CN102993233A - Simple method for preparing sulfonated cobalt phenylphosphinate - Google Patents
Simple method for preparing sulfonated cobalt phenylphosphinate Download PDFInfo
- Publication number
- CN102993233A CN102993233A CN2012105744254A CN201210574425A CN102993233A CN 102993233 A CN102993233 A CN 102993233A CN 2012105744254 A CN2012105744254 A CN 2012105744254A CN 201210574425 A CN201210574425 A CN 201210574425A CN 102993233 A CN102993233 A CN 102993233A
- Authority
- CN
- China
- Prior art keywords
- acid
- cobalt
- sulfonation
- phosphenylic acid
- crude product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a simple method for preparing sulfonated cobalt phenylphosphinate. The simple method is characterized in that phenyl phosphonic acid and sulfur trioxide carry out sulfonation reaction to obtain a sulfonated phenyl phosphonic acid crude product containing sulfuric acid impurities and the sulfuric acid impurities in the water solution of the sulfonated phenyl phosphonic acid crude product are unnecessary to be removed and can be directly added to the cobalt salt to react to obtain the sulfonated cobalt phenylphosphinate product. The simple method has the advantages that by utilizing the characteristic that cobalt sulfate is soluble in water, the sulfuric acid is unnecessary to be removed from the water solution of the sulfonated phenyl phosphonic acid crude product when sulfonated cobalt phenylphosphinate is prepared, thus omitting the processes of adding vast barium chloride and using cation exchange resins to remove barium ions; vast barium chloride is saved and barium sulfate waste discharge is reduced; and the processes of utilizing the cation exchange resins for ion exchange and spending vast time in activating the ion exchange resins with hydrochloric acid are omitted.
Description
Technical field
The present invention relates to a kind of easy method for preparing sulfonation phosphenylic acid cobalt.Sulfonation phosphenylic acid cobalt can be used for the fields such as proton conductor, sensor and solid acid catalysis, proton exchange film preparation.
Background technology
Insoluble solid proton acid is that a class has the widely functional materials of purposes, can be used for the fields such as proton conductor, solid acid catalyst, sensor, compound proton exchange membrane additive.
Sulfonation phosphniline hydrochlorate, a class lamellar compound such as sulfonation Pillared Zirconium Phenylphosphonate (ZrSPP), the zirconium ion of its a plurality of phosphonyl groups and+4 valencys forms the lamellar compound of polymkeric substance formula, its interlamellar spacing is at 1.3～1.5nm, the sulfonic acid group of its interlayer is with hydrogen bonded, can show strongly-acid, so this compounds is subject to people's attention in the application of commonly used such material of organic solvent such as water, alcohol as solid acid.The preparation of ZrSPP generally is to adopt the mixture of phosphenylic acid and phosphoric acid and the reaction of chlorine oxygen zirconium, obtain the mixture of Pillared Zirconium Phenylphosphonate and phosphoric acid hydrogen zirconium, then can obtain mixture (the Stein Sr.E W of sulfonation Pillared Zirconium Phenylphosphonate, Pillared Zirconium Phenylphosphonate and phosphoric acid hydrogen zirconium with the oleum sulfonation, et al.Solid State Ionics (solid ionic) .1996,83:113).Li Zhongfang etc. reported also that phosphenylic acid and chlorine oxygen zirconium reacted the preparation (Zhongfang Li, et al.J Membr Sci(membrane science magazine) that rear sulfonation prepares the method for sulfonation Pillared Zirconium Phenylphosphonate and is used for high temperature proton exchange film, 2010,351:50; Li Zhongfang etc., Chinese invention patent, the patent No.: ZL200810160560.8).
Preparation technology's flow process of sulfonation Pillared Zirconium Phenylphosphonate is as follows:
The sulfonation degree of the sulfonation Pillared Zirconium Phenylphosphonate of this method preparation is subjected to the restriction of sulfonating conditions, if sulfonation degree is higher than 100%, then the sulfonation Pillared Zirconium Phenylphosphonate forms colloidal solution and is difficult to obtain precipitation in water.Certainly, this method also can't prepare sulfonation degree greater than 100% product.
The patent of Li Zhongfang etc. the report (ZL200810160561.2 such as Li Zhongfang; The preparation method of the sulfonation phosphniline hydrochlorate of ZL201010011829.3) reporting is that at first, then phosphenylic acid and metal oxide or salt (subsalt) reaction preparation phosphniline hydrochlorate precipitation is carried out sulfonation to the phosphniline hydrochlorate and prepared sulfonation phosphniline hydrochlorate.The sulfonation degree of the sulfonation phosphniline hydrochlorate of the method preparation is not high (except the sulfonation degree of sulfonation Pillared Zirconium Phenylphosphonate can reach 98%, the sulfonation degree of general sulfonation phosphniline hydrochlorate is lower than 90%), say that strictly they should be the mixtures of sulfonation phosphniline hydrochlorate and phosphniline hydrochlorate.If adopt the sulfonating conditions of more strengthening, oleum can destroy the structure of the layered polymer of phosphniline hydrochlorate, then can not obtain the precipitation of sulfonation phosphniline hydrochlorate.
Li Zhongfang etc. have also reported a kind of method (Li Zhongfang etc., ZL201110025172.0 for preparing highly sulfonated (sulfonation degree is greater than 100%), pure sulfonated cerium phenylphosphinate (CeSPP); Feilong Dong, Zhongfang Li, et al.Materials Letters(material wall bulletin), 2011,65 (9): 1431) and the preparation method of other sulfonation phosphniline hydrochlorate and application thereof (Li Zhongfang etc., ZL 201110025228.2; Feilong Dong, Zhongfang Li, the international Hydrogen Energy magazine of et al.Int J Hydrogen Energy(), 2011,36:11068-11074).The preparation technology of CeSPP is: with sulfonation phosphenylic acid (SPPA), SPPA and ceric ammonium nitrate reaction prepare CeSPP by phosphenylic acid (PPA) preparation.
Preparation technology is as follows:
In the first step reaction process, because SO
3Excessive, when reaction solution is transferred in the water, have a large amount of sulfuric acid and produce and a small amount of unreacted phosphenylic acid.This just need to remove unreacted phosphenylic acid and sulfuric acid.
At first add 15%BaCl
2Solution is to remove sulfuric acid, the centrifugal BaSO that removes
4Precipitation.Because the amount of sulfuric acid is larger, so, need to consume a large amount of bariumchlorides.Filtrate joined carry out ion-exchange 24h in the Zeo-karb, to remove excessive barium ion, suction filtration use the ether re-extract after gained filtrate is concentrated with Rotary Evaporators, until the ether PH after extracting is near 7, to remove unreacted phosphenylic acid.After water layer is concentrated with Rotary Evaporators, in 60 ℃ of vacuum drying ovens, dry, obtain yellow thick liquid, pure sulfonation phosphenylic acid (SPPA).
The sulfonation degree of sulfonation phosphenylic acid (DS phenyl ring and the per-cent that is connected with sulfonic acid group) 〉=100%, also can obtain sulfonation degree and be 200% sulfonation phosphenylic acid (being connected with 2 sulfonic groups on each phenyl ring), certainly, can prepare the sulfonation phosphenylic acid of sulfonation degree between 100%～200%.The reaction of this sulfonation phosphenylic acid and ceric ammonium nitrate, its phosphonate group can with Ce
4+Generation layer shaped polymer precipitation obtains CeSPP.
In sulfonation phosphenylic acid purifying technique, remove a large amount of sulfuric acid in the reaction solution, not still time-consuming, the effort, but also to consume a large amount of bariumchlorides, produce a large amount of barium sulfate wastes, use the regeneration of a large amount of Zeo-karbs and Zeo-karb will consume a large amount of hydrochloric acid, produce a large amount of waste water.
Summary of the invention
Technical problem to be solved by this invention provides a kind of simple and easy method for preparing sulfonation phosphenylic acid cobalt, shortens technique, saves material, reduces pollutant emission.
A kind of simple and easy method for preparing sulfonation phosphenylic acid cobalt of the present invention, it is characterized in that phosphenylic acid and sulphur trioxide generation sulfonation reaction obtain containing the sulfonation phosphenylic acid crude product of sulfuric acid impurity, do not need to remove the sulfuric acid in the crude product solution, remove phosphenylic acid, the dilute acid soln that directly adds the soluble salt of cobalt in the aqueous solution of sulfonation phosphenylic acid crude product reacts, and obtains sulfonation phosphenylic acid cobalt product.
The present invention utilizes the water-soluble characteristic of rose vitriol, and when preparation sulfonation phosphenylic acid cobalt, the aqueous solution of sulfonation phosphenylic acid crude product can be removed sulfuric acid, has saved the process that adds a large amount of bariumchlorides and remove barium ion with Zeo-karb.Save a large amount of bariumchlorides, reduced the barium sulfate waste discharge.Saved and utilized Zeo-karb to carry out the process that ion-exchange, hydrochloric acid activation ion exchange resin expend the plenty of time.
Concrete operation step is:
1) preparation of sulfonation phosphenylic acid (SPPA)
With SO
3Gas slowly is passed into and contains phosphenylic acid and 1, in the mixed solution of the organic solvents such as 2-ethylene dichloride or tetrachloroethane, reaction solution is gradually by the colourless yellow that is transformed into, with round-bottomed flask after 70 ℃～90 ℃ heating in water bath reflux 14～24h, obtain being divided into the liquid of two-phase, the upper strata is organic solvent, and lower floor is the sulfonation phosphenylic acid crude product of yellow thickness.Separatory reclaims organic solvent, and the gained crude product is dissolved in deionized water, uses the ether re-extract, until the ether pH after the extraction is near 7, to remove unreacted phosphenylic acid.Water is that sulfonation phosphenylic acid crude product (containing a large amount of sulfuric acid impurities) is for subsequent use.
2) preparation of sulfonation phosphenylic acid cobalt
In the beaker of 100mL, add a certain amount of cobalt chloride (soluble salts such as Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol and rose vitriol), add 30mL(0.1～1.0 to it) molL
-1Hydrochloric acid (the inorganic dilute acid solns such as nitric acid, sulfuric acid are to prevent salt hydrolysis) solution, stir and to make its dissolving.Solution joins in the sulfonation phosphenylic acid crude product (for sulfonation phosphenylic acid and sulfuric acid mixture liquid), keep cobalt salt excessive, mixed reaction solution is behind 45 ℃～65 ℃ lower heating, stirring reaction 6～12h, obtain yellow suspension liquid, high speed centrifugation, supernatant liquid is shifted out, lower sediment repeatedly the second distillation water washing to remove the wherein acid of solubility, till being washed till clear liquid and not generating precipitation with barium chloride solution and silver nitrate solution respectively.Obtain lurid powder, 60 ℃～90 ℃ lower oven dry obtain pure sulfonation phosphenylic acid cobalt dust, and overall yield is 60%～73%.
Advantage of the present invention:
1) the present invention prepare sulfonation phosphenylic acid cobalt with the preparation sulfonated cerium phenylphosphinate technique compare, saved the sulfuric acid of removing in the reaction solution.Thus, save a large amount of bariumchlorides and Zeo-karb, reduced the discharge of pollutent barium sulfate and spent acid.Simplified a large amount of operations, saved time thus, laborsaving.
2) owing to simplified technique, so, the yield of sulfonation phosphenylic acid cobalt can greatly be improved.
3) present method can prepare the sulfonation phosphenylic acid cobalt of highly sulfonated, and sulfonation degree can reach 100%～200%.The loading capacity of such sulfonation phosphenylic acid cobalt is high.Its catalytic performance and specific conductivity are all higher.
4) can obtain pure sulfonation phosphenylic acid cobalt product.
Embodiment
Embodiment 1:
With SO
3Gas slowly is passed into and contains 2g phosphenylic acid and 100mL 1, in the 2-ethylene dichloride mixed solution, reaction solution is gradually by the colourless yellow that is transformed into, with round-bottomed flask behind 90 ℃ of heating in water bath backflow 14h, obtain being divided into the liquid of two-phase, the upper strata is colourless 1, the 2-ethylene dichloride, and lower floor is the sulfonation phosphenylic acid crude product of yellow thickness.Separatory reclaims 1,2-ethylene dichloride clear liquid, and the gained crude product is dissolved in deionized water, uses the ether re-extract, until the ether pH after the extraction is near 7, to remove unreacted phosphenylic acid.Water is that sulfonation phosphenylic acid crude product (containing a large amount of sulfuric acid impurities) is for subsequent use.
Embodiment 2:
Step just passes into SO in the tetrachloroethane mixed solution with 19.1mmol (3.02g) phosphenylic acid and 150mL with embodiment 1
3, SO
3Excessive approximately 7%, sulfonation phosphenylic acid crude product.
Embodiment 3:
The preparation of sulfonation phosphenylic acid cobalt (CoSPP)
In the beaker of 100mL, add the cobalt chloride of 0.030mol, add 30mL(0.1～1.0 to it) molL
-1Hydrochloric acid soln, stir and to make its dissolving.Solution joins in (sulfonation phosphenylic acid content is 0.030mol) sulfonation phosphenylic acid crude product (for sulfonation phosphenylic acid and sulfuric acid mixture liquid), mixed reaction solution is behind 60 ℃ of lower heating, stirring reaction 12h, obtain suspension liquid, high speed centrifugation, the upper strata stillness of night is shifted out, lower sediment repeatedly second distillation water washing is washed till till the stillness of night do not generate precipitation with barium chloride solution and silver nitrate solution respectively to remove the wherein acid of solubility.Obtain lurid powder, 60 ℃ of lower oven dry obtain pure sulfonation phosphenylic acid cobalt dust, and overall yield is 78%.
Embodiment 4:
In the beaker of 250mL, add the cobalt chloride of 0.060mol, add 60mL(0.1～1.0 to it) molL
-1Hydrochloric acid soln, stir and to make its dissolving.Solution joins in (sulfonation phosphenylic acid content is 0.060mol) sulfonation phosphenylic acid crude product (for sulfonation phosphenylic acid and sulfuric acid mixture liquid), mixed reaction solution is behind 50 ℃ of lower heating, stirring reaction 8h, obtain suspension liquid, high speed centrifugation, the upper strata stillness of night is shifted out, lower sediment repeatedly second distillation water washing is washed till till the stillness of night do not generate precipitation with barium chloride solution and silver nitrate solution respectively to remove the wherein acid of solubility.Obtain lurid powder, 60 ℃ of lower oven dry obtain pure sulfonation phosphenylic acid cobalt dust, and overall yield is 76%.
Embodiment 5:
The preparation of other sulfonation phosphniline hydrochlorate
The preparation method of other sulfonation phosphniline hydrochlorate is with embodiment 2, just wherein raw material cobaltrichloride changed into other salt compounds and gets final product.Adopt AlCl
3, CrCl
3, KAl (SO
4)
2, NiSO
4, MnSO
4Deng all not obtaining sulfonation phosphniline hydrochlorate precipitation.
Embodiment 6:
Sulfonation phosphenylic acid cobalt is as the application of high-temperature proton-conductor
Sulfonation phosphenylic acid cobalt itself namely can be used as High-temperature proton conductor material and uses, the specific conductivity during its high temperature proton conductivity test relative humidity 100% under the differing temps, and its result is as follows: 0.01Scm
-130 ℃ of@, 0.02Scm
-160 ℃ of@, 0.03Scm
-180 ℃ of@, 0.06Scm
-1100 ℃ of@, 0.08Scm
-1120 ℃ of@, 0.12Scm
-1140 ℃ of@, 0.21Scm
-1160 ℃ of@.
Embodiment 7:
The preparation of the high temperature proton exchange film of doped sulfonated phosphenylic acid cobalt
Sulfonation phosphenylic acid cobalt as the additive of proton exchange membrane for the preparation of high temperature proton exchange film.Its implementation method is with Li Zhongfang etc., Chinese invention patent, and the patent No.: the embodiment 7 among the ZL200810160560.8 is similar.Just wherein raw material sulfonation Pillared Zirconium Phenylphosphonate being changed into sulfonation phosphenylic acid cobalt gets final product.
If raw material SPPESK is changed into other macromolecular material, can prepare the high temperature proton exchange film of other type.
Embodiment 8:
Sulfonation phosphenylic acid cobalt can be used as solid acid catalyst as solid acid and is used for field of fine chemical.
The building-up reactions that is used for the catalytic plasticizer dioctyl phthalate (DOP);
Octanol, 200mL band aqua toluene and the 2.1g sulfonation phosphenylic acid cobalt catalyst, mixed solution stirring, heating, the back flow reaction 6h that in the 500mL there-necked flask of water trap, electric mixer and reflux condensing tube is housed, add respectively 0.08mol phthalic anhydride, 0.30mol, reach 99% with gas chromatographic detection phthalic anhydride transformation efficiency, the dioctyl phthalate (DOP) productive rate reaches 96%.Cooling filters out catalyzer sulfonation phosphenylic acid cobalt, and is reusable.
Embodiment 9:
Sulfonation phosphenylic acid cobalt is that catalyzer is used for catalytic dimerization cyclopentadiene and acetic acid direct esterification reaction
In being housed, the 500mL there-necked flask of water trap, electric mixer and reflux condensing tube adds the 0.105mol dicyclopentadiene, 0.20mol Glacial acetic acid, make the band aqua with the toluene of 100mL, the sulfonation phosphenylic acid cobalt catalyst that adds 2.0g, under the vigorous stirring, heating, back flow reaction 6h use liquid chromatographic detection, the transformation efficiency of dicyclopentadiene is 96%, selectivity 98%.Esterification yied 91%
Embodiment 10:
Be used for the utilization of catalysis polyster fibre waste material transesterification reaction raw material, reaction formula is as follows:
In the 500mL there-necked flask of electric mixer, reflux condensing tube is housed, add respectively the polyster fibre waste material that 5g cleans, 200mL ethanol and 0.25g sulfonation phosphenylic acid cobalt, heating, backflow, stirring reaction 12-16h, the discovery terylene waste material is dissolved, solution is water white transparency, filters out granules of catalyst, and is reusable.The productive rate that chromatography of gases detects diethyl terephthalate is 96%.
Claims (6)
1. simple and easy method for preparing sulfonation phosphenylic acid cobalt, it is characterized in that phosphenylic acid and sulphur trioxide generation sulfonation reaction obtain containing the sulfonation phosphenylic acid crude product of sulfuric acid impurity, do not need to remove the sulfuric acid in the crude product solution, remove phosphenylic acid, the dilute acid soln that directly adds the soluble salt of cobalt in the aqueous solution of sulfonation phosphenylic acid crude product reacts, and obtains sulfonation phosphenylic acid cobalt product.
2. the simple and easy method of preparation sulfonation phosphenylic acid cobalt according to claim 1 is characterized in that the aqueous solution of sulfonation phosphenylic acid crude product and the temperature of reaction of cobalt salt are 45-65 ℃.
3. the simple and easy method of preparation sulfonation phosphenylic acid cobalt according to claim 1, the soluble salt that it is characterized in that described cobalt is cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or rose vitriol.
4. the simple and easy method of preparation sulfonation phosphenylic acid cobalt according to claim 1 is characterized in that described mineral acid is hydrochloric acid, nitric acid or sulfuric acid.
5. according to claim 1, the simple and easy method of 3 or 4 described preparation sulfonation phosphenylic acid cobalts, it is characterized in that comprising the steps:
(1) with an amount of SO
3Gas slowly is passed into and contains in phosphenylic acid and the organic solvent mixed solution, the color of reaction solution is gradually by the colourless yellow that is transformed into, after 70 ℃～90 ℃ heating in water bath reflux 14～24h, leave standstill, reaction solution is divided into two-phase liquid, the upper strata is organic solvent, lower floor is the sulfonation phosphenylic acid crude product of yellow thickness, and separatory reclaims organic solvent, lower floor's gained crude product is dissolved in deionized water, use the ether re-extract, until the ether pH after the extraction is near 7, to remove unreacted phosphenylic acid, water is sulfonation phosphenylic acid crude product, and is for subsequent use;
(2) in cobalt salt, add inorganic acid solution, make its dissolving, solution joins in the sulfonation phosphenylic acid crude product aqueous solution of step 1 preparation, keep cobalt salt excessive, mixed reaction solution is behind 45 ℃～65 ℃ lower heating, stirring reaction 6～12h, obtain yellow suspension liquid, centrifugal, supernatant liquid is shifted out, removing the wherein acid of solubility, washings does not obtain lurid powder till not generating precipitation with barium chloride solution and silver nitrate solution respectively to lower sediment with distilled water wash, 60 ℃～90 ℃ lower oven dry obtain pure sulfonation phosphenylic acid cobalt dust.
6. the simple and easy method of preparation sulfonation phosphenylic acid iron according to claim 5 is characterized in that the described organic solvent of step 1 is 1,2-ethylene dichloride or tetrachloroethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210574425.4A CN102993233B (en) | 2012-12-26 | 2012-12-26 | Simple method for preparing sulfonated cobalt phenylphosphinate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210574425.4A CN102993233B (en) | 2012-12-26 | 2012-12-26 | Simple method for preparing sulfonated cobalt phenylphosphinate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102993233A true CN102993233A (en) | 2013-03-27 |
| CN102993233B CN102993233B (en) | 2015-03-25 |
Family
ID=47922399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210574425.4A Expired - Fee Related CN102993233B (en) | 2012-12-26 | 2012-12-26 | Simple method for preparing sulfonated cobalt phenylphosphinate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102993233B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775210A (en) * | 2010-01-12 | 2010-07-14 | 山东理工大学 | Preparation method of high-temperature proton conductor composite material |
| CN102443023A (en) * | 2011-01-24 | 2012-05-09 | 山东理工大学 | Preparation method of sulfonated cerium phenylphosphinate |
-
2012
- 2012-12-26 CN CN201210574425.4A patent/CN102993233B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775210A (en) * | 2010-01-12 | 2010-07-14 | 山东理工大学 | Preparation method of high-temperature proton conductor composite material |
| CN102443023A (en) * | 2011-01-24 | 2012-05-09 | 山东理工大学 | Preparation method of sulfonated cerium phenylphosphinate |
Non-Patent Citations (1)
| Title |
|---|
| MYUNGSEOP HWANG ET AL.: "Zirconium meta-sulfonphenyl phosphonic acid-incorporated Nafion membranes for reduction of methanol permeability", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102993233B (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2015032113A1 (en) | Metalporphyrin complex, preparation method therefor and method for preparing polycarbonate | |
| CN100431704C (en) | Method for preparing chitose magnetic microsphere metal palladium complex catalyst | |
| CN105148990B (en) | A kind of preparation method and applications of sulfonic acid carbon nano tube/graphene oxide composite catalyst | |
| CN102408338A (en) | Method for synthesizing salicylate | |
| CN104646057A (en) | Polyacid/nano-carbon-hybridized solid acid catalyst, preparation method and application thereof | |
| CN110479374A (en) | A kind of phosphorus heteropoly tungstic acid salt catalyst and preparation method thereof for synthesizing epoxy chloropropane | |
| CN103694203A (en) | Method of catalyzing fructose by cellulose base sulfonic acid catalyst to prepare 5-hydroxymethyl furfural | |
| CN105964306A (en) | Poly(ionic liquid)-based magnetic nanoparticle and its preparation method and use in three-ingredient reaction | |
| CN102993233B (en) | Simple method for preparing sulfonated cobalt phenylphosphinate | |
| CN105503513A (en) | Method for catalytically synthesizing 4,4'-bischloromethylbiphenyl by using silicon dioxide-loaded phosphotungstic acid | |
| CN110732347B (en) | Binuclear ionic liquid type heteropoly acid salt solid acid catalyst for synthesizing chalcone derivatives, preparation method and application | |
| CN102443023B (en) | Preparation method of sulfonated cerium phenylphosphinate | |
| CN102381947B (en) | Synthesis method of chiral 2,2 '- di-alkoxy-1, 1'-binaphthyl | |
| CN116328790A (en) | Preparation method of solid acid catalyst and application of solid acid catalyst in diethylene glycol dibenzoate synthesis | |
| CN102993232B (en) | Simple method for preparing sulfonated iron phenylphosphinate | |
| CN103055860B (en) | Composited crystal solid alkali supporter catalyst and preparation method | |
| CN102659572B (en) | Preparation method of dehydroabietic acid | |
| CN103864572B (en) | A kind of method preparing glycol | |
| CN102382148A (en) | Production technology of bis(triphenylphosphine) palladium chloride | |
| CN102408339B (en) | Clean nitration reaction of aromatic hydrocarbon of heteropolyacid pyridinium ionic liquid catalyst | |
| CN104072364A (en) | Preparation method for diflunisal and catalyst thereof | |
| CN101768045B (en) | Method for preparing halogenated hydrocarbons from strong acidic ionic liquid | |
| CN103319383B (en) | Preparation method of p-methylsulfonylbenzoic acid | |
| CN103435463A (en) | Method for preparing 9-fluorenone via four-phase transfer catalysis | |
| CN111939978A (en) | Preparation method and application of heterogeneous metal catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150325 Termination date: 20161226 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |