CN103319548B - A kind of method of purification of cane sugar-6-acetic ester - Google Patents
A kind of method of purification of cane sugar-6-acetic ester Download PDFInfo
- Publication number
- CN103319548B CN103319548B CN201310280186.6A CN201310280186A CN103319548B CN 103319548 B CN103319548 B CN 103319548B CN 201310280186 A CN201310280186 A CN 201310280186A CN 103319548 B CN103319548 B CN 103319548B
- Authority
- CN
- China
- Prior art keywords
- acetic ester
- cane sugar
- isoamyl alcohol
- purification
- primary isoamyl
- 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.)
- Active
Links
Landscapes
- Saccharide Compounds (AREA)
Abstract
The invention provides a kind of method of purification of cane sugar-6-acetic ester, concrete steps are: under temperature of reaction is 20-80 DEG C of condition, primary isoamyl alcohol is added in cane sugar-6-acetic ester crude product, treat that crystal is separated out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of primary isoamyl alcohol and cane sugar-6-acetic ester crude product is 1:1-5:1; Described method of purification selects primary isoamyl alcohol to make extraction agent, primary isoamyl alcohol is polar solvent, the polarity of sucrose is greater than the polarity of cane sugar-6-acetic ester, cane sugar-6-acetic ester can be separated out in primary isoamyl alcohol, and required amount is also little, the temperature of requirement is not high yet, lower to equipment requirements in industrial production, there is higher economic benefit simultaneously, be applicable to the needs of large-scale commercial production.
Description
Technical field
The present invention relates to a kind of method of purification of intermediate of Sucralose, especially a kind of method of purification of cane sugar-6-acetic ester.
Background technology
Sucralose, English name is Sucralose, the functional sweetener of to be unique with sucrose be raw material, and sugariness can reach more than 600 times of sucrose, be non-nutritive, efficient, without the sweeting agent of harm.
Sucralose is nonhygroscopic white crystalline powder, and chemical stability is very high in an acidic solution, and also fine at light, heat condition stability inferior, be soluble in ethanol, specific refractory power and solubleness have good linear relationship.
Usually " single radical protection method " is adopted to carry out final synthesizing trichloro at present.The advantage of this method is that single radical protection method three step can synthesize Sucralose, and step is few, simple to operate, requires also not high to processing unit.Its first step is exactly adopt suitable esterifying reagent to protect 6; obtain sucrose-6-ester; visible sucrose-6-ester is the important intermediate producing Sucralose; the synthesis of sucrose-6-ester is the committed step in three steps, and the productive rate of raising sucrose-6-ester and purity directly affect quality and the economic benefit of the Sucralose of follow-up synthesis.GB1543167 and GB2104063B discusses the purposes of sucrose ester and Sucralose.
In the Sucralose synthetic method of bibliographical information, the more of sucrose-6-ester is prepared by sucrose and esterifying agent, but about isolation andpurification less of sucrose-6-ester, the mixed solution of major part employing sucrose-6-ester is directly cooked reaction below, in mixed solution except cane sugar-6-acetic ester, also has unreacted raw material and byproduct of reaction, for alleviating the burden of following process, reduce the cost of following process, the separating-purifying of Sucralose is carried out smoothly, separating-purifying should be carried out to it.
US7626016 Purification of Suctose-6-acetate By The Method of Ion Exchanging, this method selects granularity to be that the strong-acid ion exchange resin of 50mesh ~ 100mesh makes sorbent material, aqueous acetone solution with 70% makes eluent separating-purifying cane sugar-6-acetic ester, this method needs a large amount of solvents, and the process of ion exchange resin is cumbersome, purity is also not too high; US20070227897 does recrystallization with anhydrous methanol under heated reflux condition, then room temperature is cooled to, crystal seed is made with cane sugar-6-acetic ester, spend the night, cane sugar-6-acetic ester that must be purer, this method and US7932380, US4889928, US2011168568's is similar, and the time that these class methods need is long and under the condition of reflux, cane sugar-6-acetic ester crude product color can be deepened; Also have some document Purifying Sucrose-6-Acetate by Column Chromatographies, this class methods solvent for use amount is large, and loss of product is many.
Summary of the invention
Technical problem to be solved by this invention is the method for purification providing a kind of cane sugar-6-acetic ester.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of method of purification of cane sugar-6-acetic ester, concrete steps are: under temperature of reaction is 20-80 DEG C of condition, primary isoamyl alcohol is added in cane sugar-6-acetic ester crude product, treat that crystal is separated out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of primary isoamyl alcohol and cane sugar-6-acetic ester crude product is 1:1-5:1.
Preferably, the method for purification of above-mentioned cane sugar-6-acetic ester, described cane sugar-6-acetic ester crude product is brown color viscous liquid, is under the condition of underpressure distillation, to remove most of DMF by the DMF solution of cane sugar-6-acetic ester to obtain.
Preferably, the method for purification of above-mentioned cane sugar-6-acetic ester, described temperature of reaction is 20-50 DEG C.
Preferably, the method for purification of above-mentioned cane sugar-6-acetic ester, described temperature of reaction is 20 DEG C.
Preferably, the method for purification of above-mentioned cane sugar-6-acetic ester, the volume ratio of described primary isoamyl alcohol and cane sugar-6-acetic ester crude product is 2:1-4:1.
Preferably, the method for purification of above-mentioned cane sugar-6-acetic ester, the volume ratio of described primary isoamyl alcohol and cane sugar-6-acetic ester crude product is 3:1.
The invention has the beneficial effects as follows:
The method of purification of above-mentioned cane sugar-6-acetic ester, primary isoamyl alcohol is selected to make extraction agent, primary isoamyl alcohol is polar solvent, the polarity of sucrose is greater than the polarity of cane sugar-6-acetic ester, and cane sugar-6-acetic ester can be separated out in primary isoamyl alcohol, and required amount is also little, the temperature required is not high yet, lower to equipment requirements in industrial production, there is higher economic benefit simultaneously, be applicable to the needs of large-scale commercial production.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described.
Experimental technique in following embodiment, if no special instructions, is ordinary method; Test materials used in following embodiment, if no special instructions, all can buy from routine biochemistry reagent shop and obtain; Following detection method is liquid phase chromatography, carries out with reference to reference US4889928.
Embodiment 1
A method of purification for cane sugar-6-acetic ester, concrete steps are:
The DMF solution of cane sugar-6-acetic ester is removed most of DMF under the condition of underpressure distillation, obtain the crude product of cane sugar-6-acetic ester, under 20 DEG C of conditions, add primary isoamyl alcohol, a large amount of crystal is had to separate out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of primary isoamyl alcohol used and cane sugar-6-acetic ester crude product is 3:1; Obtain cane sugar-6-acetic ester 3.7g, yield 82%, analyzes product by liquid chromatography, and cane sugar-6-acetic ester purity is 92%.
Wherein, according to liquid phase chromatography, with reference to reference US4889928, according to retention time, cane sugar-6-acetic ester is confirmed, obtain its content value according to peak area ratio.Actual conditions is as follows: Zorbax NH
2post, moving phase is V(water): V(acetonitrile)=85:15, flow velocity 1.5mL/min, sample size 2 μ L, retention time sucrose: 3.46, sucrose-4-ester: 4.66, sucrose-6-ester 8.63.
Embodiment 2
A method of purification for cane sugar-6-acetic ester, concrete steps are:
The DMF solution of cane sugar-6-acetic ester is removed most of DMF under the condition of underpressure distillation, obtain the crude product of cane sugar-6-acetic ester, under 20 DEG C of conditions, add primary isoamyl alcohol, a large amount of crystal is had to separate out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of primary isoamyl alcohol used and cane sugar-6-acetic ester crude product is 2:1; Obtain cane sugar-6-acetic ester 3.6g, yield 80%, analyzes product by liquid chromatography, and cane sugar-6-acetic ester purity is 90%.
Embodiment 3
A method of purification for cane sugar-6-acetic ester, concrete steps are:
The DMF solution of cane sugar-6-acetic ester is removed most of DMF under the condition of underpressure distillation, obtain the crude product of cane sugar-6-acetic ester, under 30 DEG C of conditions, add primary isoamyl alcohol, a large amount of crystal is had to separate out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of primary isoamyl alcohol used and cane sugar-6-acetic ester crude product is 2:1; Obtain cane sugar-6-acetic ester 3.4g, yield 76%, analyzes product by liquid chromatography, and cane sugar-6-acetic ester purity is 80%.Along with the rising of temperature, the solubleness of cane sugar-6-acetic ester in primary isoamyl alcohol increases.
Embodiment 4
A method of purification for cane sugar-6-acetic ester, concrete steps are:
The DMF solution of cane sugar-6-acetic ester is removed most of DMF under the condition of underpressure distillation, obtain the crude product of cane sugar-6-acetic ester, under 20 DEG C of conditions, add primary isoamyl alcohol, a large amount of crystal is had to separate out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of primary isoamyl alcohol used and cane sugar-6-acetic ester crude product is 4:1; Obtain cane sugar-6-acetic ester 3.5g, yield 78%, analyzes product by liquid chromatography, and cane sugar-6-acetic ester purity is 88%.
Embodiment 5
A method of purification for cane sugar-6-acetic ester, concrete steps are:
The DMF solution of cane sugar-6-acetic ester is removed most of DMF under the condition of underpressure distillation, obtain the crude product of cane sugar-6-acetic ester, under 80 DEG C of conditions, add primary isoamyl alcohol, a large amount of crystal is had to separate out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of primary isoamyl alcohol used and cane sugar-6-acetic ester crude product is 5:1; Obtain cane sugar-6-acetic ester 3.2g, yield 71%, analyzes product by liquid chromatography, and cane sugar-6-acetic ester purity is 80%.
Embodiment 6
A method of purification for cane sugar-6-acetic ester, concrete steps are:
The DMF solution of cane sugar-6-acetic ester is removed most of DMF under the condition of underpressure distillation, obtain the crude product of cane sugar-6-acetic ester, under 50 DEG C of conditions, add primary isoamyl alcohol, a large amount of crystal is had to separate out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of primary isoamyl alcohol used and cane sugar-6-acetic ester crude product is 3:1; Obtain cane sugar-6-acetic ester 3.4g, yield 76%, analyzes product by liquid chromatography, and cane sugar-6-acetic ester purity is 79%.
Embodiment 7
A method of purification for cane sugar-6-acetic ester, concrete steps are:
The DMF solution of cane sugar-6-acetic ester is removed most of DMF under the condition of underpressure distillation, obtain the crude product of cane sugar-6-acetic ester, under 30 DEG C of conditions, add primary isoamyl alcohol, a large amount of crystal is had to separate out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of primary isoamyl alcohol used and cane sugar-6-acetic ester crude product is 3:1; Obtain cane sugar-6-acetic ester 3.5g, yield 78%, analyzes product by liquid chromatography, and cane sugar-6-acetic ester purity is 86%.
Embodiment 8
A method of purification for cane sugar-6-acetic ester, concrete steps are:
The DMF solution of cane sugar-6-acetic ester is removed most of DMF under the condition of underpressure distillation, obtain the crude product of cane sugar-6-acetic ester, under 40 DEG C of conditions, add primary isoamyl alcohol, a large amount of crystal is had to separate out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of primary isoamyl alcohol used and cane sugar-6-acetic ester crude product is 4:1; Obtain cane sugar-6-acetic ester 3.4g, yield 76%, analyzes product by liquid chromatography, and cane sugar-6-acetic ester purity is 81%.
Comparative example 1
A method of purification for cane sugar-6-acetic ester, concrete steps are:
The DMF solution of cane sugar-6-acetic ester is removed most of DMF under the condition of underpressure distillation, obtain the crude product of cane sugar-6-acetic ester, under 20 DEG C of conditions, add ethyl acetate, crystal is had to separate out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of ethyl acetate used and cane sugar-6-acetic ester crude product is 2:1; Obtain cane sugar-6-acetic ester 3.2g, yield 71%, analyzes product by liquid chromatography, and cane sugar-6-acetic ester purity is 80%.
Comparative example 2
A method of purification for cane sugar-6-acetic ester, concrete steps are:
The DMF solution of cane sugar-6-acetic ester is removed most of DMF under the condition of underpressure distillation, obtain the crude product of cane sugar-6-acetic ester, under 20 DEG C of conditions, add methylene dichloride, crystal is had to separate out, filter, crystallize out is dry in vacuum drying oven, and the volume ratio of methylene dichloride used and cane sugar-6-acetic ester crude product is 2:1; Obtain cane sugar-6-acetic ester 3.5g, yield 78%, analyzes product by liquid chromatography, and cane sugar-6-acetic ester purity is 82%.
Comparative example 3
A method of purification for cane sugar-6-acetic ester, concrete steps are:
Under 20 DEG C of conditions, in the DMF solution of cane sugar-6-acetic ester, add primary isoamyl alcohol, just started have crystal to separate out, very fast crystal disappears, and becomes solution, illustrates that the solubleness of DMF in primary isoamyl alcohol is very large.
The preparation method of the DMF solution of cane sugar-6-acetic ester in above-described embodiment and comparative example, be synthesize by the method for Dibutyltin oxide, concrete steps are:
(1) in 100ml tri-mouthfuls of round-bottomed flasks, sucrose 4.0g (11.68mmol) is added, DMF(N, dinethylformamide) 14mL, heated and stirred, makes sucrose dissolve completely, is down to room temperature, obtains sucrose dissolved liquid stand-by; In gained sucrose dissolved liquid, add Dibutyltin oxide 3.06g (12.26mmol) and hexanaphthene 4mL, and install the prolong of top with water trap additional, backflow 4-5h, to water trap, no longer include water generate; Reaction solution is cooled to 5 DEG C, drip diacetyl oxide 1.31g (12.9mmol), in dropping process, temperature is lower than 10 DEG C, after dropwising, keeps thermotonus 1h;
(2) in above-mentioned reaction solution, add a small amount of water, then extract with hexanaphthene, lower floor is product, mainly the DMF solution of cane sugar-6-acetic ester; The NaOH solution of upper strata 4mol/L separates out organotin, filters, dry, reclaims organotin.
Comparison study example
Prepare sucralose-6-acetic ester:
(1) in 100mL tri-mouthfuls of reaction flasks that magneton, condenser, thermometer are housed, add DMF10mL(0.13mol) and ethyl acetate 10mL(0.11mol), under ice-water bath cooling and stirring, slow dropping sulfur oxychloride 6.64mL(0.09mol), control dropping temperature below 20 DEG C, dropwise rear be slowly warming up to 78 DEG C backflow two hours, be down to room temperature, after leaving standstill a night, in solution, generate a large amount of needle-like white crystallization.Namely the DMF solution of this crystallization be Vilsimier reagent;
(2) be dissolved in by cane sugar-6-acetic ester in appropriate DMF solution, be slowly added drop-wise in above-mentioned Vilsimier reagent afterwards, ice-water bath cools, and controls dropping temperature at 0 ~ 5 DEG C, is slowly warming up to 78 DEG C, reacts 1 hour under logical condition of nitrogen gas; Rise to 110 DEG C again, reflux 3 hours; After reaction terminates, ice-water bath cools, and the sodium hydroxide solution adding 4mol/L, to neutral, adds after 50mL ethyl acetate fully stirs, filter, filter cake again with the washing of 50mL ethyl acetate, filtrate with 25mL × 4 extraction into ethyl acetate, combined ethyl acetate layer, after ethyl acetate layer uses 25mL × 2 water washing again, add 5g activated carbon decolorizing, concentrated under 60 DEG C of high-altitudes, obtain sucralose-6-acetic ester concentrated solution.
Prepare result (total recovery of sucralose-6-acetic ester and purity) in table 1, wherein,
First group-use Purification of Suctose-6-acetate By The Method of Ion Exchanging (US7626016);
Second group-under heated reflux condition, do with anhydrous methanol the cane sugar-6-acetic ester (US20070227897) that recrystallization must be purer;
Cane sugar-6-acetic ester described in 3rd group-embodiment 1
4th group-cane sugar-6-acetic ester of not purifying
Table 1
Grouping | Total recovery | Purity |
First group | 37% | 94% |
Second group | 38% | 95% |
3rd group | 39.2% | 98% |
4th group | 35% | 92% |
Visible, the second step of synthesizing trichloro be cane sugar-6-acetic ester through superchlorination synthesizing trichloro-6-acetic ester, have sucrose, sucrose-4-acetic ester in cane sugar-6-acetic ester before not purifying, to lower one-step chlorination and purify unfavorable so that last Sucralose is difficult to recrystallization.
Above-mentioned detailed description of the method for purification of this kind of cane sugar-6-acetic ester being carried out with reference to embodiment; illustrative instead of determinate; several embodiments can be listed according to institute's limited range; therefore in the change do not departed under general plotting of the present invention and amendment, should belong within protection scope of the present invention.
Claims (5)
1. the method for purification of a cane sugar-6-acetic ester, it is characterized in that: concrete steps are: under temperature of reaction is 20-80 DEG C of condition, primary isoamyl alcohol is added in cane sugar-6-acetic ester crude product, treat that crystal is separated out, filter, crystallize out is dry in vacuum drying oven, the volume ratio of primary isoamyl alcohol and cane sugar-6-acetic ester crude product is 1:1-5:1, wherein said cane sugar-6-acetic ester crude product is brown color viscous liquid, is under the condition of underpressure distillation, to remove most of DMF by the DMF solution of cane sugar-6-acetic ester to obtain.
2. the method for purification of cane sugar-6-acetic ester according to claim 1, is characterized in that: described temperature of reaction is 20-50 DEG C.
3. the method for purification of cane sugar-6-acetic ester according to claim 1 and 2, is characterized in that: described temperature of reaction is 20 DEG C.
4. the method for purification of cane sugar-6-acetic ester according to claim 1, is characterized in that: the volume ratio of described primary isoamyl alcohol and cane sugar-6-acetic ester crude product is 2:1-4:1.
5. the method for purification of the cane sugar-6-acetic ester according to claim 1 or 4, is characterized in that: the volume ratio of described primary isoamyl alcohol and cane sugar-6-acetic ester crude product is 3:1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310280186.6A CN103319548B (en) | 2013-07-04 | 2013-07-04 | A kind of method of purification of cane sugar-6-acetic ester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310280186.6A CN103319548B (en) | 2013-07-04 | 2013-07-04 | A kind of method of purification of cane sugar-6-acetic ester |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103319548A CN103319548A (en) | 2013-09-25 |
CN103319548B true CN103319548B (en) | 2015-09-23 |
Family
ID=49188634
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310280186.6A Active CN103319548B (en) | 2013-07-04 | 2013-07-04 | A kind of method of purification of cane sugar-6-acetic ester |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103319548B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106749440B (en) * | 2016-12-07 | 2019-07-02 | 广西科技大学 | A kind of method for crystallising by sucrose and ortho-acetate synthesizing cane sugar-6-acetic ester |
CN109593107A (en) * | 2018-12-10 | 2019-04-09 | 安徽金禾实业股份有限公司 | A kind of method of purification of cane sugar-6-acetic ester |
CN111575327A (en) * | 2020-05-25 | 2020-08-25 | 安徽金禾实业股份有限公司 | Method for synthesizing sucrose-6-acetate by using rhizomucor miehei lipase as catalyst |
CN113214330A (en) * | 2021-05-13 | 2021-08-06 | 安徽金禾化学材料研究所有限公司 | Purification and chlorination process of sucrose-6-ethyl ester |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8622345D0 (en) * | 1986-09-17 | 1986-10-22 | Tate & Lyle Plc | Sucrose derivatives |
WO2007052304A2 (en) * | 2005-08-30 | 2007-05-10 | Pharmed Medicare Pvt. Ltd. | A process for purification of trichologalactosucrose based on direct extraction in organic solvent from reaction mixture followed by evaporative removal of solvent |
CN101253187A (en) * | 2005-08-30 | 2008-08-27 | 法马德医疗保险私人有限公司 | Removal of pyridine and pyridine analogs from reaction mass containing sucrose esters |
CN100418976C (en) * | 2006-04-03 | 2008-09-17 | 广州科宏食品添加物有限公司 | Process for preparing sucralose |
US7932380B2 (en) * | 2008-03-06 | 2011-04-26 | Wanhe International (Group) Co. Ltd. | Process for the preparation of sucralose |
CN101886100B (en) * | 2010-07-12 | 2012-08-08 | 江南大学 | Method for preparing sucrose-6-acetic ester by enzymatic method |
-
2013
- 2013-07-04 CN CN201310280186.6A patent/CN103319548B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN103319548A (en) | 2013-09-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108047261B (en) | Preparation method of clitorium | |
CN107089981A (en) | A kind of inhibitor Venetoclax of BCL 2 synthetic method | |
CN103319548B (en) | A kind of method of purification of cane sugar-6-acetic ester | |
CN108129288B (en) | Synthesis method of trans-3-hydroxycyclobutylformic acid | |
CN106256824B (en) | Preparation method of high-purity delafloxacin meglumine salt | |
CN105218621B (en) | Dehydroabietic acid benzimidazole Schiff base heterocyclic derivatives with anti-tumor activity and preparation method therefor and application thereof | |
CN107266370A (en) | A kind of process for purification of olaparib compound | |
CN106146560B (en) | A kind of refining methd of high-purity phosphoric acid specially azoles amine | |
CN103755648A (en) | New impurity of gefitinib and preparation method thereof | |
CN108586355A (en) | A kind of process for purification of olaparib | |
CN102199180A (en) | Preparation method of capectabine | |
CN103787924A (en) | New purification method of antitumor drug Belinostat | |
CN101735220B (en) | Crystal form of 6, 7-dihydro-6-mercapto-5H-pyrazolo[1,2-alpha][1,2,4] triazoliumchloride and preparation method thereof | |
CN101270124B (en) | Novel method for purifying and preparing high-purity fluorandiol and fluorandiol salt | |
CN103665084A (en) | Method for preparing abiraterone acetate | |
CN103374049B (en) | One prepares 5,6, the method for 4 '-trihydroxyflavone-7-0-D-glucuronic acid | |
CN105732547B (en) | A kind of preparation method of Dehydro and drographolide diacid half esters | |
CN102010455B (en) | Method for preparing decitabine | |
CN104761599A (en) | Preparation method of 5,4'-dihydroxy flavone-7-O-D-glucuronic acid | |
CN105085595B (en) | A kind of method of deacylation base protection 2,6 halosubstituted purine nucleosides of synthesis | |
CN113896732A (en) | Preparation method and application of anti-cancer drug carbamatinib | |
CN106478624A (en) | A kind of purification process of moxifloxacin hydrochloride | |
CN107304194A (en) | The method for preparing Dapagliflozin | |
CN111892488A (en) | Method for efficiently synthesizing 2, 6-dichloro-3-fluoro acetophenone | |
CN103360301B (en) | Purifying method for alvimopan intermediate |
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 |