CN1483510A - Silica gel continuous bar and preparation process thereof - Google Patents
Silica gel continuous bar and preparation process thereof Download PDFInfo
- Publication number
- CN1483510A CN1483510A CNA031287921A CN03128792A CN1483510A CN 1483510 A CN1483510 A CN 1483510A CN A031287921 A CNA031287921 A CN A031287921A CN 03128792 A CN03128792 A CN 03128792A CN 1483510 A CN1483510 A CN 1483510A
- Authority
- CN
- China
- Prior art keywords
- hours
- continuously
- time
- silica gel
- concentration
- 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
- Silicon Compounds (AREA)
Abstract
The present invention discloses a silica-gel continuous rod and its preparation process. Said invention uses alkoxysilane and polyethylene glycol as raw material, uses acetic acid as catalyst, uses ammonia alkali aqueous solution as mesopore pore-forming agent and uses the water bath temp. of 30--50 deg.C as gelling temp. so as to prepare silica-gel continuous rod with macropore 0.4-4.6 micrometer and mescopore 6-35 nm forming table structure. Said invention also provides its concrete production steps, and said preparation process not only is used in high performance liquir chromatography, but also is applicable to capillary chromatography, and said invented product has quick separation effect.
Description
The present invention relates to continuous rod of a kind of silica gel and preparation technology thereof.
Along with continuous progress in science and technology, the especially fast development of life science and pharmaceuticals industry, the anxious to be separated and preparation of complicated biological sample in enormous quantities and medicine, and traditional granular pattern packed column has run into a lot of problems in application.Imitate in order to improve post, can use the granule filler,, sharply increase but the post pressure drop reduces with the filler granularity as 1～2 μ m filler, therefore, the granular pattern packed column that the present widely used filler that is still 5～10 μ m of people is made.But the granular pattern packed column is because the restriction that post is imitated, and separate object is difficult to realize not only efficiently but also fast separate.In addition, the granular pattern packed column is to filling specification requirement height, and is careless slightly, easily causes subsiding or stopping phenomenon of cylinder.For adapting to progress of science and technology, it is a kind of not only efficient but also can realize the chromatogram packing material of separation fast to press for exploitation.
The present invention solves the above-mentioned problems in the prior art exactly, provides a kind of not only efficient but also can realize quick continuous rod of silica gel and the preparation technology thereof who separates.
For addressing the above problem, technical solution of the present invention is: a kind of silica gel is rod continuously, and it is a kind of barred body with grid structure of macropore and mesopore.
The grid structure of above-mentioned described barred body: skeleton is that 0.3～2.5 μ m, macropore are that 0.4～4.6 μ m, mesopore are 6～35nm.
A kind of above-mentioned described silica gel is the preparation technology of rod continuously, and it may further comprise the steps:
1, the gel dampness elimination silica gel preparation of rod continuously
Following proportioning all is weight percentage, with the 2%-10% preferred range is that the polyethylene glycol of 4%-5% places assay flask, adding the 53%-70% preferred range is 60%-65%, concentration is the acetic acid aqueous solution of 0.01mol/L, being stirred to polyethylene glycol dissolves fully, reacting liquid pH value is 2.0-4.0, adding 20%-45% preferable range is 30%～36% alkoxy silane, after the sealing, stirred 20-50 minute down at 0 ℃, in gained colloidal sol impouring polytetrafluoroethylene (PTFE) test tube, reach gel point in temperature is 30--50 ℃ water-bath after, ageing obtained wet silica gel rod continuously more than at least 15 hours;
2. prepare mesopore and suppress continuous excellent bending
In concentration is under the ammonia alkali aqueous solution of the 0.01-5mol/L situation about existing, and is to heat-treat under 110-130 ℃ 7-11 hour in temperature; Subsequently, continuously rod with concentration be the salpeter solution of 0.1mol/L soak be no less than 1 hour after, enter that immersion is no less than 1 hour in the water;
3. the drying of rod and the elimination of cracking phenomena continuously
The continuous rod that was soaked in water is immersed in takes out after being no less than 3 hours in the surfactant solution that concentration is 30-60% (percentage by weight) for the 10%-80% preferred range, the drying box inner drying of putting into 50～80 ℃ of constant temperature is no less than 3 hours; Surfactant comprises cationic surfactant, anion surfactant and neutral surface active agent;
4, the roasting of rod continuously
With continuous rod roasting in high temperature furnace that drying is crossed, the heating rate of high temperature furnace is no more than 200 ℃/hour, promptly obtains silica gel rod continuously after it is warmed up to 600-800 ℃ in constant temperature calcining 1-5 hour.
It is raw material that the present invention adopts alkoxy silane and polyethylene glycol, with acetate is catalyst, with the ammonia alkali is the mesopore perforating agent, adopt improved sol-gel technology, preparation has the grid structure of macropore and mesopore, the silica gel that outward appearance is straight is excellent continuously, and the continuous excellent skeleton of silica gel is that 0.3～2.5 μ m, macropore are that 0.4～4.6 μ m, mesopore are 6～35nm.Adopt special heat treatment technics, effectively suppress the silica gel distortion and the bending of rod continuously; Use surfactant, control is the rate of drying of rod continuously, eliminates the cracking phenomena of rod continuously; Adopt the temperature-gradient method mode that dried continuous rod is carried out roasting.The silica gel that obtains thus rod continuously can directly use with the form of normal-phase chromatography after coating, and also can carry out surface chemical modification to the continuous rod of silica gel by bonding on the post, forms different chromatogram modes, satisfies the preparation of different material and the need that separate.In addition, this preparation technology not only can be applicable to high performance liquid chromatography, also is applicable to capillary electric chromatogram.Product of the present invention has not only efficiently but also separating effect fast, by the silica gel excellent continuously not cracking and the bending phenomenon of this technology preparation, porosity and permeability height, mechanical strength and chemical stability are good, manufacture craft is simple relatively, and is convenient, economical, reliable.
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1: the polyethylene glycol of adding 2% in there-necked flask, adding 53% concentration again is the acetic acid aqueous solution of 0.01mol/L, being stirred to polyethylene glycol dissolves fully, the tetramethoxy-silicane of adding 45% after the sealing, stirred 20 minutes down at 0 ℃, in gained colloidal sol impouring polytetrafluoroethylene (PTFE) test tube, after temperature was to reach gel point in 30 ℃ of water-baths, ageing 30 hours obtained wet silica gel rod continuously.Under the situation that concentration exists for the 3mol/L dimethylamine, be to heat-treat under 110 ℃ 11 hours in temperature, to prepare mesopore and to suppress continuous excellent bending.Subsequently, rod soaked 2 hours, 1 hour and 4 hours with 0.1mol/L salpeter solution, water and 10% cationic surfactant DTAC or TTAB respectively continuously, after the taking-up, put into 50 ℃ of thermostatic drying chamber inner dryings 12 hours.Heating rate is 50 ℃/hour in the roasting in high temperature furnace afterwards, high temperature furnace, is heated to 600 ℃, keeps 5 hours, promptly obtains silica gel rod continuously.
Embodiment 2: the polyethylene glycol of adding 10% in there-necked flask, adding 70% concentration again is the acetic acid aqueous solution of 0.01mol/L, being stirred to polyethylene glycol dissolves fully, the tetraethoxysilane of adding 20% after the sealing, stirred 50 minutes down at 0 ℃, in gained colloidal sol impouring polytetrafluoroethylene (PTFE) test tube, after temperature was to reach gel point in 50 ℃ of water-baths, ageing 15 hours obtained wet silica gel rod continuously.Under the situation that concentration exists for 1.5mol/L urea, be to heat-treat under 130 ℃ 7 hours in temperature.Subsequently, rod soaked 3 hours, 2 hours and 6 hours with 0.1mol/L salpeter solution, water and 80% anion surfactant ammonium lauryl sulfate or alkyl sulfate diethanol amine respectively continuously, after the taking-up, put into 80 ℃ of thermostatic drying chamber inner dryings 3 hours.Heating rate is 200 ℃/hour in the roasting in high temperature furnace afterwards, high temperature furnace, is heated to 700 ℃, keeps 2 hours, promptly obtains silica gel rod continuously.
Embodiment 3: the polyethylene glycol of adding 4% in there-necked flask, adding 62% concentration again is the acetic acid aqueous solution of 0.01mol/L, being stirred to polyethylene glycol dissolves fully, the tetramethoxy-silicane of adding 34% after the sealing, stirred 30 minutes down at 0 ℃, in gained colloidal sol impouring polytetrafluoroethylene (PTFE) test tube, after temperature was to reach gel point in 40 ℃ of water-baths, ageing 20 hours obtained wet silica gel rod continuously.Under the situation that concentration exists for 1.0mol/L ammoniacal liquor, be to heat-treat under 120 ℃ 9 hours in temperature.Subsequently, rod is used 0.1mol/L salpeter solution, water and 50% neutral surface active agent's formamide or N respectively continuously, and dinethylformamide soaked 4 hours, 3 hours and 5 hours, after the taking-up, put into 60 ℃ of thermostatic drying chamber inner dryings 8 hours.Heating rate is 100 ℃/hour in the roasting in high temperature furnace afterwards, high temperature furnace, is heated to 800 ℃, keeps 1 hour, promptly obtains silica gel rod continuously.Its skeleton is that 1.2 μ m, macropore are that 2.0 μ m, mesopore are 25nm.
Embodiment 4: the polyethylene glycol of adding 5% in there-necked flask, adding 63% concentration again is the acetic acid aqueous solution of 0.01mol/L, being stirred to polyethylene glycol dissolves fully, the tetramethoxy-silicane of adding 32% after the sealing, stirred 40 minutes down at 0 ℃, in gained colloidal sol impouring polytetrafluoroethylene (PTFE) test tube, after temperature was to reach gel point in 35 ℃ of water-baths, ageing 24 hours obtained wet silica gel rod continuously.Under the situation that concentration exists for 0.01mol/L ammoniacal liquor, be to heat-treat under 115 ℃ 10 hours in temperature.Subsequently, continuously rod soaked 4 hours, 3 hours and 3 hours with the surfactant cholic acid or the dipropyl valeric acid of 0.1mol/L salpeter solution, water and 30% respectively, after the taking-up, put into 70 ℃ of thermostatic drying chamber inner dryings 6 hours.Heating rate is 150 ℃/hour in the roasting in high temperature furnace afterwards, high temperature furnace, is heated to 600 ℃, keeps 3 hours, promptly obtains silica gel rod continuously.Its skeleton is that 2.5 μ m, macropore are that 4.6 μ m, mesopore are 14nm.
Embodiment 5: the polyethylene glycol of adding 4% in there-necked flask, adding 60% concentration again is the acetic acid aqueous solution of 0.01mol/L, being stirred to polyethylene glycol dissolves fully, the tetramethoxy-silicane of adding 36% after the sealing, stirred 30 minutes down at 0 ℃, in gained colloidal sol impouring polytetrafluoroethylene (PTFE) test tube, after temperature was to reach gel point in 45 ℃ of water-baths, ageing 18 hours obtained wet silica gel rod continuously.Under the situation that concentration exists for 0.1mol/L ammoniacal liquor, be to heat-treat under 125 ℃ 8 hours in temperature.Subsequently, rod soaked 6 hours, 4 hours and 7 hours with 0.1mol/L salpeter solution, water and 60% surfactant dodecylpyridine chloride ammonium respectively continuously, after the taking-up, put into 60 ℃ of thermostatic drying chamber inner dryings 10 hours.Heating rate is 100 ℃/hour in the roasting in high temperature furnace afterwards, high temperature furnace, is heated to 700 ℃, keeps 2 hours, promptly obtains silica gel rod continuously.Its skeleton is that 0.3 μ m, macropore are that 0.4 μ m, mesopore are 19nm.
Claims (9)
1. a silica gel is excellent continuously, it is characterized in that it is a kind of barred body with grid structure of macropore and mesopore.
2, silica gel according to claim 1 is excellent continuously, and it is characterized in that described barred body grid structure: skeleton is that 0.3～2.5 μ m, macropore are that 0.4～4.6 μ m, mesopore are 6～35nm.
3 silica gel according to claim 1 are the preparation technology of rod continuously, it is characterized in that it may further comprise the steps:
(1) the gel dampness elimination silica gel preparation of rod continuously
Following proportioning all is weight percentage, the polyethylene glycol of 2%-10% is placed assay flask, and adding 53%-70%, concentration are the acetic acid aqueous solution of 0.01mol/L, are stirred to polyethylene glycol and dissolve fully, reacting liquid pH value is 2.0-4.0, the alkoxy silane that adds 20%-45% after the sealing, stirred 20-50 minute down at 0 ℃, in gained colloidal sol impouring polytetrafluoroethylene (PTFE) test tube, reach gel point in temperature is 30--50 ℃ water-bath after, ageing obtained wet silica gel rod continuously more than at least 15 hours;
(2) preparation mesopore and suppress continuous excellent bending
In concentration is under the ammonia alkali aqueous solution of the 0.01-5mol/L situation about existing, and is to heat-treat under 110-130 ℃ 7-11 hour in temperature; Subsequently, continuously rod with concentration be the salpeter solution of 0.1mol/L soak be no less than 1 hour after, enter that immersion is no less than 1 hour in the water;
(3) drying of rod and the elimination of cracking phenomena continuously
The continuous rod that was soaked in water is immersed in takes out after being no less than 3 hours in the surfactant solution that concentration is 10%-80% (percentage by weight), the drying box inner drying of putting into 50～80 ℃ of constant temperature is no less than 3 hours; Surfactant comprises cationic surfactant, anion surfactant and neutral surface active agent;
(4) roasting of cylinder
With continuous rod roasting in high temperature furnace that drying is crossed, the heating rate of high temperature furnace is no more than 200 ℃/hour, promptly obtains silica gel rod continuously after it is warmed up to 600-800 ℃ in constant temperature calcining 1-5 hour.
4, according to the continuous excellent preparation technology of the described silica gel of claim 3, it is characterized in that: the preferred range of described polyethylene glycol is 4%-5%, described acetic acid aqueous solution preferred range is 30%～36%, described alkoxy silane preferred range is 60%～65%, and described surfactant solution preferred range is 30-60%.
5, according to the continuous excellent preparation technology of the described silica gel of claim 3, it is characterized in that: described polyethylene glycol ratio is 2%, acetic acid aqueous solution is 53%, described alkoxy silane is a tetramethoxy-silicane, ratio is 45%, at 0 ℃ of following whipping temp is 20 minutes, and bath temperature is 30 ℃, and digestion time is 30 hours; The described ammonia alkali aqueous solution is dimethylamine, and concentration is 3mol/L, and when heat-treating 110 ℃ of temperature, the time is 11 hours; Continuously rod soak time in the 0.1mol/L salpeter solution is that soak time is 1 hour in 2 hours, water, soak the surfactant that uses and be cationic surfactant DTAC or TTAB, concentration is 10%, and soak time is 4 hours; Be 12 hours drying time when drying box inner drying temperature was 50 ℃; Being heated to 600 ℃ of retention times when heating rate is 50 ℃/hour in the high temperature furnace is 5 hours.
6. the preparation technology excellent continuously according to the described silica gel of claim 3, it is characterized in that: described polyethylene glycol ratio is 10%, acetic acid aqueous solution is 70%, described alkoxy silane is a tetraethoxysilane, ratio is 20%, at 0 ℃ of following whipping temp is 50 minutes, and bath temperature is 50 ℃, and digestion time is 15 hours; The described ammonia alkali aqueous solution is urea, and concentration is 1.5mol/L, heat-treats temperature when being 130 ℃, and the time is 7 hours; Continuously rod soak time in the 0.1mol/L salpeter solution is that soak time is 2 hours in 3 hours, water, soak the surfactant that uses and be anion surfactant ammonium lauryl sulfate or alkyl sulfate diethanol amine, concentration is 80%, and soak time is 6 hours; Be 3 hours drying time when drying box inner drying temperature was 80 ℃; Being heated to 700 ℃ of retention times when heating rate is 200 ℃/hour in the high temperature furnace is 2 hours.
7. the preparation technology excellent continuously according to the described silica gel of claim 3, it is characterized in that: described polyethylene glycol ratio is 4%, acetic acid aqueous solution is 62%, described alkoxy silane is a tetramethoxy-silicane, ratio is 34%, at 0 ℃ of following whipping temp is 30 minutes, and bath temperature is 40 ℃, and digestion time is 20 hours; The described ammonia alkali aqueous solution is ammoniacal liquor, and concentration is 1.0mol/L, heat-treats temperature when being 120 ℃, and the time is 9 hours; Continuously rod soak time in the 0.1mol/L salpeter solution is that soak time is 3 hours in 4 hours, water, soak the surfactant that uses and be neutral surface active agent's formamide or N, and dinethylformamide, concentration is 50%, soak time is 5 hours; Be 8 hours drying time when drying box inner drying temperature was 60 ℃; Being heated to 800 ℃ of retention times when heating rate is 100 ℃/hour in the high temperature furnace is 1 hour.
8. the preparation technology excellent continuously according to the described silica gel of claim 3, it is characterized in that: described polyethylene glycol is 5%, acetic acid aqueous solution is 63%, described alkoxy silane is a tetramethoxy-silicane, ratio is 32%, at 0 ℃ of following whipping temp is 40 minutes, and bath temperature is 35 ℃, and digestion time is 24 hours; The described ammonia alkali aqueous solution is ammoniacal liquor, and concentration is 0.01mol/L, heat-treats temperature when being 115 ℃, and the time is 10 hours; Continuously rod soak time in the 0.1mol/L salpeter solution is that soak time is 3 hours in 4 hours, water, soaks the surfactant that uses and is cholic acid or dipropyl valeric acid, and concentration is 30%, and soak time is 3 hours; Be 6 hours drying time when drying box inner drying temperature was 70 ℃; Being heated to 600 ℃ of retention times when heating rate is 150 ℃/hour in the high temperature furnace is 3 hours.
9. the preparation technology excellent continuously according to the described silica gel of claim 3, it is characterized in that: described polyethylene glycol is 4%, acetic acid aqueous solution is 60%, described alkoxy silane is a tetramethoxy-silicane, ratio is 36%, at 0 ℃ of following whipping temp is 30 minutes, and bath temperature is 45 ℃, and digestion time is 18 hours; The described ammonia alkali aqueous solution is ammoniacal liquor, and concentration is 0.1mol/L, heat-treats temperature when being 125 ℃, and the time is 8 hours; Continuously rod soak time in the 0.1mol/L salpeter solution is that soak time is 4 hours in 6 hours, water, soaks the surfactant that uses and is the dodecylpyridine chloride ammonium, and concentration is 60%, and soak time is 7 hours; Be 10 hours drying time when drying box inner drying temperature was 60 ℃; Being heated to 700 ℃ of retention times when heating rate is 100 ℃/hour in the high temperature furnace is 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03128792 CN1260003C (en) | 2003-05-11 | 2003-05-11 | Silica gel continuous bar and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03128792 CN1260003C (en) | 2003-05-11 | 2003-05-11 | Silica gel continuous bar and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1483510A true CN1483510A (en) | 2004-03-24 |
| CN1260003C CN1260003C (en) | 2006-06-21 |
Family
ID=34153395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03128792 Expired - Fee Related CN1260003C (en) | 2003-05-11 | 2003-05-11 | Silica gel continuous bar and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1260003C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460321C (en) * | 2005-05-31 | 2009-02-11 | 中国石油化工股份有限公司 | Diplopore silica gel material, and preparation method |
| CN102883806A (en) * | 2010-03-15 | 2013-01-16 | F·帕尔芒捷 | Multicapillary monolith |
| CN103395794A (en) * | 2013-07-29 | 2013-11-20 | 扬州大学 | Preparation method of monodispersed silicon dioxide grains with uniform grain sizes |
| CN104258805A (en) * | 2014-09-16 | 2015-01-07 | 天津大学 | Preparation method of hybridized silica gel monolithic column |
| WO2022013250A1 (en) * | 2020-07-16 | 2022-01-20 | Lifescientis | Process for synthesizing nanoscale and sub-micron-sized porous silica particles by soft chemistry |
-
2003
- 2003-05-11 CN CN 03128792 patent/CN1260003C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460321C (en) * | 2005-05-31 | 2009-02-11 | 中国石油化工股份有限公司 | Diplopore silica gel material, and preparation method |
| CN102883806A (en) * | 2010-03-15 | 2013-01-16 | F·帕尔芒捷 | Multicapillary monolith |
| CN102883806B (en) * | 2010-03-15 | 2016-05-04 | F·帕尔芒捷 | Multiple capillary entirety |
| CN103395794A (en) * | 2013-07-29 | 2013-11-20 | 扬州大学 | Preparation method of monodispersed silicon dioxide grains with uniform grain sizes |
| CN104258805A (en) * | 2014-09-16 | 2015-01-07 | 天津大学 | Preparation method of hybridized silica gel monolithic column |
| WO2022013250A1 (en) * | 2020-07-16 | 2022-01-20 | Lifescientis | Process for synthesizing nanoscale and sub-micron-sized porous silica particles by soft chemistry |
| FR3112539A1 (en) * | 2020-07-16 | 2022-01-21 | Lifescientis | Process for the synthesis of nanometric and submicron porous silica particles by soft chemistry |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1260003C (en) | 2006-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8889749B2 (en) | Preparation method of hydrophobic monolith type silica aerogel | |
| CN106477587B (en) | The preparation method of polyolefin catalyst carrier silica gel | |
| CN103224239A (en) | Chiral mesoporous silica nano-rod and preparation method thereof | |
| US3243262A (en) | Process for preparing microspheroidal silica | |
| CN105129806A (en) | High-specific surface area silica for washing powder and its preparation method and use | |
| CN104402197A (en) | Low water content quartz glass material preparation method | |
| CN106215909A (en) | A kind of monodisperse porous silica gel chromatographic column filling material and preparation method thereof | |
| CN109053131A (en) | Oxidization fiber aerogel blanket and preparation method thereof | |
| CN102838143B (en) | Preparation method for spherical alumina | |
| CN103342367B (en) | A kind of hydrophilic SiO 2the preparation method of aerogel | |
| CN1260003C (en) | Silica gel continuous bar and preparation process thereof | |
| CN104447323A (en) | Method for synthesizing diadipate by using solid super acid as catalyst | |
| CN101746818B (en) | Preparation method of hydrophobic nano-titanium dioxide | |
| CN106315596A (en) | Production process of white carbon with low CTAB specific area and low heat build-up | |
| CN103191588B (en) | A kind of preparation method of hydrophabic silica | |
| CN111892060A (en) | Preparation method of mesoporous silica microspheres | |
| CN1657571A (en) | Preparation method of microspherical silica used as alkene polymerization catalyst carrier | |
| CN106732518A (en) | The preparation method of inexpensive bigger serface cerium-aluminium composite oxide | |
| CN109053061A (en) | A kind of environmental protection diatom ooze and preparation method thereof | |
| CN104291343B (en) | A kind of synthetic method of mesoporous SBA-3 molecular sieve | |
| CN107651702A (en) | A kind of mesoporous γ Al2O3The preparation method of cotton-shaped microballoon | |
| CN104492407B (en) | A kind of low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of big pore volume | |
| CN101716490A (en) | Composing method for SBA-15 molecular sieve having organic absorbing property | |
| CN203728595U (en) | Dehydration device for precursor of nano-zirconium oxide powder material | |
| CN106430265A (en) | Method for preparing alumina aerogel through extracting aluminum from bauxite |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |