CN103566782A - Preparation of novel cyclodextrin thermally induced micropore polyimide gas separation membrane - Google Patents
Preparation of novel cyclodextrin thermally induced micropore polyimide gas separation membrane Download PDFInfo
- Publication number
- CN103566782A CN103566782A CN201310594757.3A CN201310594757A CN103566782A CN 103566782 A CN103566782 A CN 103566782A CN 201310594757 A CN201310594757 A CN 201310594757A CN 103566782 A CN103566782 A CN 103566782A
- Authority
- CN
- China
- Prior art keywords
- cyclodextrin
- polyimide
- membrane
- film
- separation
- 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
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses preparation of a novel cyclodextrin thermally induced micropore polyimide gas separation membrane. A polyimide material containing certain cyclodextrin is synthesized based on a clathrate compound formed by cyclodextrin and an aromatic diamine monomer; the following purposes are achieved by utilizing a principle of lower cyclodextrin thermolysis temperature and controlling the temperature and the heat treatment time in a nitrogen atmosphere: 1) the size of a new pore in polyimide after thermal rearrangement is intended to be controlled by introducing cyclodextrin monomers in different sizes, and 2) the porosity of the new pore after the thermal rearrangement is intended to be controlled by different thermolysis temperatures and different thermolysis quantities of the cyclodextrin monomers; a series of pore diameter controllable thermal rearrangement polyimide membranes with high gas permeability, high separation property and apparent whole are prepared by taking the gas permeation separation property as a feedback basis; finally the polyimide membrane suitable for separation of current common acid gas such as CO2 and H2S, separation of O2/N2, separation and recovery of organic vapor, and separation of H2 is obtained. Moreover, the problems of smaller gas permeability, higher membrane component cost and the like of a polyimide membrane material in a gas separation application are solved to a certain extent.
Description
Technical field
The present invention relates to polymeric membrane for separation technology, specifically first make polyimides main chain be inlaid in the cyclodextrin material of easy thermal decomposition, after film forming, by controlled thermal rearrangement, process, keep in situation that polyimides main chain section is complete, attempt controlling size and the porosity of cyclodextrin new micropore that substance decomposition forms, thereby prepare the controlled thermal rearrangement polyimide gas separating film of micropore of series of new.
Background technology
Membrane separation technique is a new and effective common technology that adapts to contemporary industry development, is acknowledged as one of Scientific And Technical of the significant problems such as the energy that 21 century solves facing mankind, resource and environment.The development of gas film separation starts from the system research of J.K.Mitchell in 1831 to natural rubber gas permeability.1979 Nian， U.S. Monsanto companies successfully develop prism gas film separator for separating of H
2/ N
2, indicate gas film separation industrialization for the first time truly.Gas membrane Seperation Technology fast development subsequently, oneself develops into independently chemical engineering unit operation Membrane Gas Separation Processes, and is successfully applied to H
2separation and recovery, oxygen enrichment (O
2), rich nitrogen (N
2), natural gas (CH
4) purification, separation and recovery and the sour corrosion gas (CO of organic steam (ethene, propylene and chloromethanes etc.)
2, SO
2and H
2the key areas such as removal S etc.).
Gas film separation is developed so far, the research of its membrane module and device is gradually improved, and oneself transfers the pointed membrane material of research and development by original simple natural high polymer and the engineering plastics (as cellulose acetate, silicon rubber, polysulfones and polyether sulfone etc.) of adopting the development of its core membrane material.Wherein polyimide film material is because of its excellent heat endurance, chemical stability, mechanical performance and gas separating property, receive much more more and more concerns, the desirable polyimide gas separating film that research and development have high gas permeability and high separating property, high mechanical strength and good filming performance concurrently becomes the target that numerous researchers pursue.Current business-like separation membrane is mainly polyimides, because it has excellent machinery and thermal stability and gas separating property.Yet it is lower that its gas flux and rubbery state film are compared flux, under same treatment amount, the larger and then high expensive of the membrane area needing, this point becomes the resistance that limits its further large-scale promotion and application.Can predict, in the coming years, researching and developing the polyimide film that tool has superelevation gas flux concurrently will become the emphasis of gas film separate study.
This patent is in the situation that guaranteeing that polyimides main chain is not destroyed, after film forming, carrying out the thermal rearrangement of uniform temperature processes, by decomposition, remove different content and the different types of cyclodextrin material containing on main chain, portion increases part free volume newly within it, its gas flux can be largely increased, and due to main chain section undecomposed fracture, its original high gas permeability can be kept, and the integrality of main chain section make it after thermal rearrangement, still can keep good mechanical performance.
Summary of the invention
The object of the invention is to prepare cyclodextrin thermic micropore polyimide gas separating film.
For achieving the above object, the technical solution used in the present invention is:
Polyimides main chain is inlaid in the cyclodextrin material of easy thermal decomposition, after film forming, by controlled thermal rearrangement, process, keep in situation that polyimides main chain section is complete, attempt controlling size and the porosity of cyclodextrin new micropore that substance decomposition forms, thereby prepare the controlled thermal rearrangement polyimide gas separating film of micropore of series of new.
Specifically, its step of preparation method of the present invention is as follows:
A. the formation of diamines inclusion compound: get a certain amount of aromatic diamine in water, add hot reflux under nitrogen atmosphere, can be observed diamines water insoluble.Get a certain amount of cyclodextrin soluble in water again, add hot reflux after most of two amine solvents, filter out the diamines into dissolving, a period of time crystallization of solution stand at low temperature, filters and obtains crystal, puts into 50～120 ℃ of vacuum drying ovens and dries 12～24h;
B. press the molar ratio of diamine monomer and dianhydride monomer 1:1～1.1, drop into a certain amount of aromatic diamine inclusion compound, aromatic diamine and aromatic series dianhydride are at normal temperatures, nitrogen atmosphere high speed stirs 2～48h to solution thickness, then the catalyst of triethylamine and the dehydrating agent acetic anhydride that add 2～10 times of diamine monomer moles, continue high-speed stirred 2～48h to solution again thickness, then polymer solution is poured into sedimentation in a large amount of methyl alcohol, then polymer is put into 50～150 ℃ of vacuum drying ovens and dry 24～48h, prepare the polyimide material that main chain contains different content and variety classes cyclodextrin standby,
C. the preparation of anisotropic membrane: get the polyimide material that a certain amount of main chain preparing contains different content and variety classes cyclodextrin and be dissolved in a certain amount of solvent, control solution temperature between 20～100 ℃, then use scraper knifing on nonwoven, after film again between 50～300 μ m, standing 0～1000s, by film as for solubility in the non-solvent between 0～100 ℃, there is the anisotropic membrane that inversion of phases obtains, put into water 1～5 day, then film is put into 50～120 ℃ of vacuum drying ovens and dry 5～24h.The film thickness obtaining, between 50～300 μ m, is prepared and is contained different content and different types of polyimide asymmetric membrane;
D. thermic micropore process control: get and contain different content and different types of polyimide asymmetric membrane, according to its TGA thermogravimetic analysis (TGA), control the temperature and time decomposing, between 200～500 ℃, carry out thermal decomposition, time, at 5～1000min, is finally prepared the thermic polyimide asymmetric membrane that forms micropore by control loop dextrin decomposition amount;
E. the preservation of film: film leaves in drier to be preserved under normal temperature;
2 according to new type polyimide gas separation membrane claimed in claim 1, it is characterized in that, in step (1 and 2), cyclodextrin material used is as alpha-cyclodextrin, beta-schardinger dextrin-and gamma-cyclodextrin etc.
3 according to new type polyimide gas separation membrane claimed in claim 1, it is characterized in that, in step (2), the dianhydride of synthesis of polyimides used and diamine monomer are as dianhydride monomer: 6FDA (4,4 '-hexafluoroisopropyli,ene-phthalic anhydride), BPDA (4,4 '-biphenyl dicarboxylic acid acid anhydride), BTDA (3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride), PMDA (1,2,4,5-tetracarboxylic acid dianhydride), ODPA (the two phthalic anhydrides of 4,4 '-oxygen) etc.; Diamine monomer: ODA (4,4 '-diaminodiphenyl ether), TMPDA (2,4,6-trimethyl-1,3-phenylenediamine), MPDA (1,3-phenylenediamine), MDA (4,4 '-diaminodiphenyl-methane), 6FDAM (2,2 '-bis-(4-aminophenyl) HFC-236fa), TMPDA-durene (durol diamines) etc.
4. according to new type polyimide gas separation membrane claimed in claim 1, it is characterized in that, step (2) cyclodextrin content is 0.1～50wt%.
5. according to new type polyimide gas separation membrane claimed in claim 1, it is characterized in that, solvent is some polar solvents as CHCl in step (1)
3(chloroform) THF (oxolane), DMAc (DMA), DMF(N, dinethylformamide), NMP (METHYLPYRROLIDONE), DMSO (dimethyl sulfoxide (DMSO)) etc.
The specific embodiment
Tool of the present invention has the following advantages:
1. by the control of cyclodextrin decomposition amount, reach the control of the inner newly-increased micropore of polyimide film.
2. obtain the polyimide gas separating film that flux is large and separating property is good.
Diffusion barrier gas permeability is measured by constant voltage variable volume method gas permeation instrument.
The infiltration coefficient P of gas A in polymer film
a(em
3(STP) cm
-2s
-1cmHg
-1) be calculated as follows:
Wherein, subscript A represents gas A; J
afor infiltration air flux (em3 (STP)/s); A is sample film effective area (cm
2); (p
2-p
1) be the pressure reduction (cmHg) of the upper and lower both sides of film.
The ideal separation factor α of gas A/B in polymer film
a/Bbe calculated as follows:
Embodiment 1
The 6FDA-ODA27g getting containing the about 2wt% of beta-schardinger dextrin-adds in 50mlNMP and 23mlTHF mixed solvent, 60 ℃ of stirring 24h, and solution is poured on knifing on 60 ℃ of heating platforms, parks 10s in air, the water of then the putting into room temperature film forming of walking around mutually.Film is put into water 2 days, then film is put into 120 ℃ of vacuum drying ovens and dries 24h.The film thickness obtaining, in 200 μ m left and right, is then put into film the tube furnace under nitrogen atmosphere, 320 ℃ of heat treatment 10min, and then cooling taking-up thermogravimetric is clapped polyimide film.
Test gas separating property:
P
CO2=30.3GPU
(1GPU=10-6cm3(STP)/(cm2scmHg))
α
CO2／CH4=36.42α
CO2／N2=19.53
Embodiment 2
The 6FDA-ODA27g getting containing the about 9.5wt% of beta-schardinger dextrin-adds in 50mlNMP and 23mlTHF mixed solvent, 60 ℃ of stirring 24h, and solution is poured on knifing on 60 ℃ of heating platforms, parks 10s in air, the water of then the putting into room temperature film forming of walking around mutually.Film is put into water 2 days, then film is put into 120 ℃ of vacuum drying ovens and dries 24h.The film thickness obtaining, in 200 μ m left and right, is then put into film the tube furnace under nitrogen atmosphere, 320 ℃ of heat treatment 10min, and then cooling taking-up thermogravimetric is clapped polyimide film.
Test gas separating property:
P
CO2=87.2GPU
α
CO2／CH4=34.78α
CO2／N2=18.65
Embodiment 3
The 6FDA-ODA27g getting containing the about 9.5wt% of alpha-cyclodextrin adds in 50mlNMP and 23mlTHF mixed solvent, and 60C stirs 24h, and solution is poured on knifing on 60 ℃ of heating platforms, parks 10s in air, the water of then the putting into room temperature film forming of walking around mutually.Film is put into water 2 days, then film is put into 120 ℃ of vacuum drying ovens and dries 24h.The film thickness obtaining, in 200 μ m left and right, is then put into film the tube furnace under nitrogen atmosphere, 320 ℃ of heat treatment 10min, and then cooling taking-up thermogravimetric is clapped polyimide film.
Test gas separating property:
P
CO2=63.6GPU
α
CO2／CH4=36.33α
CO2／N2=19.25
Embodiment 4
The 6FDA-ODA27g getting containing the about 9.5wt% of gamma-cyclodextrin adds in 50mlNMP and 23mlTHF mixed solvent, 60 ℃ of stirring 24h, and solution is poured on knifing on 60 ℃ of heating platforms, parks 10s in air, the water of then the putting into room temperature film forming of walking around mutually.Film is put into water 2 days, then film is put into 120 ℃ of vacuum drying ovens and dries 24h.The film thickness obtaining, in 200 μ m left and right, is then put into film the tube furnace under nitrogen atmosphere, 320 ℃ of heat treatment 10min, and then cooling taking-up thermogravimetric is clapped polyimide film.
Test gas separating property:
P
CO2=120.27GPU
α
CO2／CH4=34.63α
CO2/N2=18.73
Comparative example
Table 1 is the thermic micropore polyimide film in the embodiment of the present invention 1～4 and does not add the 6FDA-ODA anisotropic membrane of cyclodextrin to compare.Decomposition of the present invention removes the different content that contains on main chain and the polyimide film of different types of cyclodextrin material, and the newly-increased part free volume of portion, is greatly improved in the basic gas permeability simultaneously that keeps optionally within it.
Table 1 thermic micropore of the present invention 6FDA-ODA film and the comparison of pure 6FDA-ODA film properties
Embodiment 1 and pure 6FDA-ODA compare can find out add a small amount of beta-schardinger dextrin-polyimide film after heat treatment gas flux improved 50%.
Embodiment 1 and implementation column 2 compare can find out the content that increases beta-schardinger dextrin-, and gas flux significantly improves, and selectively still keeps better.
Implementation column 2, implementation column 3 compare and can find out that in alpha-cyclodextrin, beta-schardinger dextrin-and gamma-cyclodextrin three, cyclodextrin, in the situation that the identical heat treatment temperature of addition is identical, wherein be take gamma-cyclodextrin effect as excellent to the raising difference of polyimides film properties with embodiment 4 threes.
Claims (5)
1. a new type polyimide gas separation membrane for cyclodextrin thermic micropore, is characterized in that: the preparation method who contains asymmetric flat sheet membrane after cyclodextrin polyimide membrane material and heat treatment thereof, and its step is as follows:
A. the formation of diamines inclusion compound: get a certain amount of aromatic diamine in water, add hot reflux under nitrogen atmosphere, can be observed diamines water insoluble.Get a certain amount of cyclodextrin soluble in water again, add hot reflux after most of two amine solvents, filter out the diamines into dissolving, a period of time crystallization of solution stand at low temperature, filters and obtains crystal, puts into 50～120 ℃ of vacuum drying ovens and dries 12～24h;
B. press the molar ratio of diamine monomer and dianhydride monomer 1:1～1.1, drop into a certain amount of aromatic diamine inclusion compound, aromatic diamine and aromatic series dianhydride are dissolved in polar solvent at normal temperatures, nitrogen atmosphere high speed stirs 2～48h to solution thickness, then the catalyst of triethylamine and the dehydrating agent acetic anhydride that add 2～10 times of diamine monomer moles, continue high-speed stirred 2～48h to solution again thickness, then polymer solution is poured into sedimentation in a large amount of methyl alcohol, then polymer is put into 50～150 ℃ of vacuum drying ovens and dry 24～48h, prepare the polyimide material that main chain contains different content and variety classes cyclodextrin standby,
C. the preparation of anisotropic membrane: get the polyimide material that a certain amount of main chain preparing contains different content and variety classes cyclodextrin and be dissolved in a certain amount of solvent, control solution temperature between 20～100 ℃, then use scraper knifing on nonwoven, after film again between 50～300 μ m, standing 0～1000s, by film as for solubility in the non-solvent between 0～100 ℃, there is the anisotropic membrane that inversion of phases obtains, put into water and within 1～5 day, remove wherein unreacted crosslinking agent, then film is put into 50～120 ℃ of vacuum drying ovens and dry 5～24h.The film thickness obtaining, between 50～300 μ m, is prepared and is contained different content and different types of polyimide asymmetric membrane;
D. thermic micropore process control: get and contain different content and different types of polyimide asymmetric membrane, according to its TGA thermogravimetic analysis (TGA), control the temperature and time decomposing, between 200～500 ℃, carry out thermal decomposition, time, at 5～1000min, is finally prepared the thermic polyimide asymmetric membrane that forms micropore by control loop dextrin decomposition amount;
The preservation of e film: film leaves in drier to be preserved under normal temperature.
2. according to new type polyimide gas separation membrane claimed in claim 1, it is characterized in that, in step a and b, cyclodextrin material used is as alpha-cyclodextrin, beta-schardinger dextrin-and gamma-cyclodextrin etc.
3. according to new type polyimide gas separation membrane claimed in claim 1, it is characterized in that, in step b, the dianhydride of synthesis of polyimides used and diamine monomer are as dianhydride monomer: 4, and 4 '-hexafluoroisopropyli,ene-phthalic anhydride-6FDA, 4,4 '-biphenyl dicarboxylic acid acid anhydride-BPDA, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride-BTDA, 1,2,4,5-tetracarboxylic acid dianhydride-PMDA, 4, the two phthalic anhydride-ODPA of 4 '-oxygen etc.; Diamine monomer: 4,4 '-diaminodiphenyl ether-ODA, 2,4,6-trimethyl-1,3-phenylenediamine-TMPDA, 1,3-phenylenediamine-MPDA, 4,4 '-diaminodiphenyl-methane-MDA, 2,2 '-bis-4-aminophenyl HFC-236fa-6FDAM, durol diamines-TMPDA-durene etc.
4. according to new type polyimide gas separation membrane claimed in claim 1, it is characterized in that, step b cyclodextrin content is 0.1～50wt%.
5. according to new type polyimide gas separation membrane claimed in claim 1, it is characterized in that, in step c, solvent is some polar solvents as chloroform, oxolane, DMA, DMF, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO) etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310594757.3A CN103566782A (en) | 2013-11-19 | 2013-11-19 | Preparation of novel cyclodextrin thermally induced micropore polyimide gas separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310594757.3A CN103566782A (en) | 2013-11-19 | 2013-11-19 | Preparation of novel cyclodextrin thermally induced micropore polyimide gas separation membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103566782A true CN103566782A (en) | 2014-02-12 |
Family
ID=50040012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310594757.3A Pending CN103566782A (en) | 2013-11-19 | 2013-11-19 | Preparation of novel cyclodextrin thermally induced micropore polyimide gas separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103566782A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921037A (en) * | 2016-06-22 | 2016-09-07 | 辽宁科技大学 | Method for preparing porous gas separation membrane material with thermally-induced rigid structure |
| CN105964155A (en) * | 2016-05-13 | 2016-09-28 | 天津工业大学 | Design and preparation of supramolecular beta-cyclodextrin-ionic liquid-polyimide CO2 gas separation membrane material |
| CN111621055A (en) * | 2020-06-05 | 2020-09-04 | 中国科学技术大学 | Supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect and preparation method thereof |
| CN111763503A (en) * | 2020-07-10 | 2020-10-13 | 西南石油大学 | Hydrogen sulfide inhibitor for drilling fluid and preparation method thereof |
-
2013
- 2013-11-19 CN CN201310594757.3A patent/CN103566782A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105964155A (en) * | 2016-05-13 | 2016-09-28 | 天津工业大学 | Design and preparation of supramolecular beta-cyclodextrin-ionic liquid-polyimide CO2 gas separation membrane material |
| CN105964155B (en) * | 2016-05-13 | 2019-05-14 | 天津工业大学 | Supermolecular beta-cyclodextrin-ionic liquid-polyimides CO2The design and preparation of gas separation membrane material |
| CN105921037A (en) * | 2016-06-22 | 2016-09-07 | 辽宁科技大学 | Method for preparing porous gas separation membrane material with thermally-induced rigid structure |
| CN111621055A (en) * | 2020-06-05 | 2020-09-04 | 中国科学技术大学 | Supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect and preparation method thereof |
| CN111621055B (en) * | 2020-06-05 | 2021-08-13 | 中国科学技术大学 | Supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect and preparation method thereof |
| CN111763503A (en) * | 2020-07-10 | 2020-10-13 | 西南石油大学 | Hydrogen sulfide inhibitor for drilling fluid and preparation method thereof |
| CN111763503B (en) * | 2020-07-10 | 2021-01-15 | 西南石油大学 | Hydrogen sulfide inhibitor for drilling fluid and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105964155B (en) | Supermolecular beta-cyclodextrin-ionic liquid-polyimides CO2The design and preparation of gas separation membrane material | |
| Xu et al. | Aromatic polyimide and crosslinked thermally rearranged poly (benzoxazole-co-imide) membranes for isopropanol dehydration via pervaporation | |
| Nafisi et al. | Gas separation properties of ZIF-8/6FDA-durene diamine mixed matrix membrane | |
| Swaidan et al. | Pure-and mixed-gas CO2/CH4 separation properties of PIM-1 and an amidoxime-functionalized PIM-1 | |
| CN106139936B (en) | Polyimide gas separating film and its preparation method and application | |
| Rafiq et al. | Separation of CO2 from CH4 using polysulfone/polyimide silica nanocomposite membranes | |
| Kim et al. | Thermally rearranged (TR) polybenzoxazole hollow fiber membranes for CO2 capture | |
| Alaslai et al. | High-performance intrinsically microporous dihydroxyl-functionalized triptycene-based polyimide for natural gas separation | |
| Yahaya et al. | Cardo-type random co-polyimide membranes for high pressure pure and mixed sour gas feed separations | |
| CN104829853A (en) | Polyimide gas separation membrane as well as preparation method and applications thereof | |
| JPS6153103B2 (en) | ||
| Hu et al. | Highly permeable polyimides incorporating Tröger's base (TB) units for gas separation membranes | |
| Low et al. | Carbon molecular sieve membranes derived from pseudo-interpenetrating polymer networks for gas separation and carbon capture | |
| CN103566782A (en) | Preparation of novel cyclodextrin thermally induced micropore polyimide gas separation membrane | |
| Maya et al. | Partially pyrolyzed membranes (PPMs) derived from copolyimides having carboxylic acid groups. Preparation and gas transport properties | |
| Lau et al. | A vapor-phase surface modification method to enhance different types of hollow fiber membranes for industrial scale hydrogen separation | |
| Munoz et al. | Thermal treatment of poly (ethylene oxide)-segmented copolyimide based membranes: An effective way to improve the gas separation properties | |
| Ma et al. | Bifunctionalized intrinsically microporous polyimides with simultaneously enhanced gas permeability and selectivity | |
| Deng et al. | Gas transport property of the binaphthyl-based polyimide membranes | |
| Gye et al. | PEG-imidazolium-incorporated polyimides as high-performance CO2-selective polymer membranes: The effects of PEG-imidazolium content | |
| Zhang | Synthesis and characterization of bis (phenyl) fluorene-based cardo polyimide membranes for H2/CH4 separation | |
| JP2009082850A (en) | New gas separation membrane, its manufacturing method, and gas treating method using it | |
| Weng et al. | Preparation and characterization of PPSU/PBNPI blend membrane for hydrogen separation | |
| Huang et al. | Water vapor permeation properties of aromatic polyimides | |
| Huang et al. | Water vapor sorption and transport in dense polyimide membranes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140212 |