxidation of laccol or polymerisate reaction form the benzylalcohol structure, the difference that possesses like this monomer polarity after the formalizing reaction of pyrocatechol structure becomes large, also can reduce simultaneously the sensitization of raw lacquer, thin-layer chromatography and liquid phase analysis formal product, the laccol polarity of finding part diminishes, the Rf value is about 1 under original thin layer condition, regulating chromatographic solution is 99.7% sherwood oil and 0.3% ethyl acetate, finds the component of Rf value 0.8-0.95, and formal reaction product appearance time lags behind in liquid phase simultaneously.Can easily this part material be separated from system like this.The material of separating is used H-NMR analyze it for the Urushiol-Formaldehyde product, carry out next step experiment.
The employing boron tribromide removes the methylene radical above the formal laccol, boron tribromide is a kind of material to moisture-sensitive, should note removing of system moisture during operation, the dichloromethane solution of configuration boron tribromide, methylene dichloride need carry out first processed, to guarantee that reaction is to the requirement of moisture; The formal laccol adds N in the reaction flask
2Protection slowly splashes into reaction system with the dichloromethane solution of boron trifluoride, and reaction is controlled temperature-40--20 ℃ as for the low-temp reaction device, and the reaction times is 1-2h.
The formalizing method is applied to the modification of pyrocatechol structure, the intermediate of the important organic compounds such as synthetic pepper base class medicine, agricultural chemicals.At present, the pyrocatechol formal has two large synthetic routes, a kind of is to adopt excessive methylene dichloride and pyrocatechol to react at head type reactor mesohigh, but this method transformation efficiency is lower, excessive methylene dichloride has also increased synthetic cost simultaneously, under alkaline condition, equimolar amount methylene dichloride and pyrocatechol carry out synthesis under normal pressure both can reach higher turnover ratio.
Use the Urushiol-Formaldehyde thing of formalizing reaction synthesizing new and use this process reduction laccol monomer polarity so that monomer is easy to separate, then by hydrogenation reaction, take off methylene radical and prepare the innovative point that the high purity urushiol is this patent invention.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of high purity formal laccol and urushiol, this method namely can be prepared highly purified formal laccol and urushiol by succinct technical process, is a kind of short-cut method for preparing urushiol and formal derivatives thereof.
The preparation method of a kind of high purity urushiol and formal derivatives thereof, its key step is as follows:
The first step: the extraction of laccol
Raw lacquer is by 70% laccol, 20% left and right sides water, 7% urushipolysaccharide and albumen and laccase form, the application organic solvent extracts the effective constituent-laccol of raw lacquer, select respectively methyl alcohol, ethanol, acetone, ethyl acetate, sherwood oil to extract, particular methanol, ethanol, sherwood oil, raw lacquer and organic solvent mass volume ratio are 1:10-1:100, filter, the filter residue repeated washing, until that filtrate is rendered as is colourless, using ultrasound ripple assisted extraction, extraction time is 1s-300s, extracting temperature is 0 ℃-40 ℃; It is concentrated that gained filtrate merges cryogenic vacuum, is the laccol of serial different saturation.
Second step: Urushiol-Formaldehyde reaction
1:1～1:4 prepares methylene dichloride-dimethyl sulphoxide solution by volume, the laccol mixture that the first step is extracted is with 1-5 times of dmso solution, laccol lysate and 10%-50% aqueous sodium hydroxide solution add methylene dichloride-dimethyl sulphoxide solution reaction system synchronously, 80 ℃-130 ℃ of temperature of reaction, reaction times 5h, reaction finishes vacuum concentration and obtains yellowish brown oily matter, some plate analysis reaction effect, and products therefrom polarity obviously reduces.
The 3rd step: the separation and purification of laccol
Product to the second step gained separates, adopt positive phase system that the Urushiol-Formaldehyde thing is separated, preferred silica gel is as filler, the silica gel that adopts is the 100-200 order, sample and silica gel mass ratio are 1:20, with acetone, sherwood oil, ethyl acetate, normal hexane, the normal heptane gradient elution, preferred sherwood oil and ethyl acetate be as eluent, and 0.1% to increase gradient to ethyl acetate be 10% to stop, and each gradient elution volume is 3-10 times of bed volume, preferred 5 times column volume, capture range are the component of 0.5-3%;
The 4th step: the hydrogenation reaction of laccol
Using palladium carbon is catalyzer, the Urushiol-Formaldehyde compound is carried out hydrogenation reaction, the solvent that reaction is adopted is a kind of in methyl alcohol, ethanol, sherwood oil, ethyl acetate or the acetone, ethyl acetate and acetone, palladium-carbon catalyst consumption are 0.01-5%, and hydrogenation time is 0.5-8h, hydrogenation pressure is 0.05-1.5MPa, hydrogenation finishes final vacuum concentration response thing, obtains little yellow oil, and room temperature is placed crystallizable solidifying.
The 5th step: the methylene radical that takes off of formal laccol reacts
The formal laccol that the 4th step was separated takes off the methylene radical reaction, and the formal laccol mixes with the dichloromethane solution of boron tribromide at-80 ℃-0 ℃, carries out the reaction of anhydrous and oxygen-free, stirs 0.5-15h, obtains urushiol, purity 94-98%.
Raw lacquer is a kind of water-in-oil emulsion, and wherein contain urushipolysaccharide and protein matter, use the effect that organic solvent reaches breakdown of emulsion, alcohols material can make the species precipitate of polysaccharide and protein simultaneously, the laccol of oily is separated with albumen with polysaccharide, used organic solvent comprises sherwood oil, ethyl acetate, acetone, ethanol and methyl alcohol in the test, and preferred alcohol, acetone and methyl alcohol are as extracting reagent.
Laccol is easy to oxidation, the laccol hydroxyl loses hydrogen ion and becomes negative oxygen ion under the effect of Laccase Catalyzed agent, two key conjugation of negative oxygen ion and phenyl ring form metastable conjugated system, the negative oxygen ion of the adjacency pair position of laccol and phenolic hydroxyl group becomes the site of reflection and forms C-C like this, the polymkeric substance of C-O structure, the pyrocatechol structure is consumed, the laccol polymkeric substance that the D-A reaction forms the side side structure can occur in the laccol conjugated double bond simultaneously, the analysis showed that through liquid matter the polymkeric substance of laccol and monomer flow out simultaneously in reverse phase silica gel, this patent is used the reaction of formal, because the laccol monomer has the pyrocatechol structure, polarity occurs to change significantly, thereby this method can optionally be screened the laccol monomer that the pyrocatechol structure is arranged, Urushiol-Formaldehyde adopts the methylene dichloride reaction, under the effect of sodium hydroxide, laccol forms laccol sodium, and the carbon atom in the methylene dichloride is with extremely strong positive polarity, and both are easy to nucleophilic reaction occurs and the laccol that forms formal; The benzene ring structure of simultaneously attack of laccol negative oxygen ion laccol, methylene dichloride also can react with the sodium hydroxide of surplus, thereby should be by both relative rate of addition one reverse side of adjusting so that laccol be suitable with the sodium hydroxide amount of substance in the process, control on the other hand laccol concentration, reduce the chance of laccol molecule copolymerization, laccol and solvent DMSO volume ratio are 1:1-1:10, and the control rate of addition is 0.5-6d/s, preferred 0.5-1d/s; The 10-50% sodium hydroxide solution, control rate of addition 0.05-0.6d/s, preferred 0.05-0.3d/s.
Carry out normal phase column after the polarity of formal laccol has occured to change significantly and separate, optional organic solvent is acetone, sherwood oil, ethyl acetate, normal hexane, normal heptane, gradient elution, preferred petroleum ether-ethyl acetate system; With 0.1% step increase gradient, collect the 0-5% component, follow the tracks of to merge and collect liquid, concentrate and obtain highly purified formal laccol.
Mainly be that side chain is C in China's hair dam raw lacquer
15Laccol, the formal laccol is carried out hydrogenation reaction namely obtain saturated laccol compound, unsaturated laccol mainly is the chain alkyl that side chain contains three step saturated bonds in the hair dam raw lacquer, through the pertinent literature report as can be known, when adopting palladium carbon to be catalyzer, both can carry out smoothly hydrogenation reaction under the room temperature normal pressure, the solvent that reaction is adopted is a kind of in methyl alcohol, ethanol, sherwood oil, ethyl acetate or the acetone, ethyl acetate and acetone, the palladium-carbon catalyst consumption is 0.01-5%, hydrogenation time is 0.5-8h, and hydrogenation pressure is 0.05-1.5MPa; Temperature of reaction is 0-40 ℃, is preferably 20-30 ℃; Hydrogenation is finished concentrated, and owing to losing of two keys, the room temperature cooling obtains the saturated formal laccol of white crystals shape, purity 95-98%.
Last this patent provides the method for Deprotection of formal laccol with the preparation urushiol; the method of Deprotection is many; in conjunction with the active characteristics of laccol chemical property; select the method for boron tribromide Deprotection, temperature of reaction be-80-0 ℃, preferably-and 40--20 ℃; both material ratios are 1:1-1:10; preferred 1:2-1:4, the reaction times is 0.5-15h, preferred 0.5-2h.This reaction is the anhydrous and oxygen-free reaction, should strictly control the moisture of reaction system and the content of oxygen in the process, and gained urushiol purity is 94-96%.
Beneficial effect of the present invention shows as:
1. by the formalizing reaction, first preparation has the serial formal laccol compound of novel texture;
2. first Application formalizing reaction, laccol class material polarity and the other types material polarity that will have the pyrocatechol structure produce difference, and the laccol monomer both can be separated at forward silica gel; Adopting atmospheric hydrogenation is saturated formal laccol with unsaturated Partial Conversion, improves the yield of saturated formal laccol.
Description of drawings:
The composition of laccol in accompanying drawing 1 raw lacquer
The reaction of accompanying drawing 2 Urushiol-Formaldehydes
Accompanying drawing 3 laccols and hydrogenation laccol HPLC collection of illustrative plates
Accompanying drawing 4 thin-layer chromatographic analysis laccols (a), formal laccol (b) and saturated formal laccol (c)
The infrared spectrogram of accompanying drawing 5 formal laccols and laccol
The mass spectrum of accompanying drawing 6 urushiols
Embodiment
Following examples are more of the present invention giving an example, and should not be seen as limitation of the invention.
Case study on implementation
The extraction of case study on implementation 1 raw lacquer laccol
Get 10g hair dam raw lacquer, 1-20 times of mass volume ratio acetone extraction, the acetone of preferred 7-15 times of mass volume ratio fully stirs, ultrasonic auxiliary 10-300s, suction filtration goes out coating removal albumen, and polysaccharide etc. are got 50ml washing with acetone filter residue for several times, (the fresh raw lacquer sample until filtrate becomes colorless, the filter residue of gained becomes pure white), 20-35 ℃ of vacuum concentration obtains 7g yellowish brown oily matter, is serial unsaturated laccol.
The formal reaction of case study on implementation 2 laccols
Get gained laccol mixture and be dissolved in 1-10 times of volume dimethyl sulfoxide (DMSO), preferred 2-5 times of volume, get 1-4 times of molar weight 10-50% aqueous sodium hydroxide solution, the solution (solvent is dimethyl sulfoxide (DMSO)) of preparation 2-10ml methylene dichloride is regulated 80-130 ℃ of oil bath temperature in the 100ml there-necked flask, preferred 100-110 ℃, simultaneously the aqueous solution of sodium hydroxide and the DMSO solution of laccol are splashed into reaction flask, the control rate of addition, continue to drip 1-5h, preferred 2-3 hour, wait to dropwise additional 2ml methylene dichloride and continue backflow 2h end reaction, the deionized water that adds 0.2-2 times of volume in the system fully washs to remove the salinity that produces in the reaction process, 1-10 times of petroleum ether extraction concentrates and obtains the 5.2g yellow oil, is the formal product of series of saturation laccol.
The hydrogenation reaction of case study on implementation 3 formal laccols
The Urushiol-Formaldehyde product of getting gained in the case 2 carries out hydrogenation reaction, adopt the formal thing of acetone, methyl alcohol, sherwood oil, acetic acid ethyl dissolution laccol, preferred acetone and sherwood oil carry out hydrogenation reaction, volume ratio 1:1-1:5 times of acetone solution Urushiol-Formaldehyde product, add the 0.01-1% palladium-carbon catalyst, hydrogenation reaction 0.5-6h under 25 ℃, 0.1MPa, preferred 4-5h, removal solvent after reaction is finished, obtain light yellow oil, the room temperature cooling obtains the white crystals thing.
The purifying of case study on implementation 4 formal laccols
Formal laccol purification on normal-phase silica gel after concentrated is separated, use the petroleum ether-ethyl acetate gradient elution, per 0.1% increase gradient to the content of ethyl acetate is 4%, get 0.2%-2.0% ethyl acetate component concentrated, obtain white plates crystal 3 .8g, be the formal product of urushiol, the purity of gained formal product is 95-98%.
The preparation of case study on implementation 5 urushiols
Select boron tribromide to slough the methylene group of formal laccol, preparation boron tribromide dichloromethane solution, the dehydration of methylene dichloride drying, both volume ratios are 1:1-1:5, the saturated formal laccol of getting case 4 gained is inserted anhydrous there-necked flask and is carried out low-temp reaction, control temperature of reaction-40 ℃ dropping boron tribromide, stirring 3h stops, 5 times of washed with de-ionized water, remove solvent and have neither part nor lot in the boron tribromide of reaction, obtain white waxy solid, be the urushiol compound, reaction conversion ratio reaches 95%, and the purity of urushiol is 94-98%.
Claims (7)
1. the preparation method of a high purity urushiol and formal derivatives thereof is characterized in that being comprised of following step:
The first step: the extraction of laccol, raw lacquer and organic solvent mass volume ratio (g/ml) they are 1:10-1:100, and extraction time is 1s-300s, and extracting temperature is 0 ℃-40 ℃; Until filter residue is white, merging filtrate concentrates at vacuum and low temperature, obtains the laccol mixture of serial different saturation with organic solvent washing for extracting liquid filtering, filter residue;
Second step: Urushiol-Formaldehyde reaction, 1:1～1:4 prepares methylene dichloride-dimethyl sulphoxide solution by volume, with the laccol mixture of the first step preparation with 1-5 times of dmso solution, laccol lysate and 10%-50% aqueous sodium hydroxide solution add methylene dichloride-dimethyl sulphoxide solution reaction system synchronously, 80 ℃-130 ℃ of temperature of reaction, reaction times 1-7h;
The 3rd step: the separation of formal laccol, after the second step reaction finishes, be cooled to room temperature, with non-polar solvent equal-volume extractive reaction liquid, extract 2-5 time, combining extraction liquid, vacuum concentration obtains yellowish brown oily formal laccol;
The 4th step: hydrogenation reaction, with the formal laccol acetone solution of the 3rd step separation, hydrogenation reaction under the palladium-carbon catalyst effect, catalyst levels is the 0.01%-5% of formal laccol quality, temperature of reaction 0-40 ℃, pressure 0.05-1.5MPa, time 0.5-8h;
The 5th step: saturated formal laccol purifying, get hydrogenation reaction product, filter first, filtrate is carried out concentrate under reduced pressure at low temperature, enriched material carries out normal phase column to be separated, the mass ratio of enriched material and normal phase column filler is 1:10～40, and eluent is normal hexane-ethyl acetate gradient elution, and TLC and HPLC detect, collecting saturated formalizing laccol collection divides, vacuum concentration, enriched material are saturated formal laccol, purity 95-98%;
The 6th step: the removing of saturated formal laccol methylene radical, with saturated formal laccol and boron tribromide in mass ratio 1:1-1:5 add reactor, under-80 ℃-0 ℃, remove the methylene radical reaction, react normal pressure, reaction times 0.5～5h;
The 7th step: high purity urushiol preparation, adopt the product of the 6th step of the deionized water wash gained of 1-10 times of volume, solvent in the vacuum concentration removal system can obtain highly purified urushiol, and the turnover ratio of reaction is greater than 95%, and urushiol purity is 94-98%.
2. according to the preparation method of the described a kind of high purity urushiol of claim one and formal derivatives thereof, be primarily characterized in that organic solvent that the first step adopts is any in methyl alcohol, ethanol or the acetone.
3. according to the preparation method of the described a kind of high purity urushiol of claim one and formal derivatives thereof, be primarily characterized in that the concentrated condition of the first step vacuum and low temperature is: vacuum tightness 500mmHg-750mmHg, temperature is 0-40 ℃.
4. according to the preparation method of the described a kind of high purity urushiol of claim one and formal derivatives thereof, be primarily characterized in that also can adopt first laccol is carried out hydrogenation reaction, the laccol that hydrogenation is saturated carries out the formal reaction again.
5. according to the preparation method of the described a kind of high purity urushiol of claim one and formal derivatives thereof, be primarily characterized in that non-polar solvent extraction agent that the 3rd step adopted is any in sherwood oil, ethyl acetate or the acetone.
6. according to the preparation method of the described a kind of high purity urushiol of claim one and formal derivatives thereof, be primarily characterized in that the gradient elution agent is acetone-sherwood oil, normal hexane-ethyl acetate in the 5th step of application, normal heptane-ethyl acetate, any one in petroleum ether-ethyl acetate or the chloroform-ethyl acetate.
7. according to the preparation method of the described a kind of high purity urushiol of claim one and formal derivatives thereof, be primarily characterized in that positive phase filling is silica gel in the 5th step, any in the aluminum oxide.
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| CN109111348A (en) * | 2018-09-29 | 2019-01-01 | 南京中森生物科技有限公司 | A kind of unsaturated laccol isolation and purification method of three (lists) based on color judgement |
| CN109575770A (en) * | 2018-10-31 | 2019-04-05 | 中华全国供销合作总社西安生漆涂料研究所 | A kind of preparation method being saturated laccol base functional paint |
| CN110272679A (en) * | 2019-06-26 | 2019-09-24 | 西北农林科技大学 | Hyperbranched super-amphiphobic anticorrosive paint of ultraviolet-cured paint phenolic group and preparation method thereof |
| CN110672750A (en) * | 2019-10-25 | 2020-01-10 | 皖西学院 | Method for determining urushiol in rhus chinensis fruit oil by using UPLC-MS (ultra performance liquid chromatography-mass spectrometry) |
| CN116162018A (en) * | 2023-03-07 | 2023-05-26 | 中国林业科学研究院林产化学工业研究所 | Preparation method for obtaining urushiol dimer through ultrasonic synergistic orientation |
| CN116832389A (en) * | 2023-07-14 | 2023-10-03 | 宁波博通文化创意有限公司 | Improved process for desensitizing lacquer urushiol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111348A (en) * | 2018-09-29 | 2019-01-01 | 南京中森生物科技有限公司 | A kind of unsaturated laccol isolation and purification method of three (lists) based on color judgement |
| CN109575770A (en) * | 2018-10-31 | 2019-04-05 | 中华全国供销合作总社西安生漆涂料研究所 | A kind of preparation method being saturated laccol base functional paint |
| CN109575770B (en) * | 2018-10-31 | 2020-11-03 | 中华全国供销合作总社西安生漆涂料研究所 | Preparation method of saturated urushiol-based functional coating |
| CN110272679A (en) * | 2019-06-26 | 2019-09-24 | 西北农林科技大学 | Hyperbranched super-amphiphobic anticorrosive paint of ultraviolet-cured paint phenolic group and preparation method thereof |
| CN110272679B (en) * | 2019-06-26 | 2021-04-09 | 西北农林科技大学 | Ultraviolet light curing paint phenolic hyperbranched super-amphiphobic anticorrosive paint and preparation method thereof |
| CN110672750A (en) * | 2019-10-25 | 2020-01-10 | 皖西学院 | Method for determining urushiol in rhus chinensis fruit oil by using UPLC-MS (ultra performance liquid chromatography-mass spectrometry) |
| CN116162018A (en) * | 2023-03-07 | 2023-05-26 | 中国林业科学研究院林产化学工业研究所 | Preparation method for obtaining urushiol dimer through ultrasonic synergistic orientation |
| CN116832389A (en) * | 2023-07-14 | 2023-10-03 | 宁波博通文化创意有限公司 | Improved process for desensitizing lacquer urushiol |
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