CN102675115B - Method for synthesizing diphenyl carbonate from dimethyl carbonate - Google Patents
Method for synthesizing diphenyl carbonate from dimethyl carbonate Download PDFInfo
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- CN102675115B CN102675115B CN201110058391.9A CN201110058391A CN102675115B CN 102675115 B CN102675115 B CN 102675115B CN 201110058391 A CN201110058391 A CN 201110058391A CN 102675115 B CN102675115 B CN 102675115B
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Abstract
The invention relates to a method for synthesizing diphenyl carbonate from phenol and dimethyl carbonate. The method comprises the following process steps of: synthesizing a phenoxy metal compound by using the phenol as a raw material with an organic metal compound (RO)XM or absolute metal chloride; reacting with the dimethyl carbonate to synthesize methyl phenyl carbonate and a methoxy metal compound; and finally performing disproportionation on the methyl phenyl carbonate to synthesize the diphenyl carbonate. In the synthesis process, the methoxy metal compound produced by the reaction can be continuously subjected to synthesis with the phenol to obtain the phenoxy metal compound and recycled. The method for synthesizing the diphenyl carbonate has the advantages of simple process, mild reaction conditions and capability of meeting requirements of industrial large-scale production.
Description
Technical field
The present invention relates to a kind of synthetic method of diphenyl carbonate, particularly relating to a kind of phenol and methylcarbonate of adopting is the method for Material synthesis diphenyl carbonate.
Background technology
Diphenyl carbonate (being called for short DPC) is nontoxic, pollution-free, it is a kind of important environmental protection class organic carbonate, can be used as engineering plastics intermediate and synthesize multiple important organic compound and macromolecular material, as manufacture polycarbonate, methyl p-hydroxybenzoate, monoisocyanates, vulcabond and the softening agent preparing polymeric amide and polyester; In Chemical Manufacture, as solvent and thermal barrier.
DPC is the important source material of synthesis of bisphenol A type polycarbonate, and dihydroxyphenyl propane type polycarbonate (being called for short PC), the over-all properties excellent because of it and processing characteristics, and be widely used in electric and electronic component, mechanical textile industry component, building structural member, aviation transparencies material and the aspect such as component, structural foam; And the application of PC expands to just rapidly many high-technology fields such as aerospace, electronics, computer, CD, especially in the application of CD, development is very fast.Therefore, the synthesis of diphenyl carbonate becomes the focus of people's research and development.
The synthetic method of diphenyl carbonate mainly includes phosgenation, oxidation of phenol carbonyl process and ester-interchange method.In view of in traditional phosgenation, the huge potential safety hazard that the severe toxicity of phosgene and severe corrosive bring and problem of environmental pollution, the method is just progressively eliminated, and the catalyzer used in oxidation of phenol carbonyl process is expensive, and product yield is low, industrial manufacture process is not mature enough, and therefore ester-interchange method is the main method of current diphenyl carbonate synthesis, and wherein the synthetic route of people's most study is for raw material carries out synthesis of diphenyl carbonate by ester exchange reaction with phenol and methylcarbonate.But in the first step reaction of this synthetic route, the transesterify synthesis of methyl phenyl carbonic ether of methylcarbonate and phenol is thermodynamics reversible reaction, and the equilibrium constant is very little, and (during 453K, the equilibrium constant is 3 × 10
-4), be unfavorable for the generation of target product, make the yield of diphenyl carbonate low, speed of response is very slow.
In order to improve the yield of methyl benzol carbonate, be developed a series of synthesis technique and method.In patent EP780361, EP780360, US6600061, all use pressurization, distil process, constantly disequilibrate raising product yield, but in preparation process, temperature reaches more than 200 DEG C, and reaction conditions is difficult to control.Patent US4182726 introduces ethanoyl in the preparation process of diphenyl carbonate, uses phenyl acetate and DMC diphenyl carbonate synthesis; And for example Chinese patent CN100374204C is providing the diphenyl carbonate preparation method that a kind of employing take metallocenetype compound as catalyzer; Patent CN101423476A provides a kind of diphenyl carbonate preparation method adopting solid heteropoly compound to make catalyzer, thus alleviate above-mentioned diphenyl carbonate preparation process condition, but these method preparation process are loaded down with trivial details, require high for manufacturing condition, contributed capital is large, is not thus suitable for industrial mass production.
Summary of the invention
The invention provides a kind of method of phenol and dimethyl carbonate synthesis diphenyl carbonate, the present invention adopts in reaction raw materials, adds organometallic compound (RO)
xm or anhydrous metal muriate, first make phenol and described organometallic compound or anhydrous metal muriate generate intermediate phenoxy group metallic compound (C
6h
6o)
xm, described (C
6h
6o)
xm prepares diphenyl carbonate with dimethyl carbonate again, and reaction efficiency is high, and reaction conditions is gentle, thus overcomes in above-mentioned existing diphenyl carbonate preparation technology, reaction difficulty, the problems such as processing condition are harsh, and process complexity is loaded down with trivial details.
The method of a kind of phenol of the present invention and dimethyl carbonate synthesis diphenyl carbonate is achieved through the following technical solutions its object:
A method for phenol and dimethyl carbonate synthesis diphenyl carbonate, wherein, comprises following concrete steps:
Step one: under anhydrous and oxygen-free condition, has general formula (RO) by phenol and one or more
xthe organometallic compound of M or the mixing of anhydrous metal muriate, Reactive Synthesis phenoxy group metallic compound (C
6h6O)
xm, wherein, M is metal, and x is 1 ~ 4, R is alkyl; Wherein, temperature of reaction is preferably 100 ~ 160 DEG C, and the reaction times is preferably 2 ~ 7 hours, and more preferably reaction 3 ~ 4 hours at temperature 100 ~ 130 DEG C; Reaction equation is as follows:
Step 2: under anhydrous and oxygen-free condition, obtained phenoxy group metallic compound and dimethyl carbonate are obtained methyl benzol carbonate, this reactions steps is preferably reacts 3 ~ 6 hours under 1 ~ 10atm pressure and 130 ~ 180 DEG C of temperature condition, obtains methyl benzol carbonate and methoxide compound (CH
3o)
n(C
6h6O)
x-nm(1≤n≤X); Wherein, preferred under at pressure, to be 5atm temperature of reaction be under 150 DEG C of conditions further, 4 hours reaction times; Reaction equation is as follows:
Step 3: obtained methyl benzol carbonate is carried out disproportionation reaction, obtained diphenyl carbonate; Reaction equation is as follows:
Above-mentioned method, wherein, organometallic compound described in step one (RO)
xm, wherein R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl, and M is Ti, Al, Fe or Pb, and x is 1 ~ 4.Wherein preferably R is-CH
3or (CH
3)
2cH-, M are Ti, X is 4, that is, described organometallic compound is metatitanic acid methyl esters (tetramethoxy titanium) and isopropyl titanate (tetraisopropoxy titanium).
Above-mentioned method, wherein, also comprises step 4, will in above-mentioned steps two, and reaction obtains by product organometallic compound (CH simultaneously
3o)
n(C
6h
6o)
x-nm, adds phenol, repeats above-mentioned steps one to step 3, is recycled by by product, and preferably temperature of reaction is 120 DEG C, and the reaction times is 3 hours.
Above-mentioned method, wherein, in described step one, adopts reaction distillation or rectificating method synthesis of phenoxy metallic compound (C
6h
6o)
xm.
Above-mentioned method, wherein, in described step 3, the disproportionation reaction of described methyl benzol carbonate is for adopting reaction distillation or rectification process, and temperature is 140 ~ 180 DEG C, preferable temperature 180 DEG C.
Above-mentioned method, wherein, described step 3 adopts catalytic disproportionation reaction, and used catalyst is the compound of basic metal or cadmium, zirconium, lead, iron, copper, the compound of zinc or organo-tin compound or aluminium, titanium, vanadium.It can adopt phenoxy group metallic compound (C obtained in described step one
6h
6o)
xm, as catalyzer, is particularly preferably metatitanic acid phenyl ester (four phenoxide titaniums).
Above-mentioned method, wherein, the content of described catalyzer is 0.1 ~ 10wt%.
According to a kind of preferred embodiment of the method that the present invention is above-mentioned, wherein, comprise the following steps:
Step one: under anhydrous and oxygen-free condition, by phenol with there is general formula (RO)
4the organic titanic compound mixing of Ti, and synthesis of phenoxy titanium (C6H6O)
4ti, the mol ratio of described phenol and described organic titanium is preferably greater than or equal to 4:1;
Step 2: under anhydrous and oxygen-free condition, by obtained (C
6h
6o)
4m and methylcarbonate, under 1 ~ 10atm pressure, temperature is react at 130 ~ 180 DEG C, obtained methyl benzol carbonate, and wherein R is alkyl; Step 3: obtained methyl benzol carbonate is carried out disproportionation reaction, obtained diphenyl carbonate.
Above-mentioned method, wherein, also comprises step 4, will in above-mentioned steps two, and reaction obtains organic titanate (CH simultaneously
3o)
n(C
6h
6o)
x-npass into phenol in the organo metallic acid methyl esters of Ti, wherein 1≤n≤X, repeat above-mentioned steps one to step 3, obtained organic titanium phenyl ester is recycled.
The benefit of the method for a kind of phenol of the present invention and dimethyl carbonate synthesis diphenyl carbonate is adopted to be:
The method of a kind of phenol of the present invention and dimethyl carbonate synthesis diphenyl carbonate is first by phenol and described organometallic compound (RO)
xm or anhydrous metal muriate generate intermediate organometallic phenyl ester (C
6h
6o)
xm, described organo-metallic phenyl ester (C
6h
6o)
xm prepares diphenyl carbonate with dimethyl carbonate again, in diphenyl carbonate synthesis scheme of the present invention, to avoid in prior art methylcarbonate directly and phenol carry out transesterify synthesis of methyl phenyl carbonic ether step, thus overcome in existing diphenyl carbonate preparation technology, reaction difficulty, the problems such as process is loaded down with trivial details, make in reaction process, technique is simple, mild condition, more easily controls, and intermediate organometallic compound and disproportionation reaction by product methylcarbonate can use by iterative cycles, economize on resources cost, is satisfied with industrial mass production needs.
Accompanying drawing explanation
Fig. 1 is the synthetic schemes of the diphenyl carbonate of the method for a kind of phenol of the present invention and dimethyl carbonate synthesis diphenyl carbonate.
Embodiment
As shown in Figure 1, the method for a kind of phenol of the present invention and dimethyl carbonate synthesis diphenyl carbonate, comprises following concrete steps:
Step one: under anhydrous and oxygen-free condition, stoichiometrically by phenol with there is general formula (RO)
xthe organometallic compound of M or the mixing of anhydrous metal muriate are (wherein, R is methyl, ethyl, propyl group or sec.-propyl, butyl, isobutyl-or the tertiary butyl, M is Ti, Al, Fe or Pb, x is 1 ~ 4), at 100 ~ 160 DEG C of temperature, react 2 ~ 7 hours synthesis of phenoxy organometallic compound (C
6h
6o)
xm, and distillation or rectifying go out alcohol roh, isolate product organo-metallic phenyl ester.In reaction, the content of phenol is excessive slightly, or in reaction process, adopts the mode of progressively adding to add in phenol by organo-metallic acid esters or anhydrous metal muriate, ensures that organo metallic acid ester or anhydrous metal muriate react completely like this.
Step 2: under anhydrous and oxygen-free condition, by obtained phenoxy group metallic compound and methylcarbonate, under 1 ~ 5atm pressure, and reacts 3 ~ 6 hours under 130 ~ 180 DEG C of temperature condition, obtained methyl benzol carbonate.
Step 3: obtained methyl benzol carbonate is adopted reaction distillation or rectification process, under catalyst action, disproportionation reaction can be carried out at 140 ~ 180 DEG C, obtained diphenyl carbonate.Described catalyzer adopts the compound of basic metal or cadmium, zirconium, lead, iron, copper, the compound of zinc or organo-tin compound or aluminium, titanium, vanadium, and preferred metatitanic acid phenyl ester (four phenoxide titaniums), its consumption is 0.1 ~ 10wt%.
Step 4, obtains organo-metallic acid esters (CH in step 2 simultaneously
3o)
n(C
6h
6o)
x-nm passes into phenol (wherein 1≤n≤X), repeats above-mentioned steps one to step 3, is recycled by obtained metatitanic acid phenyl ester.
We adopt way of example more specifically to elaborate content of the present invention below, but content of the present invention is not limited to the following example:
embodiment 1
Step one:. the phenol after dehydration is with butyl (tetra) titanate in molar ratio for 4:1 mixes, and adopt synthesis under normal pressure distillation synthesis metatitanic acid phenyl ester, temperature of reaction is 150 DEG C, and the reaction times is 2 hours, distills out butanols, is separated and obtains metatitanic acid phenyl ester.
Step 2: metatitanic acid phenyl ester and methylcarbonate in molar ratio 1:4 mix, and react, reacts and carries out in closed reactor, and pressure is 5atm, and temperature of reaction is 150 DEG C, and the reaction times is 4 hours, obtains methyl benzol carbonate.
Step 3: products obtained therefrom methyl benzol carbonate carries out disproportionation reaction, adopt synthesis under normal pressure distil process, temperature of reaction is 180 DEG C, and catalyzer is metatitanic acid phenyl ester, and its content is 4wt%, and the reaction times is 4 hours, obtains diphenyl carbonate.
Step 4: step 2 reaction mixture is carried out decompression separation, finally obtains metatitanic acid methyl esters, is stoichiometrically mixed by metatitanic acid methyl esters with phenol, Reactive Synthesis metatitanic acid phenyl ester phenyl ester, adopt synthesis under normal pressure distil process to distill out methyl alcohol, temperature of reaction is 120 DEG C, results metatitanic acid phenyl ester.
embodiment 2
Step one:. the phenol after dehydration is with isopropyl titanate in molar ratio for 4:1 mixes, and adopt synthesis under normal pressure distillation synthesis metatitanic acid phenyl ester, temperature of reaction is 140 DEG C, and the reaction times is 3 hours, distills out butanols, is separated and obtains metatitanic acid phenyl ester.
Step 2: metatitanic acid phenyl ester and methylcarbonate in molar ratio 1:4 mix, and react, reacts and carries out in closed reactor, and pressure is 8atm, and temperature of reaction is 160 DEG C, and the reaction times is 4 hours, obtained methyl benzol carbonate.
Step 3: products obtained therefrom methyl benzol carbonate carries out disproportionation reaction, adopt synthesis under normal pressure distil process, temperature of reaction is 180 DEG C, and catalyzer is metatitanic acid phenyl ester, and its content is 4wt%, and the reaction times is 4 hours, prepares diphenyl carbonate.
Step 4: step 2 reaction mixture is carried out decompression separation, finally obtains metatitanic acid methyl esters, is stoichiometrically mixed by metatitanic acid methyl esters with phenol, Reactive Synthesis metatitanic acid phenyl ester phenyl ester, adopt synthesis under normal pressure distil process to distill out methyl alcohol, temperature of reaction is 120 DEG C, reclaims and obtains metatitanic acid phenyl ester.
embodiment 3
Step one:. the phenol after dehydration is with isopropyl titanate in molar ratio for 4:1 mixes, and adopt synthesis under normal pressure distillation synthesis metatitanic acid phenyl ester, temperature of reaction is 130 DEG C, and the reaction times is 3 hours, distills out butanols, is separated and obtains metatitanic acid phenyl ester.
Step 2: metatitanic acid phenyl ester and methylcarbonate in molar ratio 1:4 mix, and react, reacts and carries out in closed reactor, and pressure is 10atm, and temperature of reaction is 150 DEG C, and the reaction times is 4 hours, obtained methyl benzol carbonate.
Step 3: products obtained therefrom methyl benzol carbonate carries out disproportionation reaction, adopt synthesis under normal pressure distil process, temperature of reaction is 180 DEG C, and catalyzer is metatitanic acid phenyl ester, and its content is 4wt%, and the reaction times is 4 hours, prepares diphenyl carbonate.
Step 4: step 2 reaction mixture is carried out decompression separation, finally obtains metatitanic acid methyl esters, is stoichiometrically mixed by metatitanic acid methyl esters with phenol, Reactive Synthesis metatitanic acid phenyl ester phenyl ester, adopt synthesis under normal pressure distil process to distill out methyl alcohol, temperature of reaction is 120 DEG C, reclaims and obtains metatitanic acid phenyl ester.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (8)
1. a method for phenol and dimethyl carbonate synthesis diphenyl carbonate, is characterized in that, comprises following concrete steps:
Step one: under anhydrous and oxygen-free condition, has general formula (RO) by phenol and one or more
xthe organometallic compound of M or the mixing of anhydrous metal muriate, Reactive Synthesis phenoxy group metallic compound (C
6h
6o)
xm; Wherein M is Ti, Al, Fe or Pb, and x is 1 ~ 4, R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl;
Step 2: under anhydrous and oxygen-free condition, obtains methyl benzol carbonate by obtained phenoxy group metallic compound and dimethyl carbonate;
Step 3: obtained methyl benzol carbonate is carried out disproportionation reaction, obtained diphenyl carbonate;
Wherein, in described step 2, described reaction conditions controls in 1 ~ 10atm pressure and 130 ~ 180 DEG C of temperature.
2. method according to claim 1, is characterized in that, in described step one, adopts reaction distillation or rectificating method synthesis of phenoxy metallic compound (C
6h
6o)
xm.
3. method according to claim 1, is characterized in that, in described step 3, the disproportionation reaction of described methyl benzol carbonate is for adopting reaction distillation or rectification process, and temperature is 140 ~ 180 DEG C.
4. method according to claim 1, it is characterized in that, add catalyzer in disproportionation reaction described in step 3, described catalyzer is the compound of basic metal or cadmium, zirconium, lead, iron, copper, the compound of zinc or organo-tin compound or aluminium, titanium, vanadium.
5. method according to claim 4, is characterized in that, the phenoxy group metallic compound obtained in described step one in disproportionation reaction as catalyst application.
6. the method according to claim 4 or 5, is characterized in that, the consumption of described disproportionation reaction catalyzer is 0.1 ~ 10wt%.
7. method according to claim 1, is characterized in that, comprises the following steps:
Step one: under anhydrous and oxygen-free condition, by phenol with there is general formula (RO)
4the organic titanic compound mixing of Ti, and synthesis of phenoxy titanium (C
6h
6o)
4ti;
Step 2: under anhydrous and oxygen-free condition, by obtained phenoxy group metallic compound phenoxide titanium (C
6h
6o)
4ti and methylcarbonate, under 1 ~ 5atm pressure, temperature is react at 130 ~ 180 DEG C, obtained methyl benzol carbonate; Step 3: obtained methyl benzol carbonate is carried out disproportionation reaction, obtained diphenyl carbonate.
8. method according to claim 7, is characterized in that, the mol ratio of described phenol and organic titanic compound is more than or equal to 4:1.
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| CN106977401A (en) * | 2017-04-28 | 2017-07-25 | 濮阳市宏源石油化工有限公司 | Using ionic liquid as the method for accelerator diphenyl carbonate synthesis |
| CN109675623B (en) * | 2017-10-19 | 2021-05-11 | 中国石油化工股份有限公司 | Preparation and application of monodisperse catalyst for preparing diphenyl carbonate by ester exchange |
| CN109675630B (en) * | 2017-10-19 | 2021-03-26 | 中国石油化工股份有限公司 | Preparation and application of monodisperse solid catalyst for preparing diphenyl carbonate by ester exchange |
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Non-Patent Citations (2)
| Title |
|---|
| Ring-opening polymerization of ε-caprolactone initiated with titanium n-propoxide or titanium phenoxide;Julien Cayuela, et al.;《Macromolecules》;20060128;第39卷(第4期);第1338-1346页 * |
| 钛酸酯催化碳酸二甲酯与苯酚的酯交换反应;高俊杰等;《催化学报》;20010731;第22卷(第4期);第405-407页 * |
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