CN103819527B - The preparation method of tea saponin decylate tensio-active agent and product - Google Patents
The preparation method of tea saponin decylate tensio-active agent and product Download PDFInfo
- Publication number
- CN103819527B CN103819527B CN201410053604.2A CN201410053604A CN103819527B CN 103819527 B CN103819527 B CN 103819527B CN 201410053604 A CN201410053604 A CN 201410053604A CN 103819527 B CN103819527 B CN 103819527B
- Authority
- CN
- China
- Prior art keywords
- tea saponin
- decylate
- tensio
- active agent
- preparation
- 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
Landscapes
- Steroid Compounds (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of tea saponin decylate tensio-active agent, comprising: catalyzer, tea saponin and capric acid acyl chlorides are joined in organic solvent, carries out esterification, until react completely; Aftertreatment obtains tea saponin decylate tensio-active agent.Present invention also offers a kind of tensio-active agent prepared by above-mentioned preparation method.Preparation technology of the present invention is simple, and environmental friendliness, the tea saponin decylate tensio-active agent prepared by the method has better surfactivity, has good market outlook.
Description
Technical field
The present invention relates to tensio-active agent preparing technical field, specifically relate to a kind of preparation method and product of tea saponin decylate tensio-active agent.
Background technology
Tensio-active agent has the performances such as dispersion, infiltration, solubilising, foaming, and be widely used in the fields such as food, medicine, agricultural chemicals, daily use chemicals, ore dressing, oil field, its kind and consumption increase day by day.But people use the tensio-active agent of synthetic for a long time always, larger threat is existed to HUMAN HEALTH and environment.The tensio-active agent of nontoxic, easy degraded is more and more subject to people and payes attention to.Carboxylate surface active agent synthesizes by natural matter, readily biodegradable, is subject to people's favor always.But common carboxylate anion's tensio-active agent is deposited and is unstable under acidic conditionly even lost the defects such as surfactivity.
Tea saponin has another name called theasaponin, is a class Triterpenoids sapogenins saponins compound, is made up of sapogenin, sugared body and organic acid three part, is extensively present in the root of plant of theaceae, stem, leaf, flower, fruit.Tea saponin is a kind of natural surface active agent of good performance; it can be widely used in the fields such as light industry, chemical industry, agricultural chemicals, feed, cultivation, weaving, oil recovery, mining, building materials and expressway construction, for the manufacture of emulsifying agent, cleaning agent, inert ingredient, fodder additives, crab shrimp aquaculture protective material, textile auxiliary agent, oilfield foaming agent, mining flotation agent and gas concrete suds-stabilizing agent and concrete admixture-frostproofer etc.The tea seed output of China occupies first place in the world, and extract in the by-product oil leached tea oil slag after tea oil, the content of tea saponin can reach about 10%, fully advances the deep processing of tea saponin, to comprehensive utilization oil tea resource, has very important social benefit and economic worth.
Tea saponin is natural nonionogenic tenside of good performance, and it has and reduces the surface tension of water, emulsification, dispersion, the performance such as wetting, and the emulsion particle formed is little, is evenly distributed, good stability; In addition, tea saponin has stronger latherability, and foam stability can be good.There is a large amount of hydroxyl etc. can modification group in tea saponin molecule, expand its range of application by chemical modification, overcome the deficiency in tea saponin use procedure.At present the research of tea saponin chemical modification is also got more and more.Such as, application publication number is the preparation method disclosing a kind of theasaponin high-grade aliphatic ester in the patent documentation of CN102030806A, in the presence of a catalyst, theasaponin is mixed with high fatty alcohol, reacts, after separating catalyst, obtain theasaponin high-grade fatty ester.Application publication number is the preparation method disclosing a kind of theasaponin derivative in the patent documentation of CN102030803A, is prepared from by following steps: (1) gets triphenylmethyl chloride and theasaponin reacts; Then, bromobenzyl is added and theasaponin reacts; (2) get phosphorus tribromide to react with sugar; React with bromobenzyl again; (3) get theasaponin that step (1) prepares and the sugar mixing that step (2) prepares, then add trityl deprotection agent, reaction; Then, in the presence of a catalyst, add benzyl deprotection agent, reaction, obtains theasaponin derivative.
But above-mentioned two kinds of method of modifying for tea saponin, all there is respective defect: in such as method disclosed in CN102030806A, the catalyzer adopted is N, the mixture of N-dicyclohexylcarbodiimide and 4-dimethylamino pyridine, N on the one hand, N-dicyclohexylcarbodiimide has pungency to skin and eyes, larger to the health threat of field staff; On the other hand, N, N-dicyclohexylcarbodiimide is expensive, and the cost preparing theasaponin high-grade aliphatic ester is higher, is unsuitable for industrial mass production.In CN102030803A in open method, not only high pungency and highly toxic bromobenzyl, phosphorus tribromide, and technique is comparatively complicated, and preparation cost is higher, industrialization is very difficult, and the modified surface active's agent prepared cannot meet the multiple demand of current Surfactant.Therefore, a kind of multi-functional, eco-friendly tensio-active agent of exploitation, has great importance.
Summary of the invention
The invention provides a kind of preparation method of tea saponin decylate tensio-active agent, the method preparation technology is simple, environmental friendliness, the tea saponin decylate tensio-active agent prepared by the method has higher surfactivity, be suitable for using as solubilizing agent and emulsifying agent, and reaction conditions is easy to control, and can be used for suitability for industrialized production.
A preparation method for tea saponin decylate tensio-active agent, comprising: join in organic solvent by catalyzer, tea saponin and capric acid acyl chlorides, carry out esterification, and after having reacted, aftertreatment obtains tea saponin decylate tensio-active agent.
For realizing the separation of final product tea saponin decylate, can select multiple post-treating method, for ease of operation, as the preferred technical scheme of one, described post-treating method comprises:
(1) macroporous resin is joined esterification complete after reaction system in, utilize macroporous resin adsorption tea saponin decylate wherein, after having adsorbed, filter obtain the macroporous resin being adsorbed with tea saponin decylate;
(2) macroporous resin being adsorbed with tea saponin decylate is dissolved in parsing agent, carries out parsing reaction, filter, remove the solvent in desorbed solution, obtain tea saponin decylate tensio-active agent.
For removing unreacted capric acid acyl chlorides, improving the purity of the tea saponin decylate tensio-active agent finally obtained, can select by the pH value in regulation system, the product in system is separated; As preferably, before adding macroporous resin, the reaction solution acidifying after esterification being completed can be adopted, the pH value of adjustment reaction solution is less than 4 or 4, remove unreacted capric acid acyl chlorides with sherwood oil and ethyl acetate mixed extractant solvent with the form of capric acid, and then carry out above-mentioned process with macroporous resin.
At least one in an acidic catalyst that described catalyzer can select esterification to commonly use or basic catalyst; Conventional an acidic catalyst can select mineral acid or organic acid, such as can select dilute hydrochloric acid, dilute sulphuric acid, acetic acid etc., conventional basic catalyst can select mineral alkali or organic bases, such as mineral alkali can select salt of wormwood, sodium carbonate, sodium hydroxide, sodium alkoxide etc., and organic bases can select triethylamine, pyridine or diethylamine etc.
Described organic solvent can be selected multiplely has better deliquescent solvent to reaction substrate, and for ease of carrying out fast of reaction, preferred organic solvent comprises at least one in DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO), acetone etc.
The temperature of described esterification can be carried out at normal temperatures, also can suitably heat.For ease of controlling, the temperature of described esterification is preferably 20-30 degree Celsius, and temperature too high easily causing, side reaction occurred, and hot conditions can increase preparation cost and control difficulty.The reaction times of esterification is different according to the difference of real reaction substrate, can determine according to actual needs.
The decanoyl chloride added and the molar weight of catalyzer can be determined according to actual needs, by controlling the two add-on, change the substitution value of carboxyl on tea saponin, obtain the modification tea saponin esterification products of partial esterification or all esterifications, to meet different use occasion demands.For avoiding wastage of material, reduce the preparation cost of tea saponin decylate tensio-active agent, the mol ratio that described tea saponin, decanoyl chloride and catalyzer add is preferably 1:0.5-50:0.5-50.For further conservation, as preferred further, the mol ratio that described tea saponin, decanoyl chloride and catalyzer add is preferably 1:1-15:1-15, under normal temperature state, when tea saponin and decanoyl chloride mol ratio reach about 1:20, the hydroxyl primitive reaction that activity on tea saponin is higher is complete, so more preferably 1:5-8:10-20 again.
Macroporous resin is also known as full porous resin, be prepared from through polyreaction by additives such as polymerization single polymerization monomer and linking agent, pore-creating agent, dispersion agents, after polymer formation, pore-creating agent is removed, and leaves hole that is big and small, different, that interpenetrate in resin.Therefore macroporous resin has higher porosity in its inside in the dry state, and aperture is comparatively large, between 100 ~ 1000nm.For improving macroporous resin to the adsorption efficiency of target product, in last handling process, macroporous resin generally selects nonpolar macroporous resin.Preferred nonpolar macroporous resin comprises AB-8 type macroporous resin, the tea saponin decylate that the alternative absorption reaction of AB-8 type macroporous resin obtains, and subsequent solves process efficiency is high, easily controls.The quality needs of the macropore resin added are determined according to actual adsorption effect, generally to be as the criterion, the tea saponin decylate absorption in system by TLC Real-Time Monitoring in adsorption process, until adsorbed completely.When the concentration of the reaction solution of esterification is higher, before adding macropore resin, the concentration by adding the reaction solution that esterification obtains by water does suitably dilution, so that the uniform adsorption of macropore resin, prevent due to excessive concentration, cause impurity synchronously to be adsorbed.In in last handling process, described adsorption temp is generally 20-35 degree Celsius, can adjust according to physical condition.
In last handling process, described resolution temperature can select normal temperature, also can suitably heat, and for ease of controlling, preferred resolution temperature is 20-40 degree Celsius.The parsing time can be determined according to practical situation, resolves completely be as the criterion with modification tea saponin.In last handling process, resolve agent to need to select, to tea saponin esterification products, there is better deliquescent neat solvent or mixed solvent, according to the characteristic of tea saponin esterification products itself, such as can adopt alcoholic solvent or acetone and their aqueous solution etc., preferred parsing agent is aqueous ethanolic solution, at least one in methanol aqueous solution or aqueous acetone solution, aqueous ethanolic solution, methanol aqueous solution, aqueous acetone solution all has higher avidity to polar group and non-polar group, as further preferred, in described parsing agent, the concentration of solute is 50-95%, when selecting the parsing agent of this concentration, the analyzing efficiency of modification tea saponin is higher, simultaneously compared with the pure parsing agent of employing, reduce and resolve the use cost of agent and the pollution to environment.The consumption of resolving agent is generally the 2-4 of the macroporous resin volume being adsorbed with tea saponin decylate doubly, so that the thorough parsing of tea saponin esterification products.
Present invention also offers a kind of tea saponin decylate tensio-active agent prepared by aforesaid method, the nontoxic easy degraded of this tensio-active agent, by carrying out structure of modification to tea saponin, change the part or all of hydroxyl in tea saponin molecule glycosyl into ester group, tea saponin decylate tensio-active agent of the present invention is made to have the characteristic of nonionogenic tenside and anion surfactant concurrently, overcome the defect of common carboxylate anion's tensio-active agent surfactivity difference in acid condition, the effect also reaching foaming or froth breaking by changing the pH value of solution meets the requirement of different industries.
Raw material of the present invention or reagent etc. all can adopt commercial products.Reaction process or last handling process, when not having specified otherwise, all can adopt and at room temperature carry out.
The present invention has the following advantages and effect relative to prior art tool:
(1) tea saponin decylate tensio-active agent of the present invention, has surfactivity more better than tea saponin, has good solubilising and emulsifying effectiveness.
(2) tea saponin decylate surface active agent of the present invention, from natural matter, nontoxic, easily degrades.
(3) preparation technology of the present invention is simple, and reaction conditions is easy to control, and can be used for suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
By tea saponin 1mmol, capric acid acyl chlorides 6mmol, Anhydrous potassium carbonate 12mmol joins 10mlN, in dinethylformamide, 25 degrees Celsius of lower stirring reactions 12 hours.After reaction terminates, in reaction solution, add the dilution of 10ml water, add 0.1N dilute hydrochloric acid, the pH value of reaction solution is adjusted to 4-5, utilize 10ml sherwood oil and ethyl acetate mixed solvent (volume ratio is 1:2) to extract three times, removing capric acid; Add AB-8 type macroporous resin absorption tea saponin decylate, the absorption at room temperature time is 5 hours, and TLC detects until absorption is complete.Suction filtration removing adsorption liquid, the aqueous ethanolic solution adding 80% of 2 times of volumes in the AB-8 type macroporous adsorbent resin being adsorbed with tea saponin decylate resolves tea saponin esterification products, cross the AB-8 type macroporous resin after filtering parsing, rotary evaporation concentrates desorbed solution, then obtains solid tea saponin decylate tensio-active agent through vacuum lyophilization.
Product infared spectrum shows, 1725-1659cm
-1the obvious grow of absorption peak at place, illustrates and introduces C=O base, 1300-1000cm
-1absorption peak in scope is that the stretching vibration of C-O key causes, and 950-900cm-1 is that outside-OH the face on carboxyl, formation vibration is formed.In sum, can judge that capric acid group has been received on tea saponin molecule, product is the tea saponin decylate tensio-active agent that capric acid group replaces.
Embodiment 2
By tea saponin 1mmol, capric acid acyl chlorides 5mmol, anhydrous sodium carbonate 10mmol join in 10ml dimethyl sulfoxide (DMSO), 30 degrees Celsius of lower stirring reactions 12 hours.After reaction terminates, in reaction solution, add the dilution of 10ml water, add 0.1N dilute hydrochloric acid, the pH value of reaction solution is adjusted to 4-5, utilize 10ml sherwood oil and ethyl acetate mixed solvent (volume ratio is 1:2) to extract three times, removing capric acid; Add AB-8 type macroporous resin absorption tea saponin decylate, the absorption at room temperature time is 5 hours, and TLC detects until absorption is complete.Suction filtration removing adsorption liquid, the aqueous acetone solution adding 90% of 2 times of volumes in the AB-8 type macroporous adsorbent resin being adsorbed with tea saponin decylate resolves tea saponin esterification products, cross the AB-8 type macroporous resin after filtering parsing, rotary evaporation concentrates desorbed solution, then obtains solid tea saponin decylate tensio-active agent through vacuum lyophilization.Infrared detection data consistent with Example 1.
Embodiment 3
By tea saponin 1mmol, capric acid acyl chlorides 6mmol, joins in 10ml acetone without water sodium hydroxide 12mmol, 20 degrees Celsius of lower stirring reactions 12 hours.After reaction terminates, in reaction solution, add the dilution of 10ml water, add 0.1N dilute hydrochloric acid, the pH value of reaction solution is adjusted to 4-5, utilize 10ml sherwood oil and ethyl acetate mixed solvent (volume ratio is 1:1) to extract three times, removing capric acid; Add AB-8 type macroporous resin absorption tea saponin decylate, the absorption at room temperature time is 5 hours, and TLC detects until absorption is complete.Suction filtration removing adsorption liquid, the methanol aqueous solution adding 60% of 2 times of volumes in the AB-8 type macroporous adsorbent resin being adsorbed with tea saponin decylate resolves tea saponin esterification products, cross the AB-8 type macroporous resin after filtering parsing, rotary evaporation concentrates desorbed solution, then obtains solid tea saponin decylate tensio-active agent through vacuum lyophilization.Infrared detection data consistent with Example 1.
Embodiment 4
By tea saponin 1mmol, capric acid acyl chlorides 8mmol, Anhydrous potassium carbonate 16mmol joins 10mlN, in dinethylformamide, 25 degrees Celsius of lower stirring reactions 12 hours.After reaction terminates, in reaction solution, add the dilution of 10ml water, in system, add the dilute hydrochloric acid of 0.1N, the pH value of regulation system liquid is 4-5, utilizes 10ml sherwood oil and ethyl acetate mixed solvent (volume ratio is 1:2) to extract three times, removing unreacted capric acid; Then in system liquid, add AB-8 type macroporous resin absorption tea saponin decylate, 40 degrees Celsius of lower adsorption times are 3 hours, and TLC detects until absorption is complete.Suction filtration removing adsorption liquid, the aqueous ethanolic solution adding 80% of 2 times of volumes in the AB-8 type macroporous adsorbent resin being adsorbed with tea saponin decylate resolves tea saponin esterification products, cross the AB-8 type macroporous resin after filtering parsing, rotary evaporation concentrates desorbed solution, then obtains solid tea saponin decylate tensio-active agent through vacuum lyophilization.Infrared detection data consistent with Example 1.
Surfactivity is tested:
Adopt adopting platinum plate method to measure the micelle-forming concentration (cmc) of the target product utilizing embodiment 1 ~ 4 to prepare at 20 DEG C, the results are shown in Table shown in 1.
Table 1
| Embodiment | Micelle-forming concentration (cmc), unit: g/L |
| 1 | 0.05 |
| 2 | 0.06 |
| 3 | 0.04 |
| 4 | 0.03 |
From the detected result of table 1, the tea saponin decylate tensio-active agent prepared by method of the present invention, improve about 10 times than corresponding tea saponin (cmc=0.5g/L) activity, activity is higher, is suitable for using as solubilizing agent and emulsifying agent.
Claims (6)
1. a preparation method for tea saponin decylate tensio-active agent, comprising: join in organic solvent by catalyzer, tea saponin and capric acid acyl chlorides, carry out esterification, and after having reacted, aftertreatment obtains tea saponin decylate tensio-active agent; Described catalyzer is at least one in salt of wormwood, sodium carbonate, sodium hydroxide; The temperature of described esterification is 20-30 degree Celsius; The mol ratio of described tea saponin, capric acid acyl chlorides and catalyzer is 1:5-8:10-20.
2. the preparation method of tea saponin decylate tensio-active agent according to claim 1, it is characterized in that, described post-treating method comprises:
(1) macroporous resin is joined esterification complete after reaction system in, utilize macroporous resin adsorption tea saponin decylate wherein, after having adsorbed, filter obtain the macroporous resin being adsorbed with tea saponin decylate;
(2) macroporous resin being adsorbed with tea saponin decylate is dissolved in parsing agent, carries out parsing reaction, filter, remove the solvent in desorbed solution, obtain tea saponin decylate tensio-active agent.
3. the preparation method of tea saponin decylate tensio-active agent according to claim 2, is characterized in that, described parsing agent is at least one in aqueous ethanolic solution, methanol aqueous solution, aqueous acetone solution.
4. the preparation method of tea saponin decylate tensio-active agent according to claim 2, it is characterized in that, in described parsing agent, the concentration of solute is 50-95%, and the consumption of described parsing agent is 2-4 times of the macroporous resin volume being adsorbed with tea saponin decylate.
5. the preparation method of tea saponin decylate tensio-active agent according to claim 1, it is characterized in that, described organic solvent comprises at least one in DMF, dimethyl sulfoxide (DMSO), acetone.
6. a tea saponin decylate tensio-active agent, is characterized in that, is prepared by the preparation method of the tea saponin decylate tensio-active agent described in the arbitrary claim of claim 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410053604.2A CN103819527B (en) | 2014-02-17 | 2014-02-17 | The preparation method of tea saponin decylate tensio-active agent and product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410053604.2A CN103819527B (en) | 2014-02-17 | 2014-02-17 | The preparation method of tea saponin decylate tensio-active agent and product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103819527A CN103819527A (en) | 2014-05-28 |
| CN103819527B true CN103819527B (en) | 2016-01-06 |
Family
ID=50754855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410053604.2A Expired - Fee Related CN103819527B (en) | 2014-02-17 | 2014-02-17 | The preparation method of tea saponin decylate tensio-active agent and product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103819527B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106858044A (en) * | 2016-12-29 | 2017-06-20 | 叶大仝 | A kind of nutrition equilibrium high conversion rate dinodon rufozonatum snake special feed |
| CN106858073A (en) * | 2016-12-29 | 2017-06-20 | 叶大仝 | A kind of high conversion rate snake feed easy to digest |
| CN106819416A (en) * | 2016-12-29 | 2017-06-13 | 叶大仝 | A kind of low-cost nutrition equilibrium snake special feed |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030806A (en) * | 2010-10-21 | 2011-04-27 | 华南理工大学 | Tea saponin high-grade fatty ester as well as preparation method and application thereof |
| CN102731608A (en) * | 2012-06-29 | 2012-10-17 | 浙江大学 | Preparation method of tea saponin ester succinate surfactant and product thereof |
-
2014
- 2014-02-17 CN CN201410053604.2A patent/CN103819527B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030806A (en) * | 2010-10-21 | 2011-04-27 | 华南理工大学 | Tea saponin high-grade fatty ester as well as preparation method and application thereof |
| CN102731608A (en) * | 2012-06-29 | 2012-10-17 | 浙江大学 | Preparation method of tea saponin ester succinate surfactant and product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103819527A (en) | 2014-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103804462B (en) | The preparation method of tea saponin laurate tensio-active agent and product | |
| CN102731608B (en) | Preparation method of tea saponin ester succinate surfactant and product thereof | |
| CN103804461B (en) | The preparation method of tea saponin sulfuric acid ester surfactant and product | |
| CN104372045B (en) | A kind of preparation method of high-purity sulforaphane | |
| CN103819527B (en) | The preparation method of tea saponin decylate tensio-active agent and product | |
| CN103224968B (en) | Method for preparing neohesperidin by enzymic method | |
| CN105578883A (en) | Modulation of plant immune system function | |
| CN109651480A (en) | A method of separation momordica glycoside V | |
| CN103804460B (en) | The preparation method of tea saponin tetradecanoic acid ester surfactant and product | |
| EP3397066B1 (en) | Process for separating proteins from biomass materials | |
| CN104876824A (en) | Technology for separation and purification of chlorogenic acid from coffee beans | |
| CN103819526B (en) | The preparation method of tea saponin stearate tensio-active agent and product | |
| CN104672291A (en) | Preparation method of gallate phytosterol ester | |
| CN104478706A (en) | Method for preparing steviol | |
| CN104031109B (en) | A kind of method of fermentable purifying tea saponin | |
| CN103804463B (en) | The preparation method of tea saponin octanoate tensio-active agent and product | |
| CN103819528B (en) | The preparation method of tea saponin cetylate tensio-active agent and product | |
| CN103275151B (en) | A kind of process for purification of Matachrom | |
| JP6728051B2 (en) | Method of removing geniposide, genipin, or both | |
| CN108997359B (en) | Method for extracting chlorophyll from stevioside production waste residues | |
| CN104711307B (en) | A kind of method of shaddock agricultural wastes resource higher value application | |
| CN104357527B (en) | A kind of method that microbe fermentation method extracts Tea Saponin from leached tea oil slag | |
| CN111214800A (en) | Novel high-molecular water-based extinguishing agent and preparation method thereof | |
| CN105001284B (en) | A kind of purple spring wheat wheat bran anthocyanin extracting method | |
| CN106432521A (en) | Preparation method of phosphate esterification bletilla striata polysaccharide |
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: 20160106 Termination date: 20170217 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |