CN102249964A - Process for preparing isooctyl thioglycolate - Google Patents
Process for preparing isooctyl thioglycolate Download PDFInfo
- Publication number
- CN102249964A CN102249964A CN2011101404780A CN201110140478A CN102249964A CN 102249964 A CN102249964 A CN 102249964A CN 2011101404780 A CN2011101404780 A CN 2011101404780A CN 201110140478 A CN201110140478 A CN 201110140478A CN 102249964 A CN102249964 A CN 102249964A
- Authority
- CN
- China
- Prior art keywords
- virahol
- isooctyl
- sulfhydrylation
- product
- still
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process for preparing isooctyl thioglycolate. The process provided by the invention is characterized in that chloroacetic acid is taken as a raw material, the chloroacetic acid and isooctanol are subjected to an esterification reaction in the presence of a catalyst to synthesize isooctyl chloroacetate; then the isooctyl chloroacetate and sodium thiosulfate are reacted to form a Bunte salt and the Bunte salt is subjected to acidolysis and reduction to obtain a rough product of the isooctyl thioglycolate; and the rough product is rectified to obtain the finished product of the isooctyl thioglycolate. The process for preparing the isooctyl thioglycolate has higher yield; the isopropanol is used as the solvent. the experiment shows that the yield can be about 65% and the yield is improved by about 5% compared with the yield obtained by taking methanol, ethanol and the like as the solvent; and the time for recycling the isopropanol is only about 2.5 hours and the time is shortened by about 2 hours compared with the time for recycling the methanol, ethanol and the like so that the relative energy consumption is greatly reduced.
Description
Technical field
The present invention relates to a kind of preparation technology of preparation technology, particularly a kind of isooctyl mercaptoacetate of intermediate of P V C thermo-stabilizer.
Background technology
Isooctyl mercaptoacetate is the intermediate of synthesizing efficient low toxicity organic tin P V C thermo-stabilizer, resistance side chain agent when also can be used as P V C resin polymerization simultaneously and dihydroxyphenyl propane synthetic catalyzer.
Synthetic isooctyl mercaptoacetate mainly contains two operational paths in the prior art: the one, and earlier synthetic Thiovanic acid, the direct esterification method of carrying out esterification then with isooctyl alcohol; Another route is the different monooctyl ester of first synthesis of chloroacetic acid, carries out sulfhydrylation then.For last route, by experiment, think the problem that has two aspects; The one, the synthetic Thiovanic acid cost that obtains is higher, and the ester reaction is difficult to reach the ideal transformation efficiency; The 2nd, in the separation and esterification reaction process of acid, sulfydryl is oxidized and thermal degradation easily.The factor of this two aspect all will cause production cost higher.And for a kind of method in back, what it adopted is that B u n t c salt method is carried out sulfhydrylation.
Summary of the invention
Technical problem to be solved by this invention is at the deficiencies in the prior art, and the preparation technology of the isooctyl mercaptoacetate that a kind of technology is more reasonable, productive rate is higher, energy consumption is less is provided.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of preparation technology of isooctyl mercaptoacetate, it is characterized in that, its step is as follows:
(1) esterification: earlier Mono Chloro Acetic Acid is added reactor, be metered into the isooctyl alcohol and the catalyzer vitriol oil again, divide the waterside esterification in the following distillation of reduced pressure, after reaction finishes, carry out yellow soda ash, common salt aqueous solution washing, washing again, washes removes the wastewater collection jar, esterification products de-esterifying thing storage tank; Open the water trap bottom valve, moisture is gone into wastewater trough, remaining ester-pure mixed solution is inserted in next batch; Wherein: the weight ratio of Mono Chloro Acetic Acid, isooctyl alcohol and catalyzer is 800:1000-1150:8-10;
(2) mercaptolation: the carboxylate metering of carboxylate storage tank is got to the carboxylate test tank and put into reactor, the Virahol metering is extracted into the Virahol test tank and puts into reactor, add an amount of sodium thiosulfate again, carry out the sulfhydrylation back flow reaction; Reaction finishes the back and reclaims Virahol; Add mass percent concentration then and be not less than 30% hydrochloric acid and be hydrolyzed, hydrolysis finishes the back and add a certain amount of clear water in still, and it is static to stir the back, divides water-yielding stratum to wastewater trough, the stand-by next operation of sulfhydrylation product in the still; Wherein: the weight ratio of the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine, Virahol, hydrochloric acid is 1030:1200-1300:710-800:500-600;
(3) reduction reaction: the sulfhydrylation product is added the reduction reaction still, accurately drop into zinc powder in proportion, slowly put into mass percent concentration then and be not less than 30% hydrochloric acid and carry out reduction reaction; Reaction finishes after; Add a certain amount of clear water and with an amount of yellow soda ash saturated aqueous common salt solution washing, change material over to static groove after the washing in still, after the static layering, branch vibration layer goes the sulfhydrylation waste water tank, and crude product ester layer removes the crude product storage tank; Wherein: content/6 of sulfide in the weight ratio 1030:1030 of sulfhydrylation product, zinc powder and hydrochloric acid * sulfhydrylation product: zinc powder amount * 6;
(4) rectifying: crude product is imported the smart still that steams, carry out underpressure distillation, the material temperature is no more than 190 ℃ in the reactor, the system vacuum degree is-0.1Mpa, the mass content that the mass content of collecting isooctyl mercaptoacetate respectively is lower than 98% front-end volatiles, isooctyl mercaptoacetate is the middle runnings of 98-99%, and the mass content of isooctyl mercaptoacetate is the finished product cut more than 99%.
The reaction equation of technology of the present invention is as follows:
Esterification (synthesizing of the different monooctyl ester of Mono Chloro Acetic Acid):
Synthetic (sulfhydrylation) of Thiovanic acid
(1) Bunte's is synthetic:
(2) hydrolysis of Bunte:
(3) hydrolytic side reactions of Bunte:
(4) by product reduction (reduction reaction):
The preparation technology's of above-described isooctyl mercaptoacetate preferred feature is:
1, in the step (1), the weight ratio of Mono Chloro Acetic Acid, isooctyl alcohol and catalyzer is=800:1090:9; In the step (2), the weight ratio of the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine, Virahol, hydrochloric acid is 1030:1250:760:552.
2, the recovery method of Virahol is in the step (2): the Virahol mass percent concentration that mercaptolation is steamed is 30% liquid caustic soda adjustment pH to 10 earlier, and Virahol is reclaimed in rectifying under normal pressure.
Compared with prior art, the preparation technology's of isooctyl mercaptoacetate of the present invention productive rate is higher, it uses Virahol to make solvent, can reach about 65% through its productive rate of measuring, improve productive rate about 5% than make solvent with methyl alcohol, ethanol etc., the recovery of Virahol only needed about 2.5 hours, shortened about 2 hours than the recovery time of methyl alcohol, ethanol equal solvent, had therefore also significantly reduced relative energy consumption.
Embodiment
Below further describe concrete technical scheme of the present invention,, and do not constitute restriction its right so that those skilled in the art understands the present invention further.
Embodiment 1.A kind of preparation technology of isooctyl mercaptoacetate, its step is as follows:
(1) esterification: earlier Mono Chloro Acetic Acid is added reactor, be metered into the isooctyl alcohol and the catalyzer vitriol oil again, divide the waterside esterification in the following distillation of reduced pressure, after reaction finishes, carry out yellow soda ash, common salt aqueous solution washing, washing again, washes removes the wastewater collection jar, esterification products de-esterifying thing storage tank; Open the water trap bottom valve, moisture is gone into wastewater trough, remaining ester-pure mixed solution is inserted in next batch; Wherein: the weight ratio of Mono Chloro Acetic Acid, isooctyl alcohol and catalyzer is 800:1000:8;
(2) mercaptolation: the carboxylate metering of carboxylate storage tank is got to the carboxylate test tank and put into reactor, the Virahol metering is extracted into the Virahol test tank and puts into reactor, add an amount of sodium thiosulfate again, carry out the sulfhydrylation back flow reaction; Reaction finishes the back and reclaims Virahol; Add mass percent concentration then and be not less than 30% hydrochloric acid and be hydrolyzed, hydrolysis finishes the back and add a certain amount of clear water in still, and it is static to stir the back, divides water-yielding stratum to wastewater trough, the stand-by next operation of sulfhydrylation product in the still; Wherein: the weight ratio of the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine, Virahol, hydrochloric acid is 1030:1200:710:500;
(3) reduction reaction: the sulfhydrylation product is added the reduction reaction still, accurately drop into zinc powder in proportion, slowly put into mass percent concentration then and be not less than 30% hydrochloric acid and carry out reduction reaction; Reaction finishes after; Add a certain amount of clear water and with an amount of yellow soda ash saturated aqueous common salt solution washing, change material over to static groove after the washing in still, after the static layering, branch vibration layer goes the sulfhydrylation waste water tank, and crude product ester layer removes the crude product storage tank; Wherein: content/6 of sulfide in the weight ratio 1030:1030 of sulfhydrylation product, zinc powder and hydrochloric acid * sulfhydrylation product: zinc powder amount * 6;
(4) rectifying: crude product is imported the smart still that steams, carry out underpressure distillation, the material temperature is no more than 190 ℃ in the reactor, the system vacuum degree is-0.1Mpa, the mass content that the mass content of collecting isooctyl mercaptoacetate respectively is lower than 98% front-end volatiles, isooctyl mercaptoacetate is the middle runnings of 98-99%, and the mass content of isooctyl mercaptoacetate is the finished product cut more than 99%.
Embodiment 2.A kind of preparation technology of isooctyl mercaptoacetate, its step is as follows:
(1) esterification: earlier Mono Chloro Acetic Acid is added reactor, be metered into the isooctyl alcohol and the catalyzer vitriol oil again, divide the waterside esterification in the following distillation of reduced pressure, after reaction finishes, carry out yellow soda ash, common salt aqueous solution washing, washing again, washes removes the wastewater collection jar, esterification products de-esterifying thing storage tank; Open the water trap bottom valve, moisture is gone into wastewater trough, remaining ester-pure mixed solution is inserted in next batch; Wherein: the weight ratio of Mono Chloro Acetic Acid, isooctyl alcohol and catalyzer is 800:1150:10;
(2) mercaptolation: the carboxylate metering of carboxylate storage tank is got to the carboxylate test tank and put into reactor, the Virahol metering is extracted into the Virahol test tank and puts into reactor, add an amount of sodium thiosulfate again, carry out the sulfhydrylation back flow reaction; Reaction finishes the back and reclaims Virahol; Add mass percent concentration then and be not less than 30% hydrochloric acid and be hydrolyzed, hydrolysis finishes the back and add a certain amount of clear water in still, and it is static to stir the back, divides water-yielding stratum to wastewater trough, the stand-by next operation of sulfhydrylation product in the still; Wherein: the weight ratio of the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine, Virahol, hydrochloric acid is 1030:1300:800:600;
(3) reduction reaction: the sulfhydrylation product is added the reduction reaction still, accurately drop into zinc powder in proportion, slowly put into mass percent concentration then and be not less than 30% hydrochloric acid and carry out reduction reaction; Reaction finishes after; Add a certain amount of clear water and with an amount of yellow soda ash saturated aqueous common salt solution washing, change material over to static groove after the washing in still, after the static layering, branch vibration layer goes the sulfhydrylation waste water tank, and crude product ester layer removes the crude product storage tank; Wherein: content/6 of sulfide in the weight ratio 1030:1030 of sulfhydrylation product, zinc powder and hydrochloric acid * sulfhydrylation product: zinc powder amount * 6;
(4) rectifying: crude product is imported the smart still that steams, carry out underpressure distillation, the material temperature is no more than 190 ℃ in the reactor, the system vacuum degree is-0.1Mpa, the mass content that the mass content of collecting isooctyl mercaptoacetate respectively is lower than 98% front-end volatiles, isooctyl mercaptoacetate is the middle runnings of 98-99%, and the mass content of isooctyl mercaptoacetate is the finished product cut more than 99%.
Embodiment 3.A kind of preparation technology of isooctyl mercaptoacetate, its step is as follows:
(1) esterification: earlier Mono Chloro Acetic Acid is added reactor, be metered into the isooctyl alcohol and the catalyzer vitriol oil again, divide the waterside esterification in the following distillation of reduced pressure, after reaction finishes, carry out yellow soda ash, common salt aqueous solution washing, washing again, washes removes the wastewater collection jar, esterification products de-esterifying thing storage tank; Open the water trap bottom valve, moisture is gone into wastewater trough, remaining ester-pure mixed solution is inserted in next batch; Wherein: the weight ratio of Mono Chloro Acetic Acid, isooctyl alcohol and catalyzer is 800:1090:9;
(2) mercaptolation: the carboxylate metering of carboxylate storage tank is got to the carboxylate test tank and put into reactor, the Virahol metering is extracted into the Virahol test tank and puts into reactor, add an amount of sodium thiosulfate again, carry out the sulfhydrylation back flow reaction; Reaction finishes the back and reclaims Virahol; Add mass percent concentration then and be not less than 30% hydrochloric acid and be hydrolyzed, hydrolysis finishes the back and add a certain amount of clear water in still, and it is static to stir the back, divides water-yielding stratum to wastewater trough, the stand-by next operation of sulfhydrylation product in the still; Wherein: the weight ratio of the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine, Virahol, hydrochloric acid is 1030:1250:760:552; The recovery method of Virahol is: the Virahol mass percent concentration that mercaptolation is steamed is 30% liquid caustic soda adjustment pH to 10 earlier, and Virahol is reclaimed in rectifying under normal pressure;
(3) reduction reaction: the sulfhydrylation product is added the reduction reaction still, accurately drop into zinc powder in proportion, slowly put into mass percent concentration then and be not less than 30% hydrochloric acid and carry out reduction reaction; Reaction finishes after; Add a certain amount of clear water and with an amount of yellow soda ash saturated aqueous common salt solution washing, change material over to static groove after the washing in still, after the static layering, branch vibration layer goes the sulfhydrylation waste water tank, and crude product ester layer removes the crude product storage tank; Wherein: content/6 of sulfide in the weight ratio 1030:1030 of sulfhydrylation product, zinc powder and hydrochloric acid * sulfhydrylation product: zinc powder amount * 6;
(4) rectifying: crude product is imported the smart still that steams, carry out underpressure distillation, the material temperature is no more than 190 ℃ in the reactor, the system vacuum degree is-0.1Mpa, the mass content that the mass content of collecting isooctyl mercaptoacetate respectively is lower than 98% front-end volatiles, isooctyl mercaptoacetate is the middle runnings of 98-99%, and the mass content of isooctyl mercaptoacetate is the finished product cut more than 99%.
Claims (3)
1. the preparation technology of an isooctyl mercaptoacetate is characterized in that, its step is as follows:
(1) esterification: earlier Mono Chloro Acetic Acid is added reactor, be metered into the isooctyl alcohol and the catalyzer vitriol oil again, divide the waterside esterification in the following distillation of reduced pressure, after reaction finishes, carry out yellow soda ash, common salt aqueous solution washing, washing again, washes removes the wastewater collection jar, esterification products de-esterifying thing storage tank; Open the water trap bottom valve, moisture is gone into wastewater trough, remaining ester-pure mixed solution is inserted in next batch; Wherein: the weight ratio of Mono Chloro Acetic Acid, isooctyl alcohol and catalyzer is 800:1000-1150:8-10;
(2) mercaptolation: the carboxylate metering of carboxylate storage tank is got to the carboxylate test tank and put into reactor, the Virahol metering is extracted into the Virahol test tank and puts into reactor, add an amount of sodium thiosulfate again, carry out the sulfhydrylation back flow reaction; Reaction finishes the back and reclaims Virahol; Add mass percent concentration then and be not less than 30% hydrochloric acid and be hydrolyzed, hydrolysis finishes the back and add a certain amount of clear water in still, and it is static to stir the back, divides water-yielding stratum to wastewater trough, the stand-by next operation of sulfhydrylation product in the still; Wherein: the weight ratio of the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine, Virahol, hydrochloric acid is 1030:1200-1300:710-800:500-600;
(3) reduction reaction: the sulfhydrylation product is added the reduction reaction still, accurately drop into zinc powder in proportion, slowly put into mass percent concentration then and be not less than 30% hydrochloric acid and carry out reduction reaction; Reaction finishes after; Add a certain amount of clear water and with an amount of yellow soda ash saturated aqueous common salt solution washing, change material over to static groove after the washing in still, after the static layering, branch vibration layer goes the sulfhydrylation waste water tank, and crude product ester layer removes the crude product storage tank; Wherein: content/6 of sulfide in the weight ratio 1030:1030 of sulfhydrylation product, zinc powder and hydrochloric acid * sulfhydrylation product: zinc powder amount * 6;
(4) rectifying: crude product is imported the smart still that steams, carry out underpressure distillation, the material temperature is no more than 190 ℃ in the reactor, the system vacuum degree is-0.1Mpa, the mass content that the mass content of collecting isooctyl mercaptoacetate respectively is lower than 98% front-end volatiles, isooctyl mercaptoacetate is the middle runnings of 98-99%, and the mass content of isooctyl mercaptoacetate is the finished product cut more than 99%.
2. the preparation technology of isooctyl mercaptoacetate according to claim 1, it is characterized in that: in the step (1), the weight ratio of Mono Chloro Acetic Acid, isooctyl alcohol and catalyzer is 800:1090:9; In the step (2), the weight ratio of the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine, Virahol, hydrochloric acid is 1030:1250:760:552.
3. the preparation technology of isooctyl mercaptoacetate according to claim 1, it is characterized in that: the recovery method of Virahol is in the step (2): the Virahol mass percent concentration that mercaptolation is steamed is 30% liquid caustic soda adjustment pH to 10 earlier, Virahol is reclaimed in rectifying under normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101404780A CN102249964A (en) | 2011-05-27 | 2011-05-27 | Process for preparing isooctyl thioglycolate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101404780A CN102249964A (en) | 2011-05-27 | 2011-05-27 | Process for preparing isooctyl thioglycolate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102249964A true CN102249964A (en) | 2011-11-23 |
Family
ID=44977577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101404780A Pending CN102249964A (en) | 2011-05-27 | 2011-05-27 | Process for preparing isooctyl thioglycolate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102249964A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008293A (en) * | 2016-05-13 | 2016-10-12 | 山东沾化金嘉利化工科技有限公司 | Method for recovering isooctyl thioglycolate from cauldron bottom residues |
| CN106495984A (en) * | 2016-09-23 | 2017-03-15 | 连云港升南化学有限公司 | The method that isooctyl thioglycolate distillation residual liquid reclaims isooctanol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6500854A (en) * | 1964-01-24 | 1965-07-26 | ||
| CN1058393A (en) * | 1991-08-17 | 1992-02-05 | 淄博市化工研究所 | The method for preparing thioglycollic acid-2-ethyl hexyl ester |
| CN1660735A (en) * | 2004-02-27 | 2005-08-31 | 上海化学试剂研究所 | Method for preparing hyperpure isopropyl alcohol |
| CN101613309A (en) * | 2009-07-28 | 2009-12-30 | 湖北犇星化工有限责任公司 | The preparation method of isooctyl mercaptoacetate |
-
2011
- 2011-05-27 CN CN2011101404780A patent/CN102249964A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6500854A (en) * | 1964-01-24 | 1965-07-26 | ||
| CN1058393A (en) * | 1991-08-17 | 1992-02-05 | 淄博市化工研究所 | The method for preparing thioglycollic acid-2-ethyl hexyl ester |
| CN1660735A (en) * | 2004-02-27 | 2005-08-31 | 上海化学试剂研究所 | Method for preparing hyperpure isopropyl alcohol |
| CN101613309A (en) * | 2009-07-28 | 2009-12-30 | 湖北犇星化工有限责任公司 | The preparation method of isooctyl mercaptoacetate |
Non-Patent Citations (1)
| Title |
|---|
| 杨建: "巯基乙酸异辛酯的合成", 《山东化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008293A (en) * | 2016-05-13 | 2016-10-12 | 山东沾化金嘉利化工科技有限公司 | Method for recovering isooctyl thioglycolate from cauldron bottom residues |
| CN106495984A (en) * | 2016-09-23 | 2017-03-15 | 连云港升南化学有限公司 | The method that isooctyl thioglycolate distillation residual liquid reclaims isooctanol |
| CN106495984B (en) * | 2016-09-23 | 2018-11-16 | 连云港升南化学有限公司 | The method of isooctyl thioglycolate distillation residual liquid recycling isooctanol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103333047B (en) | Preparation method of dichloropropanol | |
| CN103724279B (en) | One step to form the loop prepares the convenient synthetic method of 2-methyl-4-amino-5-amino methylpyrimidine | |
| CN105251496A (en) | Catalyst and method preparing dimethyl carbonate by using catalyst | |
| CN100491346C (en) | Preparation method of 3-mercaptopropionic acid | |
| CN103641780B (en) | A kind of method of purifying isoquinoline from coal tar crude product | |
| CN103641710A (en) | Synthesis method for trimesoyl chloride | |
| CN102249964A (en) | Process for preparing isooctyl thioglycolate | |
| CN101863785A (en) | Environmental-protection preparation method of betaine hydrochloride | |
| CN102351697A (en) | Preparation method of methyl formylcaprylate | |
| CN101270051A (en) | Method for preparing tri-n-butyl citrate | |
| CN102010295B (en) | Method for preparing dichloropropanol by glycerol method | |
| CN101613309A (en) | The preparation method of isooctyl mercaptoacetate | |
| CN104961760A (en) | Synthetic method for novel rubber sulfur-containing silane coupling agent--bis-[gamma-(trimethoxy)silylpropyl]tetrasulfide | |
| CN101328125B (en) | Method for preparing diethyl carbonate by two-step coupling reaction | |
| CN105061487A (en) | Method for producing methacryloxypropyltrimethoxysilane | |
| CN102285883B (en) | Method for synthesizing tributyl citrate (TBC) by adopting composite ionic liquid catalyst | |
| CN101633598A (en) | Method for preparing methane chloride by dimethyl sulfate | |
| CN102115431B (en) | Synthesis method of 2, 2-ethoxyethanol | |
| CN103709032B (en) | Preparation method for catalytically synthesizing dibutyl carbonate by proline ionic liquid | |
| CN105061276A (en) | Synthetic process of N-allyl-O- isobutyl thionocarbamate | |
| CN102872912B (en) | Catalyst for synthesizing methyl phenyl carbamate and preparation and application methods thereof | |
| CN102002033B (en) | Protection method for astaxanthin intermediate | |
| CN106883129B (en) | Method for preparing m-chloroaniline by using meta-oil | |
| CN104829457A (en) | Method for Bronsted-Lewis acidic ionic liquid catalyzed synthesis of di(glycol monoalkyl ether)terephthalate | |
| CN103506140B (en) | Lactic acid catalyst for synthesizing and synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20111123 |