CN1369508A - Nano microcrystal cellulose with crystal form of cellulose II and its preparing process - Google Patents
Nano microcrystal cellulose with crystal form of cellulose II and its preparing process Download PDFInfo
- Publication number
- CN1369508A CN1369508A CN 01107523 CN01107523A CN1369508A CN 1369508 A CN1369508 A CN 1369508A CN 01107523 CN01107523 CN 01107523 CN 01107523 A CN01107523 A CN 01107523A CN 1369508 A CN1369508 A CN 1369508A
- Authority
- CN
- China
- Prior art keywords
- acid
- cellulose
- method described
- treatment
- consumption
- 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
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
A nano microcrystal cellulose with the crystal form of cellulose II is prepared through pre-treating the natural cellulose by DMSO and strong-alkaline swelling agent, and ultrasonic oscillation under the existance of mixed acid as catalyst. Its advantages are high efficiency and clearness, and uniform granularity.
Description
The present invention relates to a kind of method that natural cellulose is degraded to nano micro crystal cellulose with crystal form of cellulose II.
Along with a large amount of exploitations of Nonrenewable resources on the earth and exhausted day by day, natural cellulose is developed and utilized, seek new chemical reaction intermediate and raw material and seem and become more and more important.Natural cellulose is the resource the most widely that distributes, and is present in the cell walls of nearly all plant and in the secretory product of marine alga, it is very abundant to originate, and is a kind of very promising renewable resources.
Having obtained the exploitation of certain degree at present for cellulosic purposes, but still rest on mostly natural cellulose has been carried out being applied to chemical field after the chemical modification, mainly is degradability and the biocompatibility that utilizes natural cellulose, makes degradation material.Natural cellulose is because complex structure, have a large amount of intermolecular and intramolecular hydrogen bonds between the cellulose long-chain, the crystalline region structure is very fine and close, and reaction reagent is difficult to be penetrated into inside, crystalline region, it is carried out functional group skewness after the chemical modification, limited some character of its various derivatives and functional.In the existing literature report, natural cellulose can obtain micron-sized Microcrystalline Cellulose and ultra tiny Mierocrystalline cellulose with certain chemistry or physical method.Microcrystalline Cellulose and ultra tiny Mierocrystalline cellulose can be used as additive, weighting agent, coating etc. and are widely used in fields such as food, medical and health.And because their median size is less, specific surface increases, so reactive behavior increases, carries out after the chemical modification some and has functionally obtained certain improvement.But owing to the restriction of reasons such as reaction solvent system, cellulose grain size distribution, grafted chain is generally shorter, and this has certain limitation to graft copolymer functional.And the particle diameter of Microcrystalline Cellulose is still bigger, is restricted in the application of some high frontiers.
The preparation success of nano micro crystal cellulose is good basis of the cellulosic basic structure of research.Because the complicacy of cellulosic structure, the research to microtextures such as cellulosic molecular chain arrangement, accumulations at present also is in the stage of calculating and deriving.The grain size of nano microcrystalline fiber is very little, can utilize laser light scattering transmission electron microscope etc. to measure its particle diameter, utilizes atomic force microscope can observe directly the fine structure of cellulose chain.
Natural cellulose is degraded to nano micro crystal cellulose, can improves cellulosic response capacity, and further study the crystalline structure of cellulose II and the aggregated structure of nano microcrystalline.Nano micro crystal cellulose can stable dispersion in aqueous phase system, can be the reaction medium grafting with water with suitable monomer, this is that other form Mierocrystalline cellulose can't be accomplished.Natural cellulose is carried out mercerization handle, can obtain that directional trend arranges, the functional regenerated cellulose that better has crystal form of cellulose II.The existing method for preparing cellulose II is the method for solvent reclamation normally, and in appropriate solvent, and the series arrangement of its molecular chain changes in this solvent, with suitable precipitation agent product is precipitated out from solvent again with cellulose dissolution.These methods are used a large amount of organic solvents, and the product crystal formation that obtains and degree of crystallinity are all bad.
The present invention further is degraded to nano level scope with natural cellulose, obtains having the nano micro crystal cellulose of crystal form of cellulose II.Present method cleaning, easy, the product that obtains detect through X-ray diffraction has very high degree of crystallinity and sharp-pointed peak shape, illustrates that its purity is very high.Nano micro crystal cellulose has the special property of nano material: particle is minimum, can reach between 20nm～50nm; Have huge specific surface and surface atom number; The strong absorption effect of broadband; Have special surface effects, as quantum tunneling effect, unsettled coordinate bond etc., make the surfactivity of nanoparticle very big, response capacity also strengthens greatly.Nano micro crystal cellulose still has cellulosic crystalline form and character simultaneously, can utilize the activity hydroxy on the glucose ring to carry out graft copolymerization.
The present invention obtained having the cellulose I crystal formation and and the basis of the Mierocrystalline cellulose nano microcrystalline of cellulose I and II mixing crystal formation on, obtained the nano micro crystal cellulose that profile is spherical or axiolitic pure cellulose II crystal formation, its size of particles is between 6.2～100nm.
Method provided by the invention is at first carried out pre-treatment to natural cellulose, and purpose is the abundant swelling in crystalline region that makes the Mierocrystalline cellulose densification, and reactive behavior point can fully be contacted with catalyzer, and dissolves the bad or irregular crystallite of some orientations district.Pre-treatment is to carry out under 70～100 ℃, and reagent is with DMSO and the two swelling agents of alkaline.Used highly basic can be potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), calcium hydroxide (Ca (OH)
2), hydrated barta (Ba (OH)
2) etc. the solubility inorganic strong alkali.Mierocrystalline cellulose through pre-treatment soaks, washs through sufficient, removes residual DMSO as far as possible, finally is washed till elutant pH value below 8.
Be hydrolysis after the pre-treatment, the method for hydrolysis is to adopt acid-catalyzed hydrolysis 30～100 ℃ (the best is 50～90 ℃).The used catalyst acid and the selection of consumption thereof are the factors of most critical.Used acid can be sulfuric acid (H
2SO
4), hydrochloric acid (HCl), phosphoric acid (H
3PO
4), Periodic acid (HIO
4), perchloric acid (HClO
4), hypochlorous acid (HClO), hypobromous acid (HBrO) sulfurous acid (H
2SO
3), hydrosulphuric acid (H
2S), the mixing acid of one or more different proportionings in hydroiodic acid HI (HI), the Hydrogen bromide inorganic liquid acid such as (HBr).The mixing acid of one or more different proportionings in the organic acids such as acetate, formic acid, phenylformic acid, Whitfield's ointment, vinylformic acid, oxalic acid, inorganic heteropolyacid phospho-wolframic acid (24WO
32H
3PO
4.48H
2O), phospho-molybdic acid (24MoO
3.P
2O
5XH
2O), polyacrylic acid, solid super-strong acid perfluorinated sulfonic resin (NafionHPEIEP) or Cs
2.5(Cs
2.5H
0.5W
12O
40) solid peracid, catalytic hydrolysis carries out under the effect of sonic oscillation, and obtaining the physical properties of product and sonic oscillation time and frequency, temperature of reaction etc. all has relation.Pre-treatment reagent and alkaline volume ratio are 1: 1～3: 1, and the consumption of pretreating reagent is 15～40 times of natural cellulose consumption, and pretreating reagent highly basic is mineral alkali KOH, NaOH, LiOH, Ca (OH)
2Or Ba (OH)
2Its concentration is 1～5mol/L, catalyst acid concentration is 10～70% (volume ratios), the acid consumption is 100～500% of a natural cellulose consumption, obtain the accurate colloid suspension liquid of emulsus, desolvate with the ultracentrifugation method, repeatedly wash, get the accurate colloidal solution in upper strata and get Microcrystalline Cellulose to more than the pH value to 5.
Embodiment 1:
Take by weighing the 0.5g linters, with 40mL concentration is after the NaOH of 5mol/L and DMSO mixed solution (volume ratio is 1: 1) are handled, suction filtration, the residual DMSO of wash-out, and be washed till the pH value below 8 with distilled water, with linters drying after treatment, add 30mL HCl and H
2SO
4Mixing acid, concentration (volume ratio) is 25%.Handle 8h with sonic oscillation under 75 ℃, repeatedly centrifugal desolvating can obtain product.
Embodiment 2:
Take by weighing the 0.5g linters, with 40mL concentration is after the NaOH of 5mol/L and DMSO mixed solution (volume ratio is 1: 1) are handled, suction filtration, the residual DMSO of wash-out, and be washed till the pH value below 8 with distilled water, with linters drying after treatment, add 30mL HCl and H
2SO
4Mixing acid, concentration (volume ratio) is 40%.Under 75 ℃, handle 8h, can obtain product after repeatedly centrifugal the desolvating with sonic oscillation.
Embodiment 3:
Taking by weighing the 1g linters, is after the NaOH of 4mol/L and DMSO mixed solution (volume ratio is 2: 1) are handled with 50mL concentration, suction filtration, is washed till the pH value about 8, with linters drying after treatment.Add 50 milliliters of H
3PO
4With HCl mixed hydrolysis catalyzer (volume ratio is 1: 3), concentration is 60%, at 80 ℃ of following sonic oscillation 10h, can obtain product after repeatedly centrifugal the desolvating.
Embodiment 4:
Taking by weighing the 2g linters, is that the KOH of 5mol/L and DMSO (volume ratio is 2: 1) are 80 ℃ of following digestion 4h, suction filtration, washing, dryings then with 100mL concentration.Add 80mL H
2SO
4With the mixing acid (volume ratio is 3: 5) of HCl, concentration is 35%, handles 10h with sonic oscillation under 80 ℃, can obtain product after repeatedly centrifugal the desolvating.
Embodiment 5:
Taking by weighing the 0.5g linters, is the Ca (OH) of 2mol/L with 40mL concentration
2After handling with DMSO mixed solution (volume ratio is 2: 1), suction filtration, be washed till the pH value about 8, drying.Adding 40mL concentration is 50% oxalic acid solution, for handling 12 hours with sonic oscillation down, obtains product after centrifugal the desolvating in 90 concentration.
Embodiment 6:
Take by weighing the 6g linters, adding 100mL concentration is NaOH and the DMSO mixed solution (volume ratio is 3: 2) of 3mol/L, grinds 2h with high-energy ball milling.Vacuum filtration after drying, adding 500ml concentration (volume ratio) are 40% HCl and H
2SO
4Mixing acid, under 75 ℃, handle 6h with sonic oscillation, can obtain product.
Claims (10)
1, a kind of nano micro crystal cellulose with II crystal formation, profile is spherical or the ellipsoid shape, it is characterized in that size of particles between 6.2～100nm, and whole microcrystal grain has the crystal formation of cellulose II.
2, a kind of method for preparing nano micro crystal cellulose in the claim 1, this method is carried out pre-treatment with natural cellulose through high-speed stirring, ball milled or chemical process, use liquid mineral acid then, liquid organic acid, solid peracid or their mixture as catalyst are hydrolyzed at 30～100 ℃, again through the sonic oscillation certain hour, to remove solvent with ultracentrifugal method at last and make, the chemical process that it is characterized in that pre-treatment is two swelling agent of using simultaneously with DMSO and highly basic.
3, according to the method described in the claim 2, it is characterized in that the pre-treatment chemical process, agents useful for same DMSO and alkaline volume ratio are 1: 1～3: 1.
4,, it is characterized in that the pre-treatment reagent consumption is 15～40 times of natural cellulose consumption according to the method described in the claim 2.
5, according to the method described in the claim 2, it is characterized in that the pre-treatment reagent strong base concentrations is 1～5mol/L, used highly basic is KOH, NaOH, LiOH, Ca (OH)
2Or Ba (OH)
2
6,, it is characterized in that the liquid mineral acid of catalyst system therefor is H according to the method described in the claim 2
2SO
4, HCl, H
3PO
4, HIO
4, HCIO
4, HCIO, HBrO, H
2SO
3, H
2The mixing acid of one or more different proportionings among S, HI, the HBr.
7,, it is characterized in that the catalyzer organic acid is the mixing acid of one or more the different proportionings in acetate, formic acid, phenylformic acid, Whitfield's ointment, vinylformic acid, the oxalic acid according to the method described in the claim 2.
8, according to the method described in the claim 2.It is characterized in that the catalyzer solid peracid is inorganic heteropolyacid phospho-wolframic acid, phospho-molybdic acid, polyacrylic acid, perfluorinated sulfonic resin or Cs
2.5
9, according to the method described in the claim 2, it is characterized in that acid concentration 10%～70% volume ratio of catalyzer, consumption is 100～500% of a natural cellulose consumption.
10, according to the method described in the claim 2, it is characterized in that hydrolysis temperature is 50～90 ℃, the pre-treatment temperature is 70～100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011075236A CN1142185C (en) | 2001-02-13 | 2001-02-13 | Nano microcrystal cellulose with crystal form of cellulose II and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011075236A CN1142185C (en) | 2001-02-13 | 2001-02-13 | Nano microcrystal cellulose with crystal form of cellulose II and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1369508A true CN1369508A (en) | 2002-09-18 |
| CN1142185C CN1142185C (en) | 2004-03-17 |
Family
ID=4656444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011075236A Expired - Fee Related CN1142185C (en) | 2001-02-13 | 2001-02-13 | Nano microcrystal cellulose with crystal form of cellulose II and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1142185C (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005108497A1 (en) * | 2004-05-07 | 2005-11-17 | The Hong Kong Polytechnic University | Nano-wool emulsion and nano-wool powders, the manufacturing method for them and their uses |
| CN1321135C (en) * | 2005-10-20 | 2007-06-13 | 中山大学 | Method for preparing nano micro crystal cellulose using chlorine oxidation degradation |
| CN100374629C (en) * | 2002-12-18 | 2008-03-12 | 香港理工大学 | Method for pulverizing natural organic matter into nano-grade fiber material |
| CN101759807A (en) * | 2010-03-12 | 2010-06-30 | 福建农林大学 | Method for preparing nanocrystal cellulose I by applying acid cation exchange resin |
| CN101481424B (en) * | 2009-02-06 | 2010-11-17 | 北京大学 | Ultra-fine microcrystalline cellulose and preparation thereof |
| CN102182089A (en) * | 2011-03-30 | 2011-09-14 | 西南大学 | Short fiber food waste residue-based nano cellulose and preparation method thereof |
| CN102585017A (en) * | 2012-03-27 | 2012-07-18 | 东华大学 | Preparation method of nanoscale solidago canadensis L. microcrystalline cellulose |
| CN102604127A (en) * | 2012-03-21 | 2012-07-25 | 东北师范大学 | Method for preparing water insoluble polysaccharide nano particles by catalyzing and hydrolyzing of solid heteropolyacid |
| CN103060937A (en) * | 2013-01-29 | 2013-04-24 | 武汉大学 | Preparation method of cellulose nanofiber |
| CN103194027A (en) * | 2013-03-29 | 2013-07-10 | 东北林业大学 | Method for preparing nano-crystalline cellulose/lignin photoresist film |
| CN103881117A (en) * | 2014-02-19 | 2014-06-25 | 浙江理工大学 | Method for preparing surface-functionalized cellulose nanospheres |
| CN104558210A (en) * | 2013-10-15 | 2015-04-29 | 中国科学院青岛生物能源与过程研究所 | Method for preparing nano-cellulose |
| CN108084278A (en) * | 2018-01-02 | 2018-05-29 | 青岛大学 | A kind of preparation method of small size Cellulose nanocrystal |
| CN108187499A (en) * | 2018-01-02 | 2018-06-22 | 昆明理工大学 | A kind of preparation method of biodegradable anion-exchange membrane |
| CN108264569A (en) * | 2017-01-03 | 2018-07-10 | 中国科学院金属研究所 | A kind of nanocrystalline particle of cellulose II type and its preparation method and application |
| TWI684693B (en) * | 2018-06-08 | 2020-02-11 | 行政院原子能委員會核能研究所 | Method of Fabricating Nanoscaled Cellulose with Ionic Liquid Heteropolyacid Catalyst |
| CN111501343A (en) * | 2020-05-08 | 2020-08-07 | 安徽省农业科学院棉花研究所 | Nano cotton fiber super-hydrophobic composite material and preparation method thereof |
-
2001
- 2001-02-13 CN CNB011075236A patent/CN1142185C/en not_active Expired - Fee Related
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374629C (en) * | 2002-12-18 | 2008-03-12 | 香港理工大学 | Method for pulverizing natural organic matter into nano-grade fiber material |
| WO2005108497A1 (en) * | 2004-05-07 | 2005-11-17 | The Hong Kong Polytechnic University | Nano-wool emulsion and nano-wool powders, the manufacturing method for them and their uses |
| CN1321135C (en) * | 2005-10-20 | 2007-06-13 | 中山大学 | Method for preparing nano micro crystal cellulose using chlorine oxidation degradation |
| CN101481424B (en) * | 2009-02-06 | 2010-11-17 | 北京大学 | Ultra-fine microcrystalline cellulose and preparation thereof |
| CN101759807A (en) * | 2010-03-12 | 2010-06-30 | 福建农林大学 | Method for preparing nanocrystal cellulose I by applying acid cation exchange resin |
| CN102182089A (en) * | 2011-03-30 | 2011-09-14 | 西南大学 | Short fiber food waste residue-based nano cellulose and preparation method thereof |
| CN102182089B (en) * | 2011-03-30 | 2013-03-20 | 西南大学 | Short fiber food waste residue-based nano cellulose and preparation method thereof |
| CN102604127A (en) * | 2012-03-21 | 2012-07-25 | 东北师范大学 | Method for preparing water insoluble polysaccharide nano particles by catalyzing and hydrolyzing of solid heteropolyacid |
| CN102585017A (en) * | 2012-03-27 | 2012-07-18 | 东华大学 | Preparation method of nanoscale solidago canadensis L. microcrystalline cellulose |
| CN103060937A (en) * | 2013-01-29 | 2013-04-24 | 武汉大学 | Preparation method of cellulose nanofiber |
| CN103194027B (en) * | 2013-03-29 | 2014-12-10 | 东北林业大学 | Method for preparing nano-crystalline cellulose/lignin photoresist film |
| CN103194027A (en) * | 2013-03-29 | 2013-07-10 | 东北林业大学 | Method for preparing nano-crystalline cellulose/lignin photoresist film |
| CN104558210A (en) * | 2013-10-15 | 2015-04-29 | 中国科学院青岛生物能源与过程研究所 | Method for preparing nano-cellulose |
| CN103881117A (en) * | 2014-02-19 | 2014-06-25 | 浙江理工大学 | Method for preparing surface-functionalized cellulose nanospheres |
| CN103881117B (en) * | 2014-02-19 | 2016-02-24 | 浙江理工大学 | A kind of preparation method of surface-functionalized cellulose nanospheres |
| CN108264569A (en) * | 2017-01-03 | 2018-07-10 | 中国科学院金属研究所 | A kind of nanocrystalline particle of cellulose II type and its preparation method and application |
| WO2018126959A1 (en) * | 2017-01-03 | 2018-07-12 | 中国科学院金属研究所 | Cellulose type ii nanocrystalline particle and manufacturing method and application therefor |
| CN108264569B (en) * | 2017-01-03 | 2020-01-03 | 中国科学院金属研究所 | Cellulose II type nanocrystalline particles and preparation method and application thereof |
| JP2020504224A (en) * | 2017-01-03 | 2020-02-06 | 中国科学院金属研究所 | Cellulose type II nanocrystalline particles and their preparation method and application |
| EP3567057A4 (en) * | 2017-01-03 | 2020-08-26 | Institute Of Metal Research Chinese Academy Of Sciences | Cellulose type ii nanocrystalline particle and manufacturing method and application therefor |
| US11149095B2 (en) | 2017-01-03 | 2021-10-19 | Institute Of Metal Research Chinese Academy Of Sciences | Cellulose II nanocrystal particles and preparation method and use thereof |
| JP7002563B2 (en) | 2017-01-03 | 2022-01-20 | 中国科学院金属研究所 | Cellulose type II nanocrystal particles and their preparation methods and applications |
| CN108187499A (en) * | 2018-01-02 | 2018-06-22 | 昆明理工大学 | A kind of preparation method of biodegradable anion-exchange membrane |
| CN108084278A (en) * | 2018-01-02 | 2018-05-29 | 青岛大学 | A kind of preparation method of small size Cellulose nanocrystal |
| TWI684693B (en) * | 2018-06-08 | 2020-02-11 | 行政院原子能委員會核能研究所 | Method of Fabricating Nanoscaled Cellulose with Ionic Liquid Heteropolyacid Catalyst |
| CN111501343A (en) * | 2020-05-08 | 2020-08-07 | 安徽省农业科学院棉花研究所 | Nano cotton fiber super-hydrophobic composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1142185C (en) | 2004-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1142185C (en) | Nano microcrystal cellulose with crystal form of cellulose II and its preparing process | |
| CN1171904C (en) | Nm-class microcrystal cellulose and its preparing process | |
| CN111793223B (en) | Method for preparing nano-grade regenerated cellulose by adopting molten salt system | |
| CN105080503A (en) | Method for preparing high-adsorption nano-crystalline cellulose polyvinylamine microgel by using biomass | |
| CN102059082A (en) | Method for preparing nano manganese dioxide/carbon composite microsphere | |
| CN109767927A (en) | A kind of preparation method of the supercapacitor biomass porous carbon of high-performance N doping | |
| US10961324B2 (en) | Method for preparation of novel modified bio based materials | |
| CN105733315B (en) | A kind of preparation method of sodium carboxymethylcellulose intercalation modifying montmorillonite | |
| CN102432686B (en) | Micro-nano cellulose and preparation method thereof | |
| CN104211036A (en) | Hydroxyapatite and preparation method thereof | |
| CN1594338B (en) | Process for preparing super-strong anti-hard-water sodium (potassium) humate | |
| CN107123555A (en) | Empty nanotube and its preparation method and application in a kind of metal hydroxides | |
| CN111253597A (en) | Chitin nanofiber/polyaniline composite gel film and preparation method thereof | |
| CN103342826A (en) | Preparation method of chitin nano-fiber/montmorillonite composite membrane material | |
| CN111363064A (en) | Preparation method of carboxymethyl chitosan with high substitution degree and high molecular weight | |
| CN103157515A (en) | Catalyst and method for performing carboxyl reaction on C6 of bacterial cellulose | |
| CN110228821A (en) | A kind of preparation method that carbon dots doping induces 1T phase molybdenum disulfide and the application in energy storage material | |
| CN109485736A (en) | A method of preparing nanocrystal cellulose | |
| CN108976303B (en) | Method for preparing cellulose nano-microcrystal by solid acid catalysis sanding | |
| CN102631937B (en) | Synthesis method of supported silver iodide nanoparticle visible light photocatalyst | |
| CN114832835B (en) | Z-type heterojunction NiS/Co 3 S 4 ZnCdS nano material and preparation method and application thereof | |
| CN103420342A (en) | Preparation method for nano magnesium peroxide | |
| CN105198004A (en) | Fe3O4-SnO2 nanometer composite and preparation method thereof | |
| CN115710712A (en) | Modification method of electrolytic water catalyst | |
| CN110255631B (en) | Preparation method of rice husk-based porous metal oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| 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 |