CN103922923A - Industrial production method of 2-(4-methoxyphenoxy)sodium propionate - Google Patents
Industrial production method of 2-(4-methoxyphenoxy)sodium propionate Download PDFInfo
- Publication number
- CN103922923A CN103922923A CN201410110984.9A CN201410110984A CN103922923A CN 103922923 A CN103922923 A CN 103922923A CN 201410110984 A CN201410110984 A CN 201410110984A CN 103922923 A CN103922923 A CN 103922923A
- Authority
- CN
- China
- Prior art keywords
- methoxyphenoxy
- sodium propionate
- preparing process
- sodium
- industrialized preparing
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
Abstract
The invention relates to the technical field of a preparation method of a compound, and especially relates to an industrial production method of a sweetness inhibitor 2-(4-methoxyphenoxy)sodium propionate. The method comprises the following steps: taking methoxyphenol and methyl 2-chloropropionate as raw materials, under the effect of sodium hydroxide and a catalyst, taking water as a solvent, reacting for 6-24 hours at the temperature of 60-90 DEG C to obtain the product 2-(4-methoxyphenoxy)propionic acid; placing the 2-(4-methoxyphenoxy)propionic acid and sodium hydroxide in ethanol, heating, and reacting to obtain 2-(4-methoxyphenoxy)sodium propionate. According to the invention, water is taken as a solvent, the impurity in the generated product can be effectively removed, the synthesis and purification treatment processes are simple, the purity of the product is high, and the industrial production method is suitable for industrial production of 2-(4-methoxyphenoxy)sodium propionate.
Description
Technical field
The present invention relates to the preparing technical field of compound, relate in particular to a kind of 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate.
Background technology
Sugar has very important effect in field of food, it not only can be used as sweeting agent, can also be as anticorrosion, fresh-keeping, expansion, hyperchromic, flavouring, dispersion, loose, bonding sizing etc., have exquisiteness, lubricated mouthfeel characteristic, be a kind of indispensable basic raw material in food-processing.When some food lacks sugar, its matter structure variation, and the quality guaranteed period greatly shorten; But when sugar degree is higher, had again sweet excessively greasy sensation, and affected the mouthfeel of food, and the appearance of sweetness inhibitor has solved the problem of " crossing sweet excessively greasy " just.
2-(4-methoxyphenoxy) Sodium Propionate is a kind of in sweetness inhibitor, is a kind of crude substance being present in coffee berry, and its sterling crystal powder shape that is white in color is tasteless; Be heated and baking in process, even also very stable under low pH value condition, in shelf life of products, its property retention that suppresses sugariness is constant.1987, U.S.'s seasonings and association of production of flavor manufacturer were to 2-(4-methoxyphenoxy) application of Sodium Propionate in dessert, candy, preserved fruit and frosting assess, and result shows it is " generally recognized as safe material ".But natural 2-(4-methoxyphenoxy) Sodium Propionate purifying technique is complicated, and purification cost of material is higher, both at home and abroad the chemical preparation process of this material is studied for this reason, US Patent No. 4,544,565 have designed the preparation method of this kind of material, but the method productive rate is low, and the product purity obtaining is low, be difficult to reach the standard of using as foodstuff additive; Chinese patent CN200910273148.1 sweetness inhibitor 2-(4-methoxyphenoxy) synthetic method of Sodium Propionate, take p methoxy phenol and 2-chloropropionate is raw material, adopting dehydrated alcohol to make solvent synthesizes, the method purification step is complicated, energy consumption is high, and production cost is high, is unfavorable for suitability for industrialized production.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the object of the present invention is to provide that a kind of reaction conditions is gentle, synthetic and purifying process is simple, cost is low and applicable scale operation 2-(4-methoxyphenoxy) industrial method of Sodium Propionate.
To achieve these goals, technical scheme of the present invention is as follows:
2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate, it comprises the steps:
(1) by p methoxy phenol, sodium hydroxide, catalyzer, water, be 1:(1～3 in mass ratio): (0.01～0.03): the ratio mix and blend of (3～20), heating is increased to after 60 ℃～70 ℃ the temperature of mixture, dropping is with respect to the 2-methyl chloropropionate of 1～2 times of amount of quality of p methoxy phenol, and reaction obtains product 2-(4-methoxyphenoxy) propionic acid;
(2) by 2-(4-methoxyphenoxy) propionic acid, sodium hydroxide be 1:(1～1.1 according to mol ratio) put in organic solvent, heating for dissolving makes it reaction, obtains 2-(4-methoxyphenoxy) Sodium Propionate.
Preferably, described organic solvent is a kind of in methyl alcohol, ethanol, acetone or the trimethyl carbinol.
Preferably, the consumption of described organic solvent is 2-(4-methoxyphenoxy) 5～10 times of propionic acid quality.
Preferably, after described step (1), also comprising described product 2-(4-methoxyphenoxy) propionic acid carries out purification processes, be specially: reacted mixed solution is acid with sulphuric acid soln furnishing, cooling, centrifugal, obtains purer 2-(4-methoxyphenoxy) propionic acid; Take after the reaction that water is solvent, directly reaction product is regulated to pH value, to reach the object of purified reaction product, this process operation is simple, and cost is lower.
Preferably, the mass concentration of described sulphuric acid soln is 30%～50%.
Preferably, after described step (2), also comprise described 2-(4-methoxyphenoxy) purification of Sodium Propionate, its concrete technology is recrystallization.
Preferably, described catalyzer is potassiumiodide or sodium iodide.
Preferably, the temperature of the described reaction in described step 1 is 60 ℃～90 ℃, and the time of described reaction is 6～24 hours.
Preferably, the temperature of the described heating for dissolving in described step (2) is 70 ℃～80 ℃.
Product 2-(4-methoxyphenoxy of the present invention) structural formula of compound of Sodium Propionate following (I):
It is by p methoxy phenol (II) and 2-methyl propionate (III) under catalyst action, synthetic in water; Under alkaline condition, in organic solvent, recrystallization makes subsequently.
Its reaction formula is as follows:
The present invention adopts water to make solvent, in water, reacts, and does not use any organic solvent in this reaction, has saved cost, is also conducive to the purification processes of product simultaneously, and this reaction conditions is gentle, and technique is simple; At the direct crystallisation by cooling in organic solvent of end reaction after product, saved product extraction, the technique such as concentrated, and product purity is high, can reach the standard of using as foodstuff additive; The present invention has simplified production process, has reduced energy consumption in a word, is applicable to large-scale industrial production 2-(4-methoxyphenoxy) Sodium Propionate.
Accompanying drawing explanation
Fig. 1 .2-(4-methoxyphenoxy) HPLC of Sodium Propionate standard substance figure;
Fig. 2. the 2-(4-methoxyphenoxy that the present invention is synthetic) the HPLC figure of Sodium Propionate.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Embodiment 1
Sweetness inhibitor 2-(4-methoxyphenoxy) industrialized preparing process for Sodium Propionate, concrete procedure of processing comprises:
(1) get following raw material: p methoxy phenol 10kg, sodium hydroxide 10kg, potassiumiodide 0.12kg, water 100kg, join in reaction vessel, stir at normal temperatures 30 minutes, mix and rear this reaction vessel is heated, make above mixed raw material be warming up to 60 ℃, and make its temperature remain on 60 ℃～70 ℃, drip wherein the 2-methyl chloropropionate of 11.85kg, under the effect of catalyzer iodate potassium, p methoxy phenol and 2-methyl chloropropionate react, temperature while keeping reaction is at 60 ℃～90 ℃, simultaneously sodium hydroxide constantly with react in the acid of generation neutralize, reaction is carried out towards the direction of positive reaction always, reaction is carried out finishing after 12h,
(2) product is cooled to normal temperature, to the sulphuric acid soln that drips massfraction 30% in reacted mixed solution, dropping to pH of mixed is 2.0 o'clock, stop dripping, mixeding liquid temperature is reduced to below 45 ℃ subsequently, centrifugal to mixed solution, obtain white solid 2-(4-methoxyphenoxy) propionic acid 14.28kg;
(3) subsequently by the 2-(4-methoxyphenoxy of gained) propionic acid and 3.05kg sodium hydroxide puts in 75kg ethanol; be heated to subsequently 75 ℃; making 2-(4-methoxyphenoxy) propionic acid and sodium hydroxide dissolves completely; standing subsequently; crystallisation by cooling; the centrifugal ethanol of removing; obtain white or faint yellow solid; this white or faint yellow solid are dried to 2 hours in the vacuum drying oven of 60 ℃～90 ℃; obtain white 2-(4-methoxyphenoxy) Sodium Propionate solid 12.52kg, yield is 71.2%;
(4) product detects: the 2-(4-methoxyphenoxy of getting obtained white) Sodium Propionate solid 0.2259g dissolves and is settled to 100mL with pure water, upper machine testing after filtering; Wherein
Detecting instrument: Shimadzu SPD-M10AVP detector;
Chromatographic column: Yi Lite post Hypersil ODS25 μ m4.6mm*250mm;
Chromatographic condition: moving phase: Yi Jing ︰ pure water (with phosphoric acid adjust pH 4-5)=30 ︰ 70;
Flow velocity: 1.0mL/min;
Sample size: 2 μ L;
As shown in Figure 2, wherein external standard concentration (ESTD concentration) is 2237.276 μ g/mL to detected result, according to following formula:
Obtaining product purity is thus 99.03%, meets the use standard of foodstuff additive.
Embodiment 2
Sweetness inhibitor 2-(4-methoxyphenoxy) industrialized preparing process for Sodium Propionate, concrete procedure of processing comprises:
(1) p methoxy phenol 10kg, sodium hydroxide 10kg, sodium iodide 0.12kg, water 100kg are added in reaction vessel, stir at normal temperatures 30 minutes, raw material is mixed and to reaction vessel heating, make mixed raw material thing be warming up to 60 ℃ afterwards, and to keep mixed material temperature be 60 ℃～70 ℃, add wherein 2-methyl chloropropionate 11.85kg, limit edged stirs, and has added after 2-methyl chloropropionate, continues heating, make temperature of reaction remain on 90 ℃, after reaction times 12h, finish;
(2) product is cooled to normal temperature, to dripping massfraction in reacted mixed solution, it is 50% sulphuric acid soln, dropping to pH of mixed is 2.0 o'clock, stop dripping, centrifugal while subsequently mixeding liquid temperature being brought down below to 45 ℃, obtain white solid 2-(4-methoxyphenoxy) propionic acid 13.2kg;
(3) by the 2-(4-methoxyphenoxy of gained) propionic acid and 2.82kg sodium hydroxide puts in 75kg alcoholic solution, the optional methyl alcohol of alcoholic solution herein, ethanol, a kind of in acetone or the trimethyl carbinol, be heated to 70 ℃～80 ℃, make 2-(4-methoxyphenoxy) propionic acid and dissolution of sodium hydroxide, standing subsequently, crystallisation by cooling, the centrifugal alcoholic solution of sloughing, obtain white or faint yellow solid, this white or faint yellow solid are dried to 2 hours in the vacuum drying oven of 60 ℃～90 ℃, obtain white or flaxen 2-(4-methoxyphenoxy) Sodium Propionate, its quality is 12kg, total recovery is 68%,
(4) product detects with embodiment 1, its detected result: product purity >=99.00%, meets the use standard of foodstuff additive.
Comparative example
Sweetness inhibitor 2-(4-methoxyphenoxy) Industrialized synthesis method for Sodium Propionate, specifically comprises the following steps:
First p methoxy phenol 10kg, 2-chloropropionate 12.5kg, salt of wormwood 13kg, catalyzer iodate potassium or sodium iodide 0.16kg, dehydrated alcohol 65L are added in reaction vessel and mixed, the about 6h of heating reflux reaction, cold filtration, filtrate Distillation recovery ethanol;
Subsequently above-mentioned filtration gained leach thing in add ethyl acetate 80L and deionized water 10L, static layering is removed unreacted raw material, collect water layer and water layer is adjusted to pH to 2.0 with food grade hydrochloric acid, a large amount of white solid to be generated, gradation adds the solid in ether dissolution water layer, and each 65L, extracts three times altogether, then by the ether layer of collection again by deionized water 32L washed twice to remove residual potassium ion, distillation is removed solvent ether and is obtained white solid 2-(4-methoxyphenoxy) propionic acid;
Then by gained 2-(4-methoxyphenoxy) propionic acid dissolution of solid is in equimolar aqueous sodium hydroxide solution, then under 80 ℃ of conditions vacuum distilling except anhydrating, obtain 2-(4-methoxyphenoxy) Sodium Propionate, its total mass is 10.75kg, productive rate 61.37%, and product detects to such an extent that product purity is on the low side, be only 95.10%, do not meet the use standard of foodstuff additive.
By above experiment, contrast known beneficial effect of the present invention:
(1) adopt water to make solvent, in water, react, do not use any organic solvent in this reaction, saved cost, be also conducive to the purification processes of product simultaneously, and this reaction conditions is gentle, technique is simple;
(2) take in the reaction product that water is solvent, directly reaction product is regulated to pH value, can reach the object of purified reaction product, this process operation is simple, and cost is lower;
(3), at the direct crystallisation by cooling in organic solvent of end reaction after product, saved product extraction, the technique such as concentrated, and product purity is high, can reach the standard of using as foodstuff additive;
The present invention has simplified production process, has reduced energy consumption in a word, and productive rate is high and product purity is high, is applicable to large-scale industrial production sweetness inhibitor 2-(4-methoxyphenoxy) Sodium Propionate.
Above-described embodiment, is preferred embodiment of the present invention, is not used for limiting the scope of the present invention, and the equivalence of being done with the structure described in the claims in the present invention, feature and principle therefore all changes or modifies, within all should being included in the claims in the present invention scope.
Claims (9)
1. 2-(4-methoxyphenoxy) industrialized preparing process for Sodium Propionate, is characterized in that, comprises the steps:
(1) by p methoxy phenol, sodium hydroxide, catalyzer, water, be 1:(1～3 in mass ratio): (0.01～0.03): the ratio of (3～20) is mixed, heating makes the temperature of mixture be increased to 60 ℃～70 ℃, dropping is with respect to the 2-methyl chloropropionate of 1～2 times of amount of quality of p methoxy phenol, and reaction obtains product 2-(4-methoxyphenoxy) propionic acid;
(2) by 2-(4-methoxyphenoxy) propionic acid, sodium hydroxide be 1:(1～1.1 according to mol ratio) put in organic solvent, heating for dissolving, obtains 2-(4-methoxyphenoxy) Sodium Propionate.
2. the 2-(4-methoxyphenoxy according to claim 1) industrialized preparing process of Sodium Propionate, is characterized in that: described organic solvent is a kind of in methyl alcohol, ethanol, acetone or the trimethyl carbinol.
3. 2-(4-methoxyphenoxy according to claim 1) industrialized preparing process of Sodium Propionate, is characterized in that: the consumption of described organic solvent is 2-(4-methoxyphenoxy) 5～10 times of propionic acid quality.
4. the 2-(4-methoxyphenoxy according to claim 1) industrialized preparing process of Sodium Propionate, it is characterized in that: after described step (1), also comprise described product 2-(4-methoxyphenoxy) propionic acid carries out purification processes, be specially reacted mixed solution acid with sulphuric acid soln furnishing, cooling, centrifugal, obtain purer 2-(4-methoxyphenoxy) propionic acid.
5. 2-(4-methoxyphenoxy according to claim 4) industrialized preparing process of Sodium Propionate, is characterized in that: the mass concentration of described sulphuric acid soln is 30%～50%.
6. 2-(4-methoxyphenoxy according to claim 1) industrialized preparing process of Sodium Propionate, is characterized in that: after described step (2), also comprise described 2-(4-methoxyphenoxy) purification of Sodium Propionate, its concrete technology is recrystallization.
7. 2-(4-methoxyphenoxy according to claim 1) industrialized preparing process of Sodium Propionate, is characterized in that: described catalyzer is potassiumiodide or sodium iodide.
8. 2-(4-methoxyphenoxy according to claim 1) industrialized preparing process of Sodium Propionate, is characterized in that: the temperature of the described reaction in described step 1 is 60 ℃～90 ℃, and the time of described reaction is 6～24 hours.
9. 2-(4-methoxyphenoxy according to claim 1) industrialized preparing process of Sodium Propionate, is characterized in that: the temperature of the described heating for dissolving in described step (2) is 70 ℃～80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410110984.9A CN103922923B (en) | 2014-03-24 | 2014-03-24 | A kind of 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410110984.9A CN103922923B (en) | 2014-03-24 | 2014-03-24 | A kind of 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103922923A true CN103922923A (en) | 2014-07-16 |
| CN103922923B CN103922923B (en) | 2016-03-02 |
Family
ID=51141352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410110984.9A Active CN103922923B (en) | 2014-03-24 | 2014-03-24 | A kind of 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103922923B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725219A (en) * | 2015-02-11 | 2015-06-24 | 华中农业大学 | Preparation method of S-2-(4-methoxyphenoxy) sodium propionate |
| CN109111355A (en) * | 2018-08-31 | 2019-01-01 | 浙江工业大学 | A kind of chemical synthesis process of (R) -2- phenoxy propionic acid |
| CN113788749A (en) * | 2021-10-26 | 2021-12-14 | 武汉罗化科技有限公司 | Industrial preparation method and application of sweet inhibitor sodium 2- (4-methoxyphenyl) propionate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001068592A1 (en) * | 2000-03-13 | 2001-09-20 | Eli Lilly And Company | Sulfonamide derivatives |
| CN101492359A (en) * | 2009-02-27 | 2009-07-29 | 黄贤明 | Process for producing phenoxy alkane acid derivative |
| CN101735037A (en) * | 2009-12-11 | 2010-06-16 | 华中农业大学 | Synthesis method of sweet taste inhibitor 2-(4- methoxyphenyl) sodium propionate |
| CN102010326A (en) * | 2010-10-28 | 2011-04-13 | 华南理工大学 | Industrial method for synthesizing 2-(4-methoxyphenoxy)-propionic acid through phase transfer |
-
2014
- 2014-03-24 CN CN201410110984.9A patent/CN103922923B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001068592A1 (en) * | 2000-03-13 | 2001-09-20 | Eli Lilly And Company | Sulfonamide derivatives |
| CN101492359A (en) * | 2009-02-27 | 2009-07-29 | 黄贤明 | Process for producing phenoxy alkane acid derivative |
| CN101735037A (en) * | 2009-12-11 | 2010-06-16 | 华中农业大学 | Synthesis method of sweet taste inhibitor 2-(4- methoxyphenyl) sodium propionate |
| CN102010326A (en) * | 2010-10-28 | 2011-04-13 | 华南理工大学 | Industrial method for synthesizing 2-(4-methoxyphenoxy)-propionic acid through phase transfer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725219A (en) * | 2015-02-11 | 2015-06-24 | 华中农业大学 | Preparation method of S-2-(4-methoxyphenoxy) sodium propionate |
| CN104725219B (en) * | 2015-02-11 | 2017-08-08 | 华中农业大学 | The preparation method of S 2 (4 methoxyphenoxy) sodium propionate |
| CN109111355A (en) * | 2018-08-31 | 2019-01-01 | 浙江工业大学 | A kind of chemical synthesis process of (R) -2- phenoxy propionic acid |
| CN113788749A (en) * | 2021-10-26 | 2021-12-14 | 武汉罗化科技有限公司 | Industrial preparation method and application of sweet inhibitor sodium 2- (4-methoxyphenyl) propionate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103922923B (en) | 2016-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102816188B (en) | Production technology of sucralose | |
| CN102503800B (en) | Refining method of C11-C18 long-chain diacid | |
| CN102911036A (en) | Method for obtaining high pure dicarboxylic acid | |
| CN104744237A (en) | Preparation method of 2-(4-bromomethylphenyl) propionic acid | |
| CN103570609A (en) | Preparation method for 2,3-dichloropyridine | |
| CN103922923B (en) | A kind of 2-(4-methoxyphenoxy) industrialized preparing process of Sodium Propionate | |
| CN101759728A (en) | Method for preparing and refining sucralose | |
| CN1315818C (en) | Synthesis method of ranitidine alkali and its hydrochloride | |
| CN102453011A (en) | Preparation method of high-purity naringenin | |
| CN113773286A (en) | Synthetic method of furanone | |
| CN104086545A (en) | Synthesis method of 1-(2-fluorobenzyl)-1H-pyrazolo[3,4-b]pyridyl-3-formamidine hydrochloride | |
| CN112552167B (en) | Preparation method of calcium gluconate | |
| CN104829590A (en) | Trelagliptin purification method | |
| CN101735037B (en) | Synthesis method of sweet taste inhibitor 2-(4- methoxyphenyl) sodium propionate | |
| CN112876354B (en) | 2- (4-methoxyphenoxy) propionic acid derivative with sweet taste inhibiting effect and industrial production method thereof | |
| CN103087090B (en) | Synthetic method of 2-dipalmitoyl-sn-glycero-3-phosphoethanolamine | |
| CN102964396B (en) | A kind of method of trichloro-cane-6-ethyl ester recrystallization | |
| CN106631745B (en) | A method of purifying phloretin from Hubei Chinese flowering crabapple leaf | |
| WO2021212535A1 (en) | Method for refining benzhexol hydrochloride | |
| CN104418810A (en) | New synthetic route of levosimendan | |
| CN106928290A (en) | A kind of preparation method of high content rutin | |
| CN113214041A (en) | Novel method for preparing 3-iodine-2 bromotoluene | |
| CN109456198A (en) | A kind of synthetic method of 2,2`- diamino-N-methyl-diethyl-amine | |
| CN102180781B (en) | Method for extracting and producing high-purity xanthohumol from residues generated by extracting hops by carbon dioxide | |
| CN103172532B (en) | A kind of preparation method of ethylenediaminetetraacidic acidic calcium disodium salt |
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 |