CN104447204B - A kind of method preparing glycol - Google Patents
A kind of method preparing glycol Download PDFInfo
- Publication number
- CN104447204B CN104447204B CN201310415242.2A CN201310415242A CN104447204B CN 104447204 B CN104447204 B CN 104447204B CN 201310415242 A CN201310415242 A CN 201310415242A CN 104447204 B CN104447204 B CN 104447204B
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- alkene
- glycol
- accordance
- reaction
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of is raw material with alkene, and with under a certain amount of oxygenant effect, the method for glycol is prepared in epoxidation generation epoxy compounds and then hydrolysis.The method adopts the TS-1 molecular sieve of supported rare earth metal oxide to be catalyzer.Detailed process is: in reaction vessel, add alkene and catalyzer, and in a certain amount of solvent, reaction at room temperature to 150 DEG C, it is 40%-85% that chromatogram records conversion of olefines rate, glycol selectivity 75%-90%.The involved in the present invention method preparing glycol, catalyst preparing is simple, and stability is high, and reaction conditions is comparatively gentle, and the selectivity of conversion of olefines rate and glycol is all higher.
Description
Technical field
The present invention relates to a kind of method preparing glycol, be specifically related to alkene epoxidation and generate the process that epoxy compounds and then hydrolysis prepare glycol.
Background technology
Dibasic alcohol is the important Chemicals of a class, has important using value.1,2-PD can be used as the raw material of unsaturated polyester resin, is also the raw material of softening agent, tensio-active agent, emulsifying agent and emulsion splitter, also can be used as mould inhibitor, fruit ripener, sanitas, frostproofer and tobacco humectant.Ethylene glycol can be used for producing vibrin, comprise fiber, film and engineering plastics, also directly can be used as refrigerant and frostproofer, be also produce the indispensable materials of product such as Synolac, softening agent, paint, tackiness agent, tensio-active agent, explosive and capacitor electrolyte simultaneously.
Epoxide is the intermediate of multiple Industrial products, is also the important source material of the field of fine chemical such as spices, pharmacy.Along with going deep into of molecular sieve research, Ti-Si zeolite (TS-1, Ti-β etc.), as a kind of selective oxidation catalytic material efficiently, the epoxidation of a lot of alkene can a step be completed, and reaction conditions is gentle,
Oxygenant is easy to get safely, there is no problem of environmental pollution, and wherein the epoxidation of propylene achieves industrialization, for the production of dibasic alcohol provides evolutionary path.
The people such as MasazumiTamura (Chem.Eur.J.2011,17,1142811431) report cerium dioxide can prepare acid amides by a kind of effective catalyst hydrolysis nitrile; Our research work (J.Am.Chem.Soc.2013,135,15061515) proves, cerium dioxide has certain acidity, can hydrolytic cleavage ether-oxygen bond.
Although be hydrolyzed about alkene epoxidation and epoxide and be seen in report more, alkene epoxidation is hydrolyzed a step, and to prepare the research of dibasic alcohol less.Therefore, development has bifunctional catalyzer and realizes a step and prepare the extensive concern that dibasic alcohol causes investigator.
Summary of the invention
Meaning of the present invention is to overcome the shortcoming prepared at present and exist in glycol process, as: preparation process is complicated, needs two steps to complete, reaction preference difference etc.The TS-1 catalyzer of this process rare-earth oxide load used, has epoxidation and hydrolysis property and preparation is simple, and stability is high, and transformation efficiency and selectivity are all higher.
A kind of glycol of the present invention's design prepares scheme, it is characterized in that: adopt the TS-1 molecular sieve of supported rare earth metal oxide as catalyzer, add alkene and catalyzer, in a solvent, obtain product glycol under oxygenant existence condition in reaction vessel.In the TS-1 molecular sieve of described supported rare earth metal oxide, rare-earth oxide is: lanthanum sesquioxide, cerous oxide, cerium dioxide, europiumsesquioxide, yttria; Preferably rare-earth oxide be cerium dioxide, europiumsesquioxide one or both; The charge capacity of metal oxide in catalyzer is: 1wt%-20wt%; Better charge capacity is: 5wt%-10wt%.
The preparation process of the TS-1 molecular sieve of described supported rare earth metal oxide is as follows: be immersed in by TS-1 in the soluble salt solutions containing rare earth metal, leaves standstill 3h-48h, roasting in drying, air atmosphere.The preparation of described TS-1 can adopt the one in hydrothermal synthesis method, microwave heating method, isomorphous substitution method, wherein Ti:Si (wt:wt)=0.5%-2.5%.
The described alkene added is: one or two or more kinds in propenyl chloride, butylene, amylene, hexene, tetrahydrobenzene, vinylbenzene; Preferably alkene is: one or two or more kinds in propenyl chloride, tetrahydrobenzene or vinylbenzene; Described oxygenant is: one or two or more kinds in hydrogen peroxide, tert-butyl hydroperoxide hydrogen oxide, carbamide peroxide, hydrogen phosphide cumene; Preferably oxygenant is: one or both in hydrogen peroxide and carbamide peroxide;
The mol ratio of the described alkene that adds and water is 10-1:1, described in the alkene that adds be 0.1-1molL in the concentration of solvent
-1; Catalyst levels is 0.05g (g substrate)
-1-0.5g (g substrate)
-1; The mol ratio of oxygenant and alkene is more than or equal to 1.Described temperature of reaction is room temperature to 150 DEG C, the reaction times be 1h-72h. preferably temperature of reaction be 50 DEG C-100 DEG C, the reaction times is 3h-24h; Described solvent is: the mixture of one or two or more kinds and water in acetone, acetonitrile, methyl alcohol, or pure water, the volume content 10-50% of water in mixture.
The separation of catalyzer can adopt filters or centrifugal, and catalyzer can be reused after roasting.
The present invention, compared with the anhydrous formaldehyde preparation technology of announcement, has following several advantage: 1, reaction conditions is comparatively gentle; The selectivity of 2, conversion of olefines rate and glycol is all higher; 3, this reaction adopts the TS-1 of rare earth oxide load as catalyzer, and material is easy to get, and preparation is simple, and stability is high.
Embodiment
In order to be further elaborated to the present invention, provide several concrete case study on implementation below, but the invention is not restricted to these embodiments.
Embodiment 1
7.3g tetraethoxy is slowly added drop-wise to 12.8mL tetrapropyl aqua ammonia (20% aqueous solution) with the solution of 20mL water; at room temperature dissolved with vigorous agitation is to clarification, after 0.13g tetrabutyl titanate is dissolved in 6mL Virahol, under nitrogen protection; slowly be added drop-wise in aforementioned colloidal sol, stir about 1h.Said mixture is added in synthesis reactor, sealing, lower 6h in 180 DEG C of baking ovens; After crystallization completes, quenching, deionized water is washed till neutrality repeatedly, and dry, 550 DEG C of roasting 8h, obtain TS-1, record its Ti:Si=1%.Be immersed in cerous nitrate solution, the TS-1 of obtained CeO 2 supporting, CeO 2 supporting amount is 5wt%.In reaction flask, add 2mmol propenyl chloride and 0.02g catalyzer, add 2mL acetone and 1mL water, at 60 DEG C, react 20h, it is 78% that chromatogram records propenyl chloride transformation efficiency, glycol selectivity 90%.
Embodiment 2
9.0g tetraethoxy is slowly added drop-wise to 16.0mL tetrapropyl aqua ammonia (20% aqueous solution) with the solution of 30mL water; at room temperature dissolved with vigorous agitation is to clarification, after 0.28g tetrabutyl titanate is dissolved in 10mL Virahol, under nitrogen protection; slowly be added drop-wise in aforementioned colloidal sol, stir about 1h.Said mixture is added in synthesis reactor, sealing, Microwave-assisted firing to 150 DEG C, keeps 3h; After having heated, quenching, deionized water is washed till neutrality repeatedly, and dry, 500 DEG C of roasting 4h, obtain TS-1, record its Ti:Si=1.8%.Be immersed in europium nitrate solution, evaporate to dryness at 100 DEG C, 500 DEG C of roasting 2h, the TS-1 of obtained europiumsesquioxide load, the charge capacity of europiumsesquioxide is 10wt%.In reaction flask, add 2mmol tetrahydrobenzene and 0.02g catalyzer, add 2mL acetonitrile and 1mL water, at 80 DEG C, react 24h, it is 60% that chromatogram records cyclohexene conversion rate, glycol selectivity 85%.
Embodiment 3
7.3g tetraethoxy is slowly added drop-wise to 12.8mL tetrapropyl aqua ammonia (20% aqueous solution) with the solution of 20mL water; at room temperature dissolved with vigorous agitation is to clarification, after 0.13g tetrabutyl titanate is dissolved in 6mL Virahol, under nitrogen protection; slowly be added drop-wise in aforementioned colloidal sol, stir about 1h.Said mixture is added in synthesis reactor, sealing, lower 6h in 180 DEG C of baking ovens; After crystallization completes, quenching, deionized water is washed till neutrality repeatedly, and dry, 550 DEG C of roasting 8h, obtain TS-1, record its Ti:Si=1%.Be immersed in lanthanum nitrate hexahydrate, the TS-1 of obtained titanium dioxide two lanthanum load, charge capacity is 5wt%.In reaction flask, add 2mmol propenyl chloride and 0.02g catalyzer, add 2mL acetone and 1mL water, at 60 DEG C, react 20h, it is 75% that chromatogram records propenyl chloride transformation efficiency, glycol selectivity 90%.
Embodiment 4
9.0g tetraethoxy is slowly added drop-wise to 16.0mL tetrapropyl aqua ammonia (20% aqueous solution) with the solution of 30mL water; at room temperature dissolved with vigorous agitation is to clarification, after 0.28g tetrabutyl titanate is dissolved in 10mL Virahol, under nitrogen protection; slowly be added drop-wise in aforementioned colloidal sol, stir about 1h.Said mixture is added in synthesis reactor, sealing, Microwave-assisted firing to 150 DEG C, keeps 3h; After having heated, quenching, deionized water is washed till neutrality repeatedly, and dry, 500 DEG C of roasting 4h, obtain TS-1, record its Ti:Si=1.8%.Be immersed in europium nitrate solution, evaporate to dryness at 100 DEG C, 500 DEG C of roasting 2h, the TS-1 of obtained europiumsesquioxide load, the charge capacity of europiumsesquioxide is 10wt%.In reaction flask, add 2mmol vinylbenzene alkene and 0.02g catalyzer, add 2mL acetone and 1mL water, at 80 DEG C, react 48h, it is 70% that chromatogram records cyclohexene conversion rate, glycol selectivity 89%.
Embodiment 5
10.6g tetraethoxy is slowly added drop-wise to 12.8mL tetrapropyl aqua ammonia (20% aqueous solution) with the solution of 20mL water; at room temperature dissolved with vigorous agitation is to clarification, after 0.42g tetrabutyl titanate is dissolved in 8mL Virahol, under nitrogen protection; slowly be added drop-wise in aforementioned colloidal sol, stir about 1h.Said mixture is added in synthesis reactor, sealing, lower 8h in 185 DEG C of baking ovens; After crystallization completes, quenching, deionized water is washed till neutrality repeatedly, and dry, 500 DEG C of roasting 5h, obtain TS-1, record its Ti:Si=2.1%.Be immersed in cerous nitrate solution, the TS-1 of obtained CeO 2 supporting, CeO 2 supporting amount is 2wt%.In reaction flask, add 2mmol propenyl chloride and 0.02g catalyzer, add 2mL acetone and 1mL water, at 80 DEG C, react 24h, it is 85% that chromatogram records propenyl chloride transformation efficiency, glycol selectivity 88%.
Embodiment 6
10.6g tetraethoxy is slowly added drop-wise to 12.8mL tetrapropyl aqua ammonia (20% aqueous solution) with the solution of 20mL water; at room temperature dissolved with vigorous agitation is to clarification, after 0.42g tetrabutyl titanate is dissolved in 8mL Virahol, under nitrogen protection; slowly be added drop-wise in aforementioned colloidal sol, stir about 1h.Said mixture is added in synthesis reactor, sealing, lower 8h in 185 DEG C of baking ovens; After crystallization completes, quenching, deionized water is washed till neutrality repeatedly, and dry, 500 DEG C of roasting 5h, obtain TS-1, record its Ti:Si=2.1%.Be immersed in cerous nitrate solution, the TS-1 of obtained CeO 2 supporting, CeO 2 supporting amount is 8wt%.In reaction flask, add 2mmol propenyl chloride and 0.02g catalyzer, add 3mL water, at 80 DEG C, react 24h, it is 80% that chromatogram records propenyl chloride transformation efficiency, glycol selectivity 78%.
Claims (9)
1. prepare a method for glycol, it is characterized in that:
Adopt the TS-1 molecular sieve of supported rare earth metal oxide as catalyzer, in reaction vessel, add alkene and catalyzer, in a solvent, under oxygenant existence condition, obtain product glycol;
Rare-earth oxide is: lanthanum sesquioxide, cerous oxide, cerium dioxide, europiumsesquioxide, yttria; The charge capacity of metal oxide in catalyzer is: 1wt% ~ 20wt%;
The described alkene added is: one or two or more kinds in propenyl chloride, butylene, amylene, hexene, tetrahydrobenzene, vinylbenzene;
Described oxygenant is: one or two or more kinds in hydrogen peroxide, tertbutyl peroxide, carbamide peroxide, hydrogen phosphide cumene;
Described temperature of reaction is room temperature to 150 DEG C, and the reaction times is 1h ~ 72h.
2. in accordance with the method for claim 1, it is characterized in that:
In the TS-1 molecular sieve of described supported rare earth metal oxide, preferably rare-earth oxide be cerium dioxide, europiumsesquioxide one or both; The better charge capacity of metal oxide in catalyzer is: 5wt% ~ 10wt%.
3. in accordance with the method for claim 1, it is characterized in that:
The preparation process of the TS-1 molecular sieve of described supported rare earth metal oxide is as follows: be immersed in by TS-1 in the soluble salt solutions containing rare earth metal, leaves standstill 3h ~ 48h, roasting in drying, air atmosphere.
4., according to the method described in claim 1,2 or 3, it is characterized in that:
The preparation of described TS-1 can adopt the one in hydrothermal synthesis method, microwave heating method, isomorphous substitution method, wherein Ti:Si=0.5wt% ~ 2.5wt%.
5. in accordance with the method for claim 1, it is characterized in that:
Preferably alkene is: one or two or more kinds in propenyl chloride, tetrahydrobenzene or vinylbenzene;
Preferably oxygenant is: one or both in hydrogen peroxide and carbamide peroxide.
6., according to the method described in claim 1 or 5, it is characterized in that:
The mol ratio of the described alkene that adds and water is 10 ~ 1:1, described in the alkene that adds be 0.1 ~ 1molL in the concentration of solvent
-1; Catalyst levels is 0.05g (g substrate)
-1~ 0.5g (g substrate)
-1; The mol ratio of oxygenant and alkene is more than or equal to 1.
7. in accordance with the method for claim 1, it is characterized in that:
Preferably temperature of reaction is 50 DEG C ~ 100 DEG C, and the reaction times is 3h ~ 24h.
8. in accordance with the method for claim 1, it is characterized in that:
The separation of catalyzer can adopt filters or centrifugal, and catalyzer can be reused after roasting.
9. in accordance with the method for claim 1, it is characterized in that:
Described solvent is: the mixture of one or two or more kinds and water in acetone, acetonitrile, methyl alcohol, or pure water, the volume content 10-50% of water in mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310415242.2A CN104447204B (en) | 2013-09-12 | 2013-09-12 | A kind of method preparing glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310415242.2A CN104447204B (en) | 2013-09-12 | 2013-09-12 | A kind of method preparing glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104447204A CN104447204A (en) | 2015-03-25 |
| CN104447204B true CN104447204B (en) | 2016-01-13 |
Family
ID=52894044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310415242.2A Expired - Fee Related CN104447204B (en) | 2013-09-12 | 2013-09-12 | A kind of method preparing glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104447204B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108002977B (en) * | 2018-01-15 | 2020-12-04 | 台州泰捷化工科技有限公司 | Method for coproducing chemical products dimethylbenzyl alcohol and 1, 2-pentanediol |
| CN109704921B (en) * | 2019-02-01 | 2022-01-04 | 淄博诺奥化工有限公司 | Economic and green preparation method of vicinal dihydric alcohol |
| CN113058643B (en) * | 2021-03-29 | 2021-12-21 | 北京化工大学 | Modified TS-1 molecular sieve composite catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923777A (en) * | 2005-08-31 | 2007-03-07 | 中国科学院大连化学物理研究所 | Preparation method of 1,2-aliphatic glycol |
| CN102942451A (en) * | 2012-12-10 | 2013-02-27 | 扬州大学 | Method for preparing 1,2-diol from oxyalkylene under catalytic action of seleniferous high polymers |
| CN103168017A (en) * | 2010-10-19 | 2013-06-19 | 国际壳牌研究有限公司 | Process for the production of alkylene glycol |
-
2013
- 2013-09-12 CN CN201310415242.2A patent/CN104447204B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923777A (en) * | 2005-08-31 | 2007-03-07 | 中国科学院大连化学物理研究所 | Preparation method of 1,2-aliphatic glycol |
| CN103168017A (en) * | 2010-10-19 | 2013-06-19 | 国际壳牌研究有限公司 | Process for the production of alkylene glycol |
| CN102942451A (en) * | 2012-12-10 | 2013-02-27 | 扬州大学 | Method for preparing 1,2-diol from oxyalkylene under catalytic action of seleniferous high polymers |
Non-Patent Citations (1)
| Title |
|---|
| "Heterogeneous Ceria Catalyst with Water-Tolerant Lewis Acidic Sites for One-Pot Synthesis of 1,3-Diols via Prins Condensation and Hydrolysis Reactions";Yehong Wang et al.;《J. Am. Chem. Soc.》;20130111;第135卷;1506-1515 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104447204A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101239907B (en) | Method for preparing glycol methyl ether acetate | |
| CN101492528B (en) | Method for synthesis of alicyclic epoxy resin with catalysis of solid supported heteropoly acid catalyst | |
| CN103420424B (en) | Preparation of rod-shaped nano tungsten trioxide and technology of catalytic synthesis of adipic acid therethrough | |
| CN101485990B (en) | Solid supported heteropoly acid catalyst and preparation method thereof | |
| CN105562041A (en) | Preparation method of solid alkali catalyst and reaction method for catalytic synthesis of ionone fragrance intermediate by solid alkali catalyst | |
| CN104447204B (en) | A kind of method preparing glycol | |
| CN102126953A (en) | Preparation method of nonanal and methyl formylcaprylate | |
| CN107814939B (en) | Method for synthesizing poly (ethylene glycol methyl phosphonate) by metal oxide catalysis | |
| CN103664557B (en) | Method for preparing cyclopentanone by oxidation of cyclopentene | |
| CN110152733B (en) | Catalyst, preparation method thereof and application of catalyst in catalyzing reaction of glycerol and urea | |
| CN110078702A (en) | A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate | |
| CN103864572B (en) | A kind of method preparing glycol | |
| CN103316696B (en) | Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method | |
| CN106944050B (en) | A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol | |
| CN104326915A (en) | Method for synthesizing ethyl p-hydroxybenzoate through catalysis of modified metal oxide type solid super acid | |
| CN104447672A (en) | Method for synthesizing epsilon-caprolactone by using active carbon immobilized heteropoly acid | |
| CN102755910B (en) | Titanium silicon molecular sieve and resin composite modified catalyst and preparation method thereof | |
| CN106588819B (en) | A kind of preparation method of highly selective epoxypinane | |
| CN101972655A (en) | Olefin epoxidized catalyst and preparation method and application thereof | |
| CN101966465B (en) | Molecular sieve catalyst for use in preparation of isopulegol | |
| CN104649287A (en) | Synthetic method of Ti-SBA-15 molecular sieve | |
| CN104230708A (en) | Preparation method of methyl formate | |
| CN107602516B (en) | Method for synthesizing delta-cyclopentanolide under catalysis of amino acid ionic liquid | |
| CN111393397B (en) | Preparation method of 2, 5-furandicarboxylic acid | |
| CN115007156B (en) | Calcium-cobalt composite oxide catalyst, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| 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: 20160113 Termination date: 20180912 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |