CN1927800A - Synthesis process of 2,4,6-trimethyl benzoic acid - Google Patents
Synthesis process of 2,4,6-trimethyl benzoic acid Download PDFInfo
- Publication number
- CN1927800A CN1927800A CN 200510047925 CN200510047925A CN1927800A CN 1927800 A CN1927800 A CN 1927800A CN 200510047925 CN200510047925 CN 200510047925 CN 200510047925 A CN200510047925 A CN 200510047925A CN 1927800 A CN1927800 A CN 1927800A
- Authority
- CN
- China
- Prior art keywords
- reaction
- carboxylic acid
- synthesis technique
- sym
- trimethylbenzene
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention belongs to the field of refined chemical preparation, and is especially process of synthesizing 2, 4, 6-trimethyl benzoic acid. Compound 2, 4, 6-trimethyl benzoic acid may be used as intermediate for dye, pesticide, medicine and photoinitiator, and to synthesize trimethyl benzoyl chloride, hardening agent for polyepoxide and photoinitiator for polymer. The synthesizing process includes the following steps: 1. acylation reaction of sym-trimethyl benzene and chloroacethyl chloride via heating in the presence of acylating catalyst and subsequent filtering and acidifying the filtrate to prepare 2, 4, 6-trimethyl chloro acetophenone; 2. chloroform reaction of the product of the step 1 and sodium hypochlorite via heating in the presence of quaternary ammonium salt as phase transfer catalyst to prepare 2, 4, 6-trimethyl benzoic acid; and 3. hydrolysis reaction of the product of step 2 and subsequent extraction, acid neutralization and re-crystallization.
Description
Technical field
The invention belongs to fine chemical product preparation technology field, particularly a kind of synthesis technique of mesitylene carboxylic acid.Mesitylene carboxylic acid can be used as the intermediate of dyestuff, sterilant, medicine and light trigger; Can synthesize the stiffening agent of tri-methyl chloride, polyepoxide and the light trigger of polymkeric substance etc.
Background technology
Early stage report produces 2; 4; the method of 6-trimethylbenzoic acid mainly contains the nitric acid oxidation, 2 that isodurene is a raw material; 4, dry distillation, sym-trimethylbenzene and the urea chloride of 6-trimethylammonium amygdalic acid is the acidylate method of raw material, vitriolization 2,4; glyoxalated method of 6-Three methyl Benzene etc. but all owing to adopt special material; the technical difficulty that has is big, and product yield is low, does not therefore all carry out practical application.
It is raw material production 2 that Recent study personnel attempt with the sym-trimethylbenzene; 4; the 6-trimethylbenzoic acid; mainly containing sym-trimethylbenzene and chloroacetyl chloride is reaction raw materials, and the Friedel-crafts reaction catalyzer of employing is generally aluminum chloride, produces a large amount of acid gas in reaction and last handling process; serious to equipment corrosion; it is the acylation reaction of catalyzer that the ferric oxide of employing is also arranged, its haloform reaction that carries out of employing rate etc., and the content of this respect mainly is described in (US5; 296; 636 and Lv Jiuzhuo, 2,4; 6;-trimethylbenzoic acid synthetic, Speciality Petrochemicals, 2001.3 periodicals) in; but common ferric oxide is Powdered; in the organic synthesis process,, and make and contain a large amount of iron in the product, be difficult to guarantee the quality of product with the product separation difficulty.And the very difficult realization of pulverous ferric oxide successive organic synthesis operation, make production efficiency low.On the other hand, adopt high pollution thing Cl in the haloform reaction of (Lv Jiuzhuo, 2,4,6 ,-trimethylbenzoic acid synthetic, Speciality Petrochemicals, 2001.3 periodicals)
2As the haloform reaction raw material, make and strengthened hazard rating by operational difficulty.
Summary of the invention
The object of the present invention is to provide a kind of cost low, the productive rate height, technology is simple, and can reduce the synthesis technique of the mesitylene carboxylic acid of pollution as far as possible.
Technical solution of the present invention can realize according to following mode:
The synthesis technique of mesitylene carboxylic acid comprises acylation reaction, haloform reaction and hydrolysis reaction successively, is characterized in:
(1) acylation reaction: with sym-trimethylbenzene and chloroacetyl chloride is acylations raw material thing, adopts the acylations catalyzer, through intensification, filtration, filtrate acidification step preparation 2,4,6-trimethylammonium chloroacetophenone;
(2) haloform reaction: with step (1) products therefrom and clorox is raw material, and the employing quaternary ammonium salt is a phase-transfer catalyst, prepares mesitylene carboxylic acid through intensification, reduction reaction step;
(3) hydrolysis reaction: step (2) gained reactant promptly gets final product through extraction separatory, acid neutralization, recrystallization again.
The mass concentration of clorox is 10~20% in the haloform reaction of the present invention; Described sym-trimethylbenzene and chloroacetyl chloride are refinery byproduct C
9Cut-sym-trimethylbenzene and technical grade chloroacetyl chloride.
As a kind of preferred version, quaternary ammonium salt of the present invention can adopt benzyltrimethylammonium bromide or Tetrabutyl amonium bromide.
Described acylations catalyzer is a loading type ferric oxide catalyst, be mixture with metal oxide, zeolite molecular sieve or metal oxide and zeolite molecular sieve as carrier, be steeping fluid with the aqueous solution that contains molysite, nickel salt or cobalt salt, carry out as follows:
1) described carrier is carried out 6~12 hours dipping;
2) with soaked carrier 60~150 ℃ dry 3~8 hours down, 300~700 ℃ of following roasts 4~12 hours, obtain catalyst precursor again;
3) repeat above operation and promptly get final product.
As another kind of preferred version, metal oxide of the present invention is Al
2O
3, MgO, TiO
2Described zeolite molecular sieve is Na type zeolite, H type zeolite, X type zeolite, y-type zeolite, zeolite beta or A type zeolite or is the mixture of two or more described zeolite.
The present invention can add mass concentration in described haloform reaction be 10~20% alkali lye; Described 2,4, the mole proportioning of 6-trimethylammonium chloroacetophenone, clorox and alkali lye is 1: 8~15: 0.8~2.
Wherein, the chloroacetyl chloride consumption is 1~3 times of sym-trimethylbenzene weight, and in about 4~6 hours of reaction times, temperature is controlled at 60~90 ℃.
The method of producing mesitylene carboxylic acid that the present invention proposes has used the high activity loading type ferric oxide catalyst to carry out acylation reaction, with local resources refinery byproduct C
9Cut-sym-trimethylbenzene, technical grade chloroacetyl chloride are raw material, and haloform reaction is a raw material by adopting clorox, acylations product, add the phase-transfer catalyst quaternary ammonium salt and carry out haloform reaction; product process extraction separatory, acidifying, recrystallization has obtained highly purified 2; 4, the 6-trimethylbenzoic acid.
The acylations raw material that is wherein adopted is refinery byproduct C
9Cut-sym-trimethylbenzene, technical grade chloroacetyl chloride, chloroacetyl chloride consumption are 1~3 times of sym-trimethylbenzene weight, and in about 4~6 hours of reaction times, temperature is controlled at about 60~90 ℃, and excessive chloroacetyl chloride is recyclable.
Present method is selected the loading type ferric oxide catalyst of homemade high reactivity, highly selective for use, and the catalyst levels scope is 1 of sym-trimethylbenzene consumption~10 ‰.
The present invention has been owing to selected homemade high activity loading type ferric oxide catalyst for use, improved AlCl used on the traditional method
3, Fe
2O
3Deng conventional catalyst, improved the efficient of acylation reaction greatly, improved the purity of product, because the recyclable utilization of catalyzer also greatly reduces cost, make this method be easy to industrialization.
The inventive method has been simplified technological process, and is easy to operate, raw materials used or for byproduct or technical grade or for the chemical industry raw material that is easy to get, and realizes industrialization easily.
Embodiment
Below in conjunction with embodiment the specific embodiment of the present invention is described in detail.
Embodiment 1
1) 2,4, the preparation of 6-trimethylammonium chloroacetophenone
In the 36g sym-trimethylbenzene, add the homemade loading type ferric oxide catalyst of 0.072g, in sym-trimethylbenzene solution, drip chloroacetyl chloride 48ml, be warming up to about 80 ℃, continue reaction 6 hours, stopped reaction filters, and reclaims catalyzer, the filtrate acidifying, cooling is also stirred fast, a large amount of solid precipitations occur, weighs after the drying, obtain thick product, reclaim the excess chlorine Acetyl Chloride 98Min..The transformation efficiency of sym-trimethylbenzene is 97%, chloracetyl 2,4, and the selectivity of 6-trimethylbenzene is 98%.Product is through liquid chromatographic detection, and content is 92%.
The preparation technology of above-mentioned loading type ferric oxide catalyst is as follows:
At room temperature, by weight with 30 parts of Fe (NO
3)
3.6H
2O, 5 parts of Co (NO
3)
2.4H
2O and 65 parts of water are hybridly prepared into steeping fluid.5 gram 4A type molecular sieve carriers were joined in the steeping fluid that 25 grams prepare dipping 7 hours; Filter then, drying is 3 hours under 120 ℃, is put in the retort furnace again, with 5 ℃ of/second temperature programming to 450 ℃ roastings 4 hours, obtains loading type ferric oxide catalyst.
Activity of such catalysts provided by the invention is tested with the following method:
Acylation reaction among the present invention is to carry out in having the round-bottomed flask of reflux, adopts mechanical stirring.Reaction process is: add a certain amount of catalyzer provided by the invention in sym-trimethylbenzene, in this solution, drip chloroacetyl chloride, the back continuation that heats up is reacted, and behind the stopped reaction, filters, reclaim catalyzer, the filtrate acidifying, cooling is also stirred filtration, drying fast, obtain thick product, product is carried out analytical test.
2) preparation of mesitylene carboxylic acid
With the product that obtains in the foregoing description 1 as the haloform reaction raw material, at first with 2,4,6-trimethylammonium chloroacetophenone (10g) is dissolved in 1, in the 4-dioxane solution (11ml), splash into then that (wherein chlorine bleach liquor's mass concentration is 11%, solution quality 110g in the mixed solution of the clorox that contains benzyltrimethylammonium bromide (0.2g) and sodium hydroxide; The mass concentration of sodium hydroxide solution is 11%, solution capacity 10ml), maintain the temperature under 55 ℃ of conditions and reacted 1 hour, add the excessive clorox of bisulfite sodium reduction, continue to add 40% sodium hydroxide 10ml, be warming up to 80 ℃, continue reaction 5 hours, stopped reaction.
3) with step 2) the product extraction, separatory, a large amount of white foam precipitations appear in acidifying, filter, and weigh behind the recrystallization, and feed stock conversion is more than 95%.Product is through liquid chromatographic detection, and content is 91.5%.
Embodiment 2
1) 2,4, the preparation of 6-trimethylammonium chloroacetophenone
In the 36g sym-trimethylbenzene, add the homemade loading type ferric oxide catalyst of 0.180g, in sym-trimethylbenzene solution, drip chloroacetyl chloride 48ml, be warming up to about 80 ℃, continue reaction 6 hours, stopped reaction filters, and reclaims catalyzer, the filtrate acidifying, cooling is also stirred fast, a large amount of solid precipitations occur, weighs after the drying, obtain thick product, reclaim the excess chlorine Acetyl Chloride 98Min..The transformation efficiency of sym-trimethylbenzene is 94%, chloracetyl 2,4, and the selectivity of 6-trimethylbenzene is 95%.Product is through liquid chromatographic detection, and content is 91.7%.
Above-mentioned loading type ferric oxide catalyst is with embodiment 1, be as carrier with zeolite molecular sieve, with the aqueous solution that contains molysite, nickel salt and cobalt salt as steeping fluid, with soaked carrier drying, roast, obtain catalyst precursor, repeat drying again, roast is prepared with the ferric oxide is the loading type ferric oxide Fu Shi catalysts of active ingredient.
2) preparation of mesitylene carboxylic acid
With the product that obtains in the foregoing description 1 as the haloform reaction raw material, with 2,4,1 of 6-trimethylammonium chloroacetophenone (10g), 4-dioxane solution (11ml) splashes into that (wherein chlorine bleach liquor's mass concentration is 11% in the mixing solutions of the clorox that contains Tetrabutyl amonium bromide (0.2g) and sodium hydroxide, solution quality 110g, sodium hydroxide concentration is 11%, volume 10ml), maintains the temperature under 55 ℃ of conditions and reacted 1 hour, add the excessive clorox of bisulfite sodium reduction, continuation adding mass concentration is 40% sodium hydroxide 10ml, be warming up to 80 ℃, continue reaction 5 hours, stopped reaction.
3) with step 2) product extracts, separatory, a large amount of white foams precipitations appear in acidifying, filter, and weigh behind the recrystallization, and feed stock conversion is more than 94%.Product is through liquid chromatographic detection, and content is 90.2%.
Comparative example 1:
In the 36g sym-trimethylbenzene, add 40.95gAlCl
3, the back that stirs at normal temperatures drips chloroacetyl chloride 48ml, is warming up to about 80 ℃, continues reaction 6 hours, stopped reaction, acidifying, cooling is also stirred fast, is transferred in the frozen water, extract with ethyl acetate (200ml), weighed behind drying, the recovery solvent, obtain thick product.Reclaim the excess chlorine Acetyl Chloride 98Min..The transformation efficiency of sym-trimethylbenzene is 80%, chloracetyl 2,4, and the selectivity of 6-trimethylbenzene is 86%.Product is through liquid chromatographic detection, and content is 81%.
Comparative example 2:
In the 36g sym-trimethylbenzene, add 0.072gFe
2O
3, after stirring at normal temperatures, drip chloroacetyl chloride 48ml, be warming up to about 80 ℃, continue reaction 6 hours, stopped reaction, acidifying, cooling is also stirred fast, a large amount of solid precipitations occur, weighs after the drying, and the solid color is general redly (sneaks into Fe
2O
3), obtain thick product.Reclaim the excess chlorine Acetyl Chloride 98Min..The transformation efficiency of sym-trimethylbenzene is 96%, chloracetyl 2,4, and the selectivity of 6-trimethylbenzene is 85%, and product is through liquid chromatographic detection, and content is 84%.
Comparative example 3:
With the product that obtains in the foregoing description 1 as the haloform reaction raw material; weighing acylations product 10g; be connected with one and add 25% aqueous sodium hydroxide solution 45ml in the there-necked flask of ventpipe; feed chlorine; until saturated; the adding massfraction is 10% aqueous sodium hydroxide solution 10ml and phase-transfer catalyst quaternary ammonium salt 0.2g in another there-necked flask; in solution, add the acylations product after being heated to 50 ℃; feed chlorine after reducing by half 5 minutes, after the maintenance temperature, mended one time 40% sodium hydroxide every 30 minutes; reaction continues 2 hours; the sodium hydroxide reflux of continuation adding 40% 5 hours, stopped reaction cools off in the frozen water cryostat; acidifying; a large amount of white foam precipitations occur, filter, weigh behind the recrystallization.Product is through liquid chromatographic detection, and content is 83%.
Claims (10)
1, the synthesis technique of mesitylene carboxylic acid comprises acylation reaction, haloform reaction and hydrolysis reaction successively, it is characterized in that:
(1) acylation reaction: with sym-trimethylbenzene and chloroacetyl chloride is acylations raw material thing, adopts the acylations catalyzer, through steps such as intensification, filtration, filtrate acidifying preparation 2,4,6-trimethylammonium chloroacetophenone;
(2) haloform reaction: with step (1) products therefrom and clorox is raw material, and the employing quaternary ammonium salt is a phase-transfer catalyst, prepares mesitylene carboxylic acid through intensification, reduction reaction step;
(3) hydrolysis reaction: step (2) gained reactant promptly gets final product through extraction separatory, acid neutralization, recrystallization again.
2, the synthesis technique of mesitylene carboxylic acid according to claim 1 is characterized in that: the mass concentration of clorox is 10~20% in the described haloform reaction.
3, the synthesis technique of mesitylene carboxylic acid according to claim 1 and 2 is characterized in that: described sym-trimethylbenzene and chloroacetyl chloride are refinery byproduct C
9Cut-sym-trimethylbenzene and technical grade chloroacetyl chloride.
4, the synthesis technique of mesitylene carboxylic acid according to claim 1 and 2 is characterized in that: described quaternary ammonium salt is benzyltrimethylammonium bromide or Tetrabutyl amonium bromide.
5, the synthesis technique of mesitylene carboxylic acid according to claim 1 and 2 is characterized in that: described acylations catalyzer is a loading type ferric oxide catalyst.
6, according to claim 52,4, the synthesis technique of 6-trimethylbenzoic acid, it is characterized in that: described loading type ferric oxide catalyst with the mixture of metal oxide, zeolite molecular sieve or metal oxide and zeolite molecular sieve as carrier, with the aqueous solution that contains molysite, nickel salt or cobalt salt is steeping fluid, carries out as follows:
1) described carrier is carried out 6~12 hours dipping;
2) with soaked carrier 60~150 ℃ dry 3~8 hours down, 300~700 ℃ of following roasts 4~12 hours, obtain catalyst precursor again;
3) repeat above operation and promptly get final product.
7, the synthesis technique of mesitylene carboxylic acid according to claim 6 is characterized in that: described metal oxide is Al
2O
3, MgO, TiO
2Described zeolite molecular sieve is Na type zeolite, H type zeolite, X type zeolite, y-type zeolite, zeolite beta or A type zeolite or is the mixture of two or more described zeolite.
8, the synthesis technique of mesitylene carboxylic acid according to claim 1 and 2 is characterized in that: the adding mass concentration is 10~20% alkali lye in described haloform reaction; Described 2,4, the mole proportioning of 6-trimethylammonium chloroacetophenone, clorox and alkali lye is 1: 8~15: 0.8~2.
9, the synthesis technique of mesitylene carboxylic acid according to claim 4 is characterized in that: the adding mass concentration is 10~20% alkali lye in described haloform reaction; Described 2,4, the mole proportioning of 6-trimethylammonium chloroacetophenone, clorox and alkali lye is 1: 8~15: 0.8~2.
10, the synthesis technique of mesitylene carboxylic acid according to claim 1 and 2 is characterized in that: the chloroacetyl chloride consumption is 1~3 times of sym-trimethylbenzene weight, and in about 4~6 hours of reaction times, temperature is controlled at 60~90 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2005100479252A CN100569726C (en) | 2005-12-06 | 2005-12-06 | The synthesis technique of mesitylene carboxylic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2005100479252A CN100569726C (en) | 2005-12-06 | 2005-12-06 | The synthesis technique of mesitylene carboxylic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1927800A true CN1927800A (en) | 2007-03-14 |
CN100569726C CN100569726C (en) | 2009-12-16 |
Family
ID=37857955
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2005100479252A Expired - Fee Related CN100569726C (en) | 2005-12-06 | 2005-12-06 | The synthesis technique of mesitylene carboxylic acid |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN100569726C (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105439849A (en) * | 2014-09-02 | 2016-03-30 | 襄阳新叶生物科技有限公司 | Ibuprofen preparation method adopting solid catalyst |
CN110386868A (en) * | 2018-04-23 | 2019-10-29 | 天津墨森科技有限公司 | The preparation method of one kind 2,4,6- trimethylbenzoic acid |
CN111269106A (en) * | 2020-03-24 | 2020-06-12 | 湖州恒远生物化学技术有限公司 | Synthesis method of 4-phenoxybenzoic acid |
CN112707799A (en) * | 2020-12-28 | 2021-04-27 | 杭州宇龙化工有限公司 | Method for preparing 3,4' -dichlorodiphenyl ether from difenoconazole isomer |
CN113387853A (en) * | 2021-06-15 | 2021-09-14 | 利民化学有限责任公司 | Method for preparing 2-chloro-3-methyl-4-methylsulfonylbenzoic acid |
-
2005
- 2005-12-06 CN CNB2005100479252A patent/CN100569726C/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105439849A (en) * | 2014-09-02 | 2016-03-30 | 襄阳新叶生物科技有限公司 | Ibuprofen preparation method adopting solid catalyst |
CN110386868A (en) * | 2018-04-23 | 2019-10-29 | 天津墨森科技有限公司 | The preparation method of one kind 2,4,6- trimethylbenzoic acid |
CN111269106A (en) * | 2020-03-24 | 2020-06-12 | 湖州恒远生物化学技术有限公司 | Synthesis method of 4-phenoxybenzoic acid |
CN112707799A (en) * | 2020-12-28 | 2021-04-27 | 杭州宇龙化工有限公司 | Method for preparing 3,4' -dichlorodiphenyl ether from difenoconazole isomer |
CN112707799B (en) * | 2020-12-28 | 2022-06-21 | 杭州宇龙化工有限公司 | Method for preparing 3,4' -dichlorodiphenyl ether from difenoconazole isomer |
CN113387853A (en) * | 2021-06-15 | 2021-09-14 | 利民化学有限责任公司 | Method for preparing 2-chloro-3-methyl-4-methylsulfonylbenzoic acid |
Also Published As
Publication number | Publication date |
---|---|
CN100569726C (en) | 2009-12-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113956135B (en) | Preparation method of high-yield 4,4' -biphenol | |
CN1927800A (en) | Synthesis process of 2,4,6-trimethyl benzoic acid | |
CN1034531A (en) | The method of dehydrogenating of cyclonene | |
KR20140130747A (en) | Method for preparing solid nitrosyl ruthenium nitrate by using waste catalyst containing ruthenium | |
CN100509721C (en) | Production method of para chlorotoluene | |
CN1193972C (en) | Continuous method for production of cinnamaldehyde and dihydrocinnamaldehyde derivatives | |
CN100567240C (en) | A kind of method of synthesizing 2-ethoxy-phenol | |
CN109456161A (en) | A kind of method of visible light catalytic oxidation fracture carbon-carbon bond | |
CN101619025A (en) | Continuous preparation method for n-pentylamine | |
CN100402485C (en) | Method for reaction rectification coupling continuous preparation of and series acetate | |
CN106316763B (en) | The method of lactone compound aromatisation production aromatic hydrocarbons | |
CN102091637B (en) | Heterogeneous catalyst used in reaction of synthesizing vanillin and preparation method thereof | |
CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
CN113318730B (en) | δ-MnO2Catalyst, preparation method and application thereof | |
CN102093161B (en) | Method for preparing dihydroxyl dicyclohexyl propane | |
CN103709039A (en) | Method for synthesizing methyl (ethyl) gallate through catalysis of Cu-mordenite | |
CN113735677A (en) | Method for preparing cis-pinane by catalyzing hydrogenation of alpha-pinene with L-malic acid intercalation magnalium hydrotalcite loaded ruthenium catalyst | |
CN107879910B (en) | Green synthesis process of 2, 4-dihydroxy benzophenone | |
CN1184202C (en) | Method for preparing N-ethyl carbazole | |
CN101328129B (en) | Preparation of 3-methoxy propanamine | |
CN101037378A (en) | Method for preparing 2-bromine-4-methyl phenol and method for preparing vanillin | |
CN117209377B (en) | Continuous synthesis method of propionyl chloride | |
EP3041816B1 (en) | Lactate production process | |
CN112724086B (en) | Preparation method of 5-amino-4-nitrile-1, 3-diphenylpyrazole | |
CN114539095A (en) | Preparation method of 3- (4-hydroxy-3-methoxy-phenyl) -2-cyano-2-ethyl acrylate |
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: 20091216 Termination date: 20141206 |
|
EXPY | Termination of patent right or utility model |