CN101003480B - Ethane 1,1,2 - ethyl ester tricarboxylic acid, preparation method, and application as plasticizer - Google Patents
Ethane 1,1,2 - ethyl ester tricarboxylic acid, preparation method, and application as plasticizer Download PDFInfo
- Publication number
- CN101003480B CN101003480B CN200710051336A CN200710051336A CN101003480B CN 101003480 B CN101003480 B CN 101003480B CN 200710051336 A CN200710051336 A CN 200710051336A CN 200710051336 A CN200710051336 A CN 200710051336A CN 101003480 B CN101003480 B CN 101003480B
- Authority
- CN
- China
- Prior art keywords
- ethyl ester
- ethane
- diethyl malonate
- acid ethyl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention relates to a method for preparing ethyl ethane-1, 1, 2-tricarboxylate and its application as plasticizer. The method comprises: reacting diethyl malonate and strong alkaline solution at 70-80 deg.C for 10-30 min to obtain intermediate A, adding catalyst 0.5-1 wt.% of diethyl malonate, dropping halogenated ethyl carboxylate within 30-50 min, reacting at 70-80 deg. C for 3-15 h, removing inorganic salt impurities, and vacuum-distilling to obtain ethyl ethane-1,1,2-tricarboxylate. The method has such advantages as simple process, mild reaction conditions, short reaction time, no obvious waste discharge (only NaCl or NaBr as byproduct), and simple post-treatment.
Description
Technical field
The present invention relates to ethane-1,1,2-tricarboxylic acid ethyl ester and preparation method thereof and application as softening agent.
Background technology
Prevailing in the existing plastic plasticizer is dioctyl phthalate (DOP) (DOP) and dibutyl phthalate (DBP).But DOP, DBP itself is toxic, all is (product that comprises phthalic acid) forbidden in European Union and a lot of country.The citrate series products is present universally acknowledged nontoxic " green " environmentally-friendly plastic softening agent, be widely used in food and medical instrumentation package, makeup, daily necessities, toy, military supplies etc., have that consistency is good, plasticizing efficiency is high, nontoxic, easily by advantage such as biological degradation and volatility be little, winter hardiness, photostabilization and have excellent water-resistance, and shock resistance is arranged in resin, do not grow mould.
The prior synthesizing method of citric acid ester plasticizer is to use citric acid and alcohol to prepare in the presence of as the sulfuric acid of catalyzer, its raw material citric acid is main at present to adopt microbe fermentation method to prepare, this method technological process is longer, particularly produce a large amount of organic pollutants and solid waste, these pollutents are contaminate environment not only, and quantity discharged is big.Therefore environmental problem always is the principal element of restriction citric acid industry development for a long time, and then has also influenced the extensive promotion and application of citric acid ester plasticizer.If can or have the compound of similar structures, will greatly promote the marketing and the widespread use of citric acid ester plasticizer, but do not see research and the report that this respect is arranged at present by the direct synthesizing citric acid ester of chemical process.
Citrate and acetyl citrate are present universally acknowledged nontoxic " green " environmentally-friendly plastic softening agent, be widely used in food and medical instrumentation package, makeup, daily necessities, toy, military supplies etc., have that consistency is good, plasticizing efficiency is high, nontoxic, easily by advantage such as biological degradation and volatility be little, winter hardiness, photostabilization and have excellent water-resistance, and shock resistance is arranged in resin, do not grow mould.Citric acid ester plasticizer becomes the ideal substitute of present conventional plasticizers phthalate.
The prior synthesizing method of citric acid ester plasticizer is to use citric acid and alcohol to prepare (Song Qihuang chief editor in the presence of as the sulfuric acid of catalyzer; fine chemistry industry technology; Beijing: Chemical Industry Press; 1995:95); acetyl lemon ester plasticizer then will carry out acetylize with diacetyl oxide etc. again and make (Cao Wenjun, Hebei chemical industry, 1999 after esterification; 4,5-6).Side reaction is many in the process, refining difficulty, and equipment corrosion is serious, and the aftertreatment complexity produces industry " three wastes ", and shortcomings such as contaminate environment are used and have been subjected to very big restriction.In addition, from its raw material citric acid, the preparation of main at present employing microbe fermentation method, this method technological process is longer, particularly produces a large amount of organic pollutants and solid waste, and these pollutents are contaminate environment not only, and quantity discharged is big.Therefore environmental problem always is the principal element of restriction citric acid industry development for a long time.The Pollution abatement measure that present most of factory adopts is the method for end treatment basically, not only bad for the recycling useful resources of recovery, and equipment has high input the running expense height, cause the strained market supply of citric acid, and then also influenced the development of citric acid ester plasticizer.
Ethane-1,1,2-tricarboxylic acid ethyl ester yet there are no report as the application of softening agent.
Compare citric acid ester plasticizer, ethane-1,1, the 2-tricarboxylic acid ethyl ester three wastes in preparation process produce fewer, and it is more competitive aspect environmental protection that it becomes novel softening agent.
Summary of the invention
The object of the present invention is to provide ethane-1,1,2-tricarboxylic acid ethyl ester and preparation method thereof and application as softening agent.
Technical scheme of the present invention is:
Ethane-1,1,2-tricarboxylic acid ethyl ester is as the application of softening agent.
Ethane-1,1, the English of 2-tricarboxylic acid ethyl ester:
Triethyl ethane-1,1,2-tricarboxylate is called for short TETC.
Ethane-1,1, the preparation method of 2-tricarboxylic acid ethyl ester; get diethyl malonate and strong base solution and obtained intermediate product A in 10-30 minute 70-80 ℃ of reaction in advance; adding by the diethyl malonate weight ratio in intermediate product A then is the catalyzer of 0.5-1%; and in 30-50 minute, dropwise the halogenated carboxylic acid ethyl ester and continue reaction; dripping behind the halogenated carboxylic acid ethyl ester in temperature is reaction 3-15 hour under the 70-80 ℃ of condition; remove inorganic salt impurity after reaction finishes; underpressure distillation obtains ethane-1; 1,2-tricarboxylic acid ethyl ester; Wherein: strong base solution is the sodium methylate of mass percent concentration 18-21% or the ethanolic soln of sodium ethylate; Catalyzer is potassiumiodide, sodium iodide or iodine; The halogenated acetic acids ethyl ester is ethyl chloroacetate or ethyl bromoacetate; Diethyl malonate: sodium methylate or sodium ethylate: the mole metering of halogenated acetic acids ethyl ester is than being 1.0-1.1: 1: 1.0-1.1.
Inorganic salt impurity is the by product that reaction obtains, and using conventional washing or filter can be with principal product ethane-1,1, and 2-tricarboxylic acid ethyl ester and inorganic salt impurity are separated.
Ethane-1,1, the preparation method of 2-tricarboxylic acid ethyl ester, the step of removing inorganic salt impurity is specially: add the salt that generation is dissolved in entry, divide oil-yielding stratum, oil reservoir carries out drying and underpressure distillation, obtains ethane-1,1,2-tricarboxylic acid ethyl ester.
Ethane-1,1, the preparation method of 2-tricarboxylic acid ethyl ester, the step of removing inorganic salt impurity is specially: the salt that direct filtration generates, underpressure distillation gets ethane-1,1,2-tricarboxylic acid ethyl ester.
Ethane-1,1,2-tricarboxylic acid ethyl ester, the colourless or slightly yellowy transparent liquid of this material.Can find that by TETC and the plasticising performance contrast experiment of the plasticizer phthalic acid dioctyl ester DOP of routine the plasticizing efficiency of TETC, cold-resistant value etc. all is in same level with DOP, consistency is slightly better than DOP.
The plasticising performance compares:
| TETC | DOP | |
| Relative molecular mass | 246.26 | 390.57 |
| Flash-point (opening cup)/℃ | 215 | 210 |
| Esterification value (KOH mg/g) | 280±3 | 287±3 |
| Consistency (solubility parameter) | 9.0 | 8.9 |
| Plasticizing efficiency (Reed value) | 32 | 33.5 |
| Cold-resistant value (50) | -10～-18℃ | -10～-25℃ |
The available following general formula of reaction of the present invention is represented:
The chemical structure of triethyl citrate is as follows:
The present invention synthesizes ethane-1,1, and 2-tricarboxylic acid ethyl ester (TETC) comprises following concrete steps:
A, hydrocarbyl reaction
The diethyl malonate that in the three-necked bottle that induction stirring, thermometer, reflux condensing tube (on add drying tube) are housed, adds 0.10mol, 0.10-0.11mol sodium methylate (methyl alcohol) or sodium ethylate (ethanol) solution, after temperature reaction 10-30 minute, add little amount of catalyst potassiumiodide or iodine, begin to drip ethyl chloroacetate or the ethyl bromoacetate of 0.10mol then, the dropping time is 30-50 minute, dropwises 3-15 hour stopped reaction of back back flow reaction.
The separation of B, inorganic salt and the purifying of product
Separation and purifying can be undertaken by two kinds of methods, and a kind of method is that direct filtration goes out inorganic salt, and air distillation goes out methyl alcohol or ethanol and low-boiling point material, the cut of 140-145 ℃ (20mmHg) is collected in underpressure distillation then, get water white transparency product ethane-1,1,2-tricarboxylic acid ethyl ester (TETC); Another kind method is the inorganic salt that are dissolved in water and separate out in the mixture behind hydrocarbyl reaction, separates oil reservoir, and dry back underpressure distillation is collected the boiling spread product and got the finished product.
With synthetic the comparing of background technology acetyl tributyl citrate ethyl ester, advantage of the present invention is that preparation method's technology of (1) the present invention employing is simple, and facility investment is less demanding, the reaction conditions gentleness, and the reaction times is shorter; (2) do not use citric acid to be starting raw material, be not subjected to the restriction of citric acid market supply; (3) do not have obvious waste discharge, having only NaCl or NaBr is by product; (4) last handling process is simple; (5) do not use the material of containing benezene, and traditional citrate synthetic often uses toluene etc. to be the band aqua; (6) the present invention also contrasts by experiment and has searched out ethane-1,1, and 2-tricarboxylic acid ethyl ester is ethane-1,1 as the new application of softening agent, and 2-tricarboxylic acid ethyl ester substitutes other softening agent and found theoretical foundation.
Embodiment
Embodiment 1, ethane-1,1, the preparation method of 2-tricarboxylic acid ethyl ester; get diethyl malonate and strong base solution and obtained intermediate product A in 10 minutes 70 ℃ of reactions in advance; adding in intermediate product A by the diethyl malonate weight ratio then is 0.5% catalyzer; and in 30 minutes, dropwise the halogenated carboxylic acid ethyl ester and continue reaction; dripping behind the halogenated carboxylic acid ethyl ester in temperature is reaction 3 hours under 70 ℃ of conditions; remove inorganic salt impurity after reaction finishes; underpressure distillation obtains ethane-1; 1,2-tricarboxylic acid ethyl ester; Wherein: strong base solution is the sodium methylate of mass percent concentration 18% or the ethanolic soln of sodium ethylate; Catalyzer is potassiumiodide, sodium iodide or iodine; The halogenated acetic acids ethyl ester is ethyl chloroacetate or ethyl bromoacetate; Diethyl malonate: sodium methylate or sodium ethylate: the mole metering of halogenated acetic acids ethyl ester is than being 1.0: 1: 1.0.
Embodiment 2, ethane-1,1, the preparation method of 2-tricarboxylic acid ethyl ester; get diethyl malonate and strong base solution and obtained intermediate product A in 30 minutes 80 ℃ of reactions in advance; adding in intermediate product A by the diethyl malonate weight ratio then is 1% catalyzer; and in 50 minutes, dropwise the halogenated carboxylic acid ethyl ester and continue reaction; dripping behind the halogenated carboxylic acid ethyl ester in temperature is reaction 15 hours under 80 ℃ of conditions; remove inorganic salt impurity after reaction finishes; underpressure distillation obtains ethane-1; 1,2-tricarboxylic acid ethyl ester; Wherein: strong base solution is the sodium methylate of mass percent concentration 21% or the ethanolic soln of sodium ethylate; Catalyzer is potassiumiodide, sodium iodide or iodine; The halogenated acetic acids ethyl ester is ethyl chloroacetate or ethyl bromoacetate; Diethyl malonate: sodium methylate or sodium ethylate: the mole metering of halogenated acetic acids ethyl ester is than being 1.1: 1: 1.1.
Embodiment 3, ethane-1,1, the preparation method of 2-tricarboxylic acid ethyl ester; get diethyl malonate and strong base solution and obtained intermediate product A in 20 minutes 75 ℃ of reactions in advance; adding in intermediate product A by the diethyl malonate weight ratio then is 0.8% catalyzer; and in 40 minutes, dropwise the halogenated carboxylic acid ethyl ester and continue reaction; dripping behind the halogenated carboxylic acid ethyl ester in temperature is reaction 10 hours under 75 ℃ of conditions; remove inorganic salt impurity after reaction finishes; underpressure distillation obtains ethane-1; 1,2-tricarboxylic acid ethyl ester; Wherein: strong base solution is the sodium methylate of mass percent concentration 20% or the ethanolic soln of sodium ethylate; Catalyzer is potassiumiodide, sodium iodide or iodine; The halogenated acetic acids ethyl ester is ethyl chloroacetate or ethyl bromoacetate; Diethyl malonate: sodium methylate or sodium ethylate: the mole metering of halogenated acetic acids ethyl ester is than being 1.05: 1: 1.05.
Embodiment 4, (1) are stirred and down diethyl malonate joined mass percent concentration is in 18.0% alcohol sodium alcohol solution, and the mol ratio of diethyl malonate and sodium ethylate is 1: 1.1, is warming up to 80 ℃ of reactions 30 minutes;
(2) add the catalyzer potassiumiodide, the mass ratio of potassiumiodide and diethyl malonate is 1: 100;
(3) dripping bromine ethyl acetate, the mol ratio of ethyl bromoacetate and diethyl malonate are 1: 1, and the dropping time is 30 minutes, and 80 ℃ were reacted 3 hours, and reduced to room temperature;
(4) inorganic salt that are dissolved in water and separate out are isolated underpressure distillation behind the oil reservoir, collect the boiling spread product, reclaim unreacted raw material and etoh solvent simultaneously.In the diethyl malonate productive rate is 87%.
All the other are with embodiment 1.
Stir embodiment 5, (1) is that 19.0% methanol solution of sodium methylate joins in the diethyl malonate with mass percent concentration down, and the mol ratio of diethyl malonate and sodium methylate is 1: 1.0, is warming up to 70 ℃ of reactions 20 minutes;
(2) add catalyst simple substance iodine, the mass ratio of iodine and diethyl malonate is 1: 200;
(3) drip ethyl chloroacetate, the mol ratio of ethyl chloroacetate and diethyl malonate is 1: 1, and the dropping time is 40 minutes, and 75 ℃ were reacted 12 hours, and reduced to room temperature;
(4) filter the inorganic salt of separating out, the boiling spread product is collected in underpressure distillation, reclaims unreacted raw material and solvent methanol simultaneously.In the diethyl malonate productive rate is 86%.All the other are with embodiment 1.
Embodiment 6, (1) are stirred and down diethyl malonate joined mass percent concentration is in 20.0% alcohol sodium alcohol solution, and the mol ratio of diethyl malonate and sodium ethylate is 1: 1.1, is warming up to 80 ℃ of reactions 15 minutes;
(2) add catalyst simple substance iodine, the mass ratio of iodine and diethyl malonate is 1: 180;
(3) drip ethyl chloroacetate, the mol ratio of ethyl chloroacetate and diethyl malonate is 1: 1, and the dropping time is 50 minutes, and 80 ℃ were reacted 15 hours, and reduced to room temperature;
(4) filter the inorganic salt of separating out, the boiling spread product is collected in underpressure distillation, reclaims unreacted raw material and etoh solvent simultaneously.In the diethyl malonate productive rate is 90%.All the other are with embodiment 1.
Stir embodiment 7, (1) is that 18.0% alcohol sodium alcohol solution joins in the diethyl malonate with mass percent concentration down, and the mol ratio of diethyl malonate and sodium ethylate is 1: 1, is warming up to 80 ℃ of reactions 20 minutes;
(2) add the catalyzer sodium iodide, the mass ratio of sodium iodide and diethyl malonate is 1: 110;
(3) dripping bromine ethyl acetate, the mol ratio of ethyl bromoacetate and diethyl malonate are 1: 1, and the dropping time is 45 minutes, and 80 ℃ were reacted 5 hours, and reduced to room temperature;
(4) inorganic salt that are dissolved in water and separate out are isolated underpressure distillation behind the oil reservoir, collect the boiling spread product, reclaim unreacted raw material and etoh solvent simultaneously.In the diethyl malonate productive rate is 84%.All the other are with embodiment 1.
Embodiment 8, (1) are stirred and down diethyl malonate joined mass percent concentration is in 20.0% methanol solution of sodium methylate, and the mol ratio of diethyl malonate and sodium methylate is 1: 1.1, is warming up to 70 ℃ of reactions 10 minutes;
(2) add the catalyst simple substance potassiumiodide, the mass ratio of potassiumiodide and diethyl malonate is 1: 100;
(3) drip ethyl chloroacetate, the mol ratio of ethyl chloroacetate and diethyl malonate is 1: 1, and the dropping time is 30 minutes, and 75 ℃ were reacted 15 hours, and reduced to room temperature;
(4) filter the inorganic salt of separating out, the boiling spread product is collected in underpressure distillation, reclaims unreacted raw material and solvent methanol simultaneously.In the diethyl malonate productive rate is 87%.All the other are with embodiment 1.
Claims (1)
1. ethane-1,1, the preparation method of 2-tricarboxylic acid ethyl ester; get diethyl malonate and strong base solution and obtained intermediate product A in 10-30 minute 70-80 ℃ of reaction in advance; adding by the diethyl malonate weight ratio in intermediate product A then is the catalyzer of 0.5-1%; and in 30-50 minute, dropwise the halogenated carboxylic acid ethyl ester and continue reaction; dripping behind the halogenated carboxylic acid ethyl ester in temperature is reaction 3-15 hour under the 70-80 ℃ of condition; remove inorganic salt impurity after reaction finishes; underpressure distillation obtains ethane-1; 1,2-tricarboxylic acid ethyl ester; It is characterized in that: strong base solution is the sodium methylate of mass percent concentration 18-21% or the ethanolic soln of sodium ethylate; Catalyzer is potassiumiodide, sodium iodide or iodine; The halogenated acetic acids ethyl ester is ethyl chloroacetate or ethyl bromoacetate; Diethyl malonate: sodium methylate or sodium ethylate: the mole metering of halogenated acetic acids ethyl ester is than being 1.0-1.1: 1: 1.0-1.1; Reaction removes the inorganic salt separate impurities after finishing and purifying is undertaken by following method: direct filtration goes out inorganic salt, air distillation goes out methyl alcohol or ethanol, and 140-145 ℃ cut is collected in underpressure distillation under the 20mmHg condition then, gets water white ethane-1,1,2-tricarboxylic acid ethyl ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710051336A CN101003480B (en) | 2007-01-23 | 2007-01-23 | Ethane 1,1,2 - ethyl ester tricarboxylic acid, preparation method, and application as plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710051336A CN101003480B (en) | 2007-01-23 | 2007-01-23 | Ethane 1,1,2 - ethyl ester tricarboxylic acid, preparation method, and application as plasticizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101003480A CN101003480A (en) | 2007-07-25 |
| CN101003480B true CN101003480B (en) | 2010-05-19 |
Family
ID=38702910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710051336A Expired - Fee Related CN101003480B (en) | 2007-01-23 | 2007-01-23 | Ethane 1,1,2 - ethyl ester tricarboxylic acid, preparation method, and application as plasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101003480B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2296657A1 (en) * | 1974-12-30 | 1976-07-30 | Aquitaine Petrole | PVC plasticizers having low exudation - comprise a mixt. of esters of butane-1,2,5-tricarboxylic acid, propane-1,2,3-tricarboxylic acid and opt. succinic acid |
| CN1535675A (en) * | 2003-02-25 | 2004-10-13 | 莱雅公司 | Cosmetic omposition containing polymer granules dispersion and plasticizing polymer compound |
-
2007
- 2007-01-23 CN CN200710051336A patent/CN101003480B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2296657A1 (en) * | 1974-12-30 | 1976-07-30 | Aquitaine Petrole | PVC plasticizers having low exudation - comprise a mixt. of esters of butane-1,2,5-tricarboxylic acid, propane-1,2,3-tricarboxylic acid and opt. succinic acid |
| CN1535675A (en) * | 2003-02-25 | 2004-10-13 | 莱雅公司 | Cosmetic omposition containing polymer granules dispersion and plasticizing polymer compound |
Non-Patent Citations (3)
| Title |
|---|
| JP特开平4-342748A 1992.11.30 |
| 石万聪 等.增塑剂及其应用 1.化学工业出版社,2002,412-421. |
| 石万聪 等.增塑剂及其应用 1.化学工业出版社,2002,412-421. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101003480A (en) | 2007-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101184715B (en) | Process for the production of alpha, gamma-dichlorohydrin from glycerin and hydrochloric acid | |
| CN102757308A (en) | Method of preparing high-purity ethanol | |
| CN103827072A (en) | Method for recovering acetic acid | |
| CN101348451B (en) | Preparation of medicinal D,L-2-hydroxy-4-methylthio calcium butyrate | |
| CN102775310B (en) | Synthesis method of dibasic alcohol bi-benzoate | |
| CN100349849C (en) | Method for preparing tributyl citrate using mesoporous molecular sieve as catalyst | |
| CN105085980A (en) | Synthesis of citric acid ether ester plasticizer | |
| CN101805260B (en) | Preparation method of gefarnate | |
| CN101003480B (en) | Ethane 1,1,2 - ethyl ester tricarboxylic acid, preparation method, and application as plasticizer | |
| CN100473682C (en) | Application of propane 1, 2, 2, 3 - ethyl ester tetracarboxylic acid as plasticizer, and preparation method thereof | |
| CN101092360B (en) | Method for catalyzing and synthesizing tri-butyl citrate from methylal naphthalene sulfonic acid | |
| CN101463011A (en) | Process for synthesizing 3,4-dihydropyrimidine-2-keto | |
| CN101585776B (en) | Method for synthetizing N,N-diisopropylethylamine | |
| CN110713439A (en) | Preparation method of cyclohexane-1, 2-dicarboxylate environment-friendly plasticizer | |
| CN113045412A (en) | Preparation process and equipment of adipic acid dibasic ester | |
| CN116283654A (en) | Process for efficiently preparing dopamine hydrochloride bulk drug | |
| CN101391957B (en) | Method for preparing tributyl citrate by using rare-earth salt binary complex type solid acid as catalyst | |
| CN1974532B (en) | Prepn and application of diisopropyl diethyl carboxylate | |
| CN100537512C (en) | Preparation and application of isopropyl diethyl carboxylate | |
| CN101012167A (en) | Carboxylate and its preparing method and application | |
| CN100453521C (en) | Prepn and application of ethyl diisopropyl carboxylate | |
| CN1974530B (en) | Prepn and application of triisopropyl carboxylate | |
| CN100480229C (en) | Preparation and application of tetraisopropyl carboxylate | |
| CN101883761B (en) | New process for the synthesis of moguisteine | |
| CN101006044A (en) | Purification method of terephthal aldehyde |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100519 Termination date: 20120123 |