CN1927795A - Method of preparing resorcin by hydrolyzing m-phenylenediamine - Google Patents
Method of preparing resorcin by hydrolyzing m-phenylenediamine Download PDFInfo
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- CN1927795A CN1927795A CN 200610019367 CN200610019367A CN1927795A CN 1927795 A CN1927795 A CN 1927795A CN 200610019367 CN200610019367 CN 200610019367 CN 200610019367 A CN200610019367 A CN 200610019367A CN 1927795 A CN1927795 A CN 1927795A
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Abstract
The present invention belongs to the field of fine chemical technology, and is especially the process of hydrolyzing m-phenylenediamine to prepare resorcinol. The process includes the following steps: 1. reaction between m-phenylenediamine and strong inorganic acid to produce salt; 2. hydrolyzing the salt to obtain resorcinol material; 3. extracting the resorcinol material to obtain crude resorcinol product; 4. evaporating and dissolving the crude resorcinol product; and 5. distilling the crude resorcinol product to obtain resorcinol product. The process of the present invention has the advantages of high yield, wide material resource, mild reaction condition, short technological process, less pollution, etc.
Description
Technical field:
The invention belongs to fine-chemical intermediate raw material technical field, be specifically related to a kind of method with preparing resorcin by hydrolyzing m-phenylenediamine.
Prior art:
Its popular name of Resorcinol claims resorcin, and outward appearance is a clear crystal, under the effect of light and damp atmosphere, becomes redness.Proportion 1.28.109～111 ℃ of fusing points.280～281 ℃ of boiling points.Soluble in water, ethanol and ether, be slightly soluble in benzene, be dissolved in chloroform hardly.
Resorcinol is a kind of important Organic Chemicals, is widely used in rubber adhesive, synthetic resins, dyestuff, sanitas, medicine and fields such as analytical chemistry reagent and sensitive materials.Resorcinol and formaldehyde generate polycondensate, are used to make viscose yarn and tire cord tackiness agent; Preparation binding agent RS, RL, RE, RH etc. are as sand paper, gauze and wood working binding agent etc.Resorcinol has germicidal action, can be used as sanitas, is used for makeup and dermatosis treating medicine stick and ointment etc.Resorcinol also is the intermediate of many dye well medicine, as important dyestuff intermediate meta-aminophenol etc.; Resorcinol also is used to produce the benzophenone ultraviolet absorbers, as UV-0, UV-531, UV-9 etc.In addition, Resorcinol is commonly used on the electroless plating of plastics such as ABS and makes additive.The Resorcinol synthetic route of bibliographical information is a lot, and industrialized have only two kinds, i.e. benzene sulfonated alkali fusion method and m-Diisopropylbenzene oxidation style.
One, sulfonated alkali fusion method:
With benzene and oleum is benzene disulfonic acid between raw material reaction generates, and is neutralized into sodium 1,3-benzenedisulfate with sodium hydroxide, generates Resorcinol sodium with the sodium hydroxide congruent melting again, after hcl acidifying is a Resorcinol.Fig. 1 is seen in technical process.
The benzene sulfonation method is the traditional method of producing Resorcinol, and China, the U.S. and India all adopt this method to produce at present.These explained hereafter Resorcinol a large amount of oleums of needs and hydrochloric acid, caustic soda produce a large amount of inorganic salt Na
2SO
3, Na
2SO
4, the liquid waste disposal expense is higher, and damage ratio is more serious; Simultaneously, benzene sulfonated alkali fusion method yield is lower, and the yield of domestic manufacturer has only 60%-70% usually.Therefore, the benzene sulfonation method technology of domestic employing all is difficult to compare with external m-Diisopropylbenzene oxidation style on environmental protection and cost, only improves traditional benzene process for sulfonation and could obtain one seat in intense market competition.At benzene sulfonation method process aspect, the researchist has carried out a large amount of research both at home and abroad, and a plurality of unit operations are carried out fruitful improvement, and the industrialization of enforcement that has has obtained effect preferably.
1.1 sulfonation
Bring into use SO abroad very early
3Replace oleum as sulphonating agent, domesticly in recent years also succeeded in developing and realized industrialization.Use SO
3Sulfonation has improved the utilization ratio of sulphonating agent, and the sulfur waste acid content is few in the sulfonated products, in and the time to consume caustic soda amount low, raw materials cost descends greatly, the three wastes also reduce to some extent, economic benefit is comparatively obvious.SO
3The sulfonation technology key is, the one, and control reaction temperature relaxes reaction and carries out, and in time derives reaction heat, avoids oversulfonate; The 2nd, improve SO
3Stability, make it reduce extent of polymerization at normal temperatures, keep liquid state, usually at SO
3Middle some stablizers that add.Can produce a certain amount of sulfobenzide disulfonic acid during sulfonation, though can change a part sodium phenylate and a part Resorcinol acid sodium into when alkali fusion, phenol is not that we wish to obtain after all.We find in production practice, if SO
3For a long time excessive, the growing amount of sulfobenzide disulfonic acid is more; But if SO
3After a little while excessive, just have a small amount of Phenylsulfonic acid and further be not reacted into a benzene disulfonic acid, finally still there is phenol to produce.Therefore, SO
3Add-on be to influence one of very important index of sulfonation effect.
1.2 alkali fusion
The reaction theory amount of caustic soda and sodium 1,3-benzenedisulfate is 4: 1 during alkali fusion, because reaction generates Resorcinol sodium salt and a large amount of S-WATs, material viscosity is big especially, in order to reduce the viscosity of material, obtain good mobility, be beneficial to the carrying out that react, the mol ratio of caustic soda and the actual feeding quantity of sodium 1,3-benzenedisulfate was above 8: 1.So not only make the alkali consumption of alkali fusion increase by one times than theoretical amount, also increased the salt acid consumption of subsequent handling greatly, thereby improve production cost, quantity of three wastes has also increased.
Caustic soda consumption amount when reducing the sulfonated alkali fusion method alkali fusion, enterprise has also carried out some researchs and trial both at home and abroad.
Mitsui east pressure company finds, sodium 1,3-benzenedisulfate has diluting effect in the presence of benzene sulfonic acid sodium salt or phenol sodium salt, reduce the viscosity of molten reaction mixture so greatly, increased the flowability of material, thereby reduced the consumption of caustic soda and obtained satisfied reaction result.
Detailed process is: 300-360 ℃ of alkali fusion temperature, the caustic soda amount is carried out alkali fusion than the excessive 1%-20% of theoretical amount in the presence of benzene sulfonic acid sodium salt of doubly measuring for sodium 1,3-benzenedisulfate weight 2.5-10 or sodium phenylate.After reaction finished, reactant was dissolved in the water of equivalent, and by-product sodium sulfite salt is removed by filter, and the phenol layer is told in the filtrate acidifying, and remaining Resorcinol and phenol extract with isopropylcarbinol in water layer, and fractionation by distillation goes out Resorcinol and phenol then.The Resorcinol yield can reach 88%.
U.S. Germany and Britain Si Peike company adopts the kneading type alkali-melting vessel that has strong mixer, has overcome the low disadvantageous effect to the alkali fusion reaction of viscosity, has also reduced caustic soda consumption to a certain extent.
1.3 extraction
The extraction process key is to select inexpensive efficient extracting agent, and its principle of selecting for use should be considered following several respects: the effect of extracting to Resorcinol is good; Lower with the mutual solubility of water; Toxicity is less; Volatility is less; Low price.
Traditional extraction agent is a propyl carbinol.Propyl carbinol is fine to the effect of extracting of Resorcinol, and not volatile, toxicity is lower, but with water certain mutual solubility is arranged, in water the loss bigger, price is also higher.From environmental protection and cost angle, the extraction agent of selecting for use propyl carbinol to make Resorcinol has certain limitation.In fact, admissible extraction agent still is many, as isopropylcarbinol, ether, sherwood oil, diisopropyl ether, n-butyl acetate etc.Isopropylcarbinol and water have bigger mutual solubility, in water the loss bigger, more inferior slightly than propyl carbinol to the effect of extracting of Resorcinol, but not volatile, toxicity is lower, price is also cheap than propyl carbinol; Ether is fine to the effect of extracting of Resorcinol, and very low with the mutual solubility of water, toxicity is lower, but highly volatile requires low temperature, airtight during extraction; Sherwood oil is fine to the effect of extracting of Resorcinol, and is water insoluble, and price is also lower, but toxicity is higher, and highly volatile requires low temperature, airtight during extraction; The mutual solubility of n-butyl acetate and water is very low, and toxicity is very little, and is not volatile, but to the too late propyl carbinol of the effect of extracting of Resorcinol, price is also higher; Diisopropyl ether is fine to the effect of extracting of Resorcinol, and very low with the mutual solubility of water, toxicity is medium, but volatile, requires low temperature, airtight during extraction, and price is also higher.As for specifically selecting which kind of extraction agent for use, also to take all factors into consideration the characteristics of extraction agent and the particular case of device.
1.4 distillation
The tradition production process for resorcinol adopts simple batch distillation purification Resorcinol finished product, and the Resorcinol finished product purity that obtains is lower, generally only is about 98%, because impurity is more, the easy variable color of outward appearance can not have been satisfied the demand of downstream user.Generally adopt many plates continuous rectification purification Resorcinol abroad already, its purity can reach 99.5%, and outward appearance is fine.Because the price of high purity Resorcinol will exceed thousands of units than common product, so, take all factors into consideration or very big value is arranged though adopt the rectification and purification Resorcinol to many consumes energy than simple distillation.Recently domestic production producer also begins to attempt the utilization distillation technology and improves Resorcinol purity, and quality is near foreign level, and product competitiveness strengthens to some extent.
Two, m-Diisopropylbenzene oxidation style:
M-Diisopropylbenzene is oxidized to diperoxy hydrogen diisopropylbenzene(DIPB), then decomposes to generate Resorcinol under acidic conditions, simultaneously by-product acetone.This method is external 20th century novel procesies of developing of the mid-80, is similar to cumene oxidation and prepares the phynol/acetone process, and environmental pollution is little, process is compact, be convenient to serialization production, is representing the resorcin synthetic process developing direction.Because technical difficulty is bigger, has only Japanese 2 companies to adopt this method to realize suitability for industrialized production at present, its technological process is as follows:
(1) at liquid phase alkalescence and catalyst A lCl
3Under the condition,, obtain m-Diisopropylbenzene dihydro-peroxidase and by-product m-Diisopropylbenzene hydroxyl hydrogen superoxide with air or oxygen oxidation m-Diisopropylbenzene.
(2) be solvent with toluene, oxide compound carried out pre-treatment, by product m-Diisopropylbenzene hydroxyl hydrogen superoxide is converted into the m-Diisopropylbenzene dihydro-peroxidase, prevent its decomposition simultaneously with aqueous hydrogen peroxide solution.
(3) in the sulfuric acid and oxide compound.
(4) heating evaporation is sloughed toluene and water and is obtained concentrating material.
(5) under the acid catalyst condition, m-Diisopropylbenzene diperoxy thing is decomposed into Resorcinol and acetone.
(6) obtain the finished product of Resorcinol and acetone respectively by rectifying.Fig. 2 is seen in technical process.
Three, operational path is relatively:
Sulfonated alkali fusion method and m-Diisopropylbenzene oxidation style throughput are more or less the same at present, and from environment protection and development prospect, the m-Diisopropylbenzene oxidation style has remarkable advantages.The sulfonation method technical process is tediously long, and the three wastes are many, and yield has only about 60%-70%; And m-Diisopropylbenzene oxidation style yield height, control degree is good automatically, is easy to the serialization large-scale production; the particularly important is this method three wastes discharge amount seldom; compare with sulfonation method according to Japanese document announcement oxidation style, produce the 1t Resorcinol, oxidation style reduces 1806m than sulfonation method
3CO
2Quantity discharged.And under raw material and technology were guaranteed prerequisite, the oxidation style production cost also was starkly lower than traditional sulfonation method.But the oxidation style technology content is very big, China has how tame R﹠D institution such as Shanghai Petroleum Chemical Engineering Institute etc. to carry out the oxidation style technological development at present, studies show that all there is suitable difficulty aspects such as oxidation and extracting and separating and engineering amplification, the domestic so far progress of achieving no breakthrough property still.Sulfonation method technology is simple in addition, and is not high to equipment requirements; Main raw material is benzene, caustic soda, hydrochloric acid, is all large basic chemical feedstocks, and amount is easy to get greatly; Because of caustic soda, salt acid consumption are very big, be particularly suitable for chlor-alkali and relevant enterprise as derived product; Through technological improvement for many years and development, the quality of product and yield all can be greatly improved (external sulfonation method yield reach about 75%).
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of method with preparing resorcin by hydrolyzing m-phenylenediamine.
The present invention solves the technical scheme that its technical problem takes: a kind of method with preparing resorcin by hydrolyzing m-phenylenediamine is characterized in that comprising following processing step:
1., mphenylenediamine and inorganic acid reaction are generated salt;
2., above-mentioned generation salt hydrolysis is obtained the Resorcinol material;
3., above-mentioned materials abstraction is obtained the Resorcinol crude product;
4., above-mentioned Resorcinol crude product is steamed the molten crude product Resorcinol that obtains;
5., the crude product Resorcinol is distilled the Resorcinol finished product.
The present invention solves in the technical scheme that its technical problem takes inorganic acid that 1. adopts in the step can be hydrochloric acid.
The present invention solves in the technical scheme that its technical problem takes inorganic acid that 1. adopts in the step can also be sulfuric acid.
The present invention solves in the technical scheme that its technical problem takes specifically can adopt following technological process:
1., in reactor, add entry, mphenylenediamine successively, stir and make its dissolving, slowly drip 31% hydrochloric acid again, feed temperature is no more than 100 ℃, adds the back and stirs 0.5h; Reaction formula is as follows:
2., above-mentioned solution is warming up to 220 ℃～250 ℃, boost to 2.6MPa～4.0MPa, more than the insulation 3h, hydrolysis reaction is cooled to below 40 ℃ after finishing; Reaction formula is as follows:
3., with the material solvent extraction after the hydrolysis cooling, Resorcinol is extracted in the solvent, is neutralized to slightly acidic with buck then;
4., the Resorcinol crude product that will contain solvent boils off solvent, solvent is applied mechanically, content is about 95% crude product Resorcinol;
5., above-mentioned crude product is distilled to such an extent that content is Resorcinol finished product more than 99.0%.
The present invention solves in the technical scheme that its technical problem takes specifically can also adopt following technological process:
1., in reactor, add entry, mphenylenediamine successively, stir and make its dissolving, slowly drip 98% sulfuric acid again, feed temperature is no more than 100 ℃, adds the back and stirs 0.5h; Reaction formula is as follows:
2., above-mentioned solution is warming up to 230 ℃～250 ℃, boost to 2.6MPa～4.0MPa, more than the insulation 3h, hydrolysis reaction is cooled to below 40 ℃ after finishing; Reaction formula is as follows:
3., with the material solvent extraction after the hydrolysis cooling, Resorcinol is extracted in the solvent, is neutralized to slightly acidic with buck then;
4., the Resorcinol crude product that will contain solvent boils off solvent, solvent is applied mechanically, content is crude product Resorcinol more than 95%;
5., above-mentioned crude product is distilled to such an extent that content is Resorcinol finished product more than 99.0%.
The present invention solves any as in ether, n-butyl acetate and the sherwood oil of the solvent that uses in the technical scheme that its technical problem takes.
The waste liquid that the present invention will extract with in ammoniacal liquor or the bicarbonate of ammonia and after, through concentrate, crystallization, centrifugal byproduct ammonium chloride or ammonium sulfate.
Advantage of the present invention is: this method has overcome the big and m-Diisopropylbenzene oxidation style route technology of the benzene sulfonation alkali fusion route three wastes and has been difficult to shortcomings such as grasp, has the yield height, raw material sources are wide, advantages such as reaction conditions gentleness, technical process is short, technology is more easily grasped, the requirement of quality product conformance with standard, treated recovery ammonium chloride of waste water or ammonium sulfate, not having three-waste pollution, is not only an environmental protection but also economic synthetic route.The present invention is mainly used in and passes through preparing resorcin by hydrolyzing m-phenylenediamine.
Description of drawings:
Fig. 1 is the process flow sheet of sulfonated alkali fusion method;
Fig. 2 is a m-Diisopropylbenzene method process flow sheet.
Embodiment:
The invention will be further described below in conjunction with the preparation example.
Preparation example one:
(1) add entry 2660mL, mphenylenediamine 216g successively in the 5L reactor, stir and make its dissolving, drip 98% sulfuric acid 420g then, feed temperature is no more than 100 ℃, adds the back and stirs 0.5h;
(2) above-mentioned solution is transferred to autoclave pressure, is warming up to 230 ℃, pressure 2.6MPa～3.0MPa, insulation 5h, reaction finishes, and is cooled to normal temperature;
(3) take out reaction solution, with 400ml extracted with diethyl ether 4 times, steam solvent and get crude product 190g, content is 95.68%, through distill product 180g, content is 99.3%.
Preparation example two:
(1) add entry 2660mL successively in the 5L reactor, mphenylenediamine 216g stirs and makes its dissolving, drips 98% sulfuric acid 420g then, and feed temperature is no more than 100 ℃, adds the back and stirs 0.5h;
(2) above-mentioned solution is transferred to autoclave pressure, is warming up to 250 ℃, pressure 3.8MPa～4.0MPa, insulation 3h, reaction finishes, and is cooled to normal temperature;
(3) take out reaction solution, with 400ml extracted with diethyl ether 4 times, steam solvent and get crude product 193g, content is 95.28%, through distill product 178g, content is 99.2%.
Preparation example three:
(1) add entry 2600mL successively in the 5L reactor, mphenylenediamine 216g stirs and makes its dissolving, drips 31% hydrochloric acid 495g then, and feed temperature is no more than 100 ℃, adds the back and stirs 0.5h;
(2) above-mentioned solution is transferred to autoclave pressure, is warming up to 230 ℃, pressure 2.6MPa～3.0MPa, insulation 5h, reaction finishes, and is cooled to normal temperature;
(3) take out reaction solution, with 400ml extracted with diethyl ether 4 times, steam solvent and get crude product 192g, content is 95.1%, through distill product 182g, content is 99.4%.
Preparation example four:
(1) add entry 2600mL successively in the 5L reactor, mphenylenediamine 216g stirs and makes its dissolving, drips 31% hydrochloric acid 495g then, and feed temperature is no more than 100 ℃, adds the back and stirs 0.5h;
(2) above-mentioned solution is transferred to autoclave pressure, is warming up to 250 ℃, pressure 3.8MPa～4.0MPa, insulation 3h, reaction finishes, and is cooled to normal temperature;
(3) take out reaction solution, with 400ml extracted with diethyl ether 4 times, steam solvent and get crude product 194g, content is 95.1%, through distill product 183g, content is 99.5%.
Claims (6)
1, a kind of method with preparing resorcin by hydrolyzing m-phenylenediamine is characterized in that comprising following processing step:
1., mphenylenediamine and inorganic acid reaction are generated salt;
2., above-mentioned generation salt hydrolysis is obtained the Resorcinol material;
3., above-mentioned materials abstraction is obtained the Resorcinol crude product;
4., above-mentioned Resorcinol crude product is steamed the molten crude product Resorcinol that obtains;
5., the crude product Resorcinol is distilled the Resorcinol finished product.
2, a kind of method with preparing resorcin by hydrolyzing m-phenylenediamine according to claim 1 is characterized in that the inorganic acid that 1. adopts in the step is a hydrochloric acid.
3, a kind of method with preparing resorcin by hydrolyzing m-phenylenediamine according to claim 1 is characterized in that the inorganic acid that 1. adopts in the step is a sulfuric acid.
4, according to claims 2 described methods, it is characterized in that adopting following technological process with preparing resorcin by hydrolyzing m-phenylenediamine:
1., in reactor, add entry, mphenylenediamine successively, stir and make its dissolving, slowly drip 31% hydrochloric acid again, feed temperature is no more than 100 ℃, adds the back and stirs 0.5h;
2., above-mentioned solution is warming up to 230 ℃～250 ℃, boost to 2.6MPa～4.0Mpa, more than the insulation 3h, hydrolysis reaction is cooled to below 40 ℃ after finishing;
3., with the material solvent extraction after the hydrolysis cooling, Resorcinol is extracted in the solvent, is neutralized to slightly acidic with buck then;
4., the Resorcinol crude product that will contain solvent boils off solvent, solvent is applied mechanically, content is about 95% crude product Resorcinol;
5., above-mentioned crude product is distilled to such an extent that content is Resorcinol finished product more than 99.0%.
5, according to claims 3 described methods, it is characterized in that adopting following technological process with preparing resorcin by hydrolyzing m-phenylenediamine:
1., in reactor, add entry, mphenylenediamine successively, stir and make its dissolving, slowly drip 98% sulfuric acid again, feed temperature is no more than 100 ℃, adds the back and stirs 0.5h;
2., above-mentioned solution is warming up to 230 ℃～250 ℃, boost to 2.6MPa～4.0MPa, more than the insulation 3h, hydrolysis reaction is cooled to below 40 ℃ after finishing;
3., with the material solvent extraction after the hydrolysis cooling, Resorcinol is extracted in the solvent, is neutralized to slightly acidic with buck then;
4., the Resorcinol crude product that will contain solvent boils off solvent, solvent is applied mechanically, content is about 95% crude product Resorcinol;
5., above-mentioned crude product is distilled to such an extent that content is Resorcinol finished product more than 99.0%.
6, according to the described methods with preparing resorcin by hydrolyzing m-phenylenediamine of claims 1,2 or 3, it is characterized in that: the solvent that uses is ether, n-butyl acetate, any in the sherwood oil.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911018A (en) * | 2011-08-04 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for separating phenol-containing organic substances from m-phenylenediamine acidic hydrolysate |
| CN103304381A (en) * | 2013-07-10 | 2013-09-18 | 常熟市联创化学有限公司 | Preparation method of 2,6-dihydroxytoluene |
| CN103360266A (en) * | 2013-07-19 | 2013-10-23 | 江苏科圣化工机械有限公司 | Method for co-production of aramid fiber scale m-phenylenediamine and resorcinol |
| CN103848724A (en) * | 2014-03-18 | 2014-06-11 | 南京工业大学 | Process of producing resorcinol by hydrolyzing m-phenylenediamine |
| CN111018676A (en) * | 2019-12-11 | 2020-04-17 | 乌海时联环保科技有限责任公司 | Method for preventing resorcinol from discoloring |
| CN111592447A (en) * | 2020-06-12 | 2020-08-28 | 内蒙古盛唐国际蒙医药研究院有限公司 | Resorcinol preparation method |
| CN114149306A (en) * | 2021-12-09 | 2022-03-08 | 青岛科技大学 | Synthesis process of resorcinol |
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- 2006-06-13 CN CN 200610019367 patent/CN1927795A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102911018A (en) * | 2011-08-04 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for separating phenol-containing organic substances from m-phenylenediamine acidic hydrolysate |
| CN102911018B (en) * | 2011-08-04 | 2015-05-20 | 浙江龙盛化工研究有限公司 | Method for separating phenol-containing organic substances from m-phenylenediamine acidic hydrolysate |
| CN103304381A (en) * | 2013-07-10 | 2013-09-18 | 常熟市联创化学有限公司 | Preparation method of 2,6-dihydroxytoluene |
| CN103304381B (en) * | 2013-07-10 | 2015-12-02 | 常熟市联创化学有限公司 | The preparation method of 2,6-orcin |
| CN103360266A (en) * | 2013-07-19 | 2013-10-23 | 江苏科圣化工机械有限公司 | Method for co-production of aramid fiber scale m-phenylenediamine and resorcinol |
| CN103360266B (en) * | 2013-07-19 | 2015-04-22 | 江苏科圣化工机械有限公司 | Method for co-production of aramid fiber scale m-phenylenediamine and resorcinol |
| CN103848724A (en) * | 2014-03-18 | 2014-06-11 | 南京工业大学 | Process of producing resorcinol by hydrolyzing m-phenylenediamine |
| CN103848724B (en) * | 2014-03-18 | 2016-04-13 | 南京工业大学 | The technique of Resorcinol is produced in a kind of mphenylenediamine hydrolysis |
| CN111018676A (en) * | 2019-12-11 | 2020-04-17 | 乌海时联环保科技有限责任公司 | Method for preventing resorcinol from discoloring |
| CN111592447A (en) * | 2020-06-12 | 2020-08-28 | 内蒙古盛唐国际蒙医药研究院有限公司 | Resorcinol preparation method |
| CN115974654A (en) * | 2020-06-12 | 2023-04-18 | 内蒙古盛唐国际蒙医药研究院有限公司 | Resorcinol preparation method |
| CN114149306A (en) * | 2021-12-09 | 2022-03-08 | 青岛科技大学 | Synthesis process of resorcinol |
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