CN101543747A - Method for preparing allyl surface-active macromonomer - Google Patents
Method for preparing allyl surface-active macromonomer Download PDFInfo
- Publication number
- CN101543747A CN101543747A CN200910058759A CN200910058759A CN101543747A CN 101543747 A CN101543747 A CN 101543747A CN 200910058759 A CN200910058759 A CN 200910058759A CN 200910058759 A CN200910058759 A CN 200910058759A CN 101543747 A CN101543747 A CN 101543747A
- Authority
- CN
- China
- Prior art keywords
- allyl
- parts
- catalyst
- portions
- apes
- 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
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a method for preparing an allyl surface-active macromonomer, which is characterized by comprising the following steps: adding 20 portions of alkylphenol polyoxyethylene ether (CmH2m+1-C6H4-O-(CH2CH2O)nH, n is equal to 1 to 60, and m is equal to 1 to 20), 10 to 900 portions of solvent and 0.1 to 15 portions of catalyst into a three-mouth reaction flask with a reflux condensation device, and reacting the mixture for 1 hour under stirring at the room temperature; increasing temperature to 30 to 95 DEG C, adding 0.5 to 20 portions of allyl chloride into the reaction product, and continuously reacting for 6 to 48 hours; distilling the reaction product under reduced pressure to remove the solvent so as to obtain a crude product; and performing silica gel column chromatographic separation to obtain allyl alkylphenol polyoxyethylene ether with the yield of 70 to 95 percent. The allyl alkylphenol polyoxyethylene ether has excellent surface activity, and can be directly used as a surfactant. A water-soluble copolymer synthesized by taking the allyl alkylphenol polyoxyethylene ether as a surface-active macromonomer has the function of tackifying, or reducing solution surface tension and water-oil interfacial tension, and can be taken as a tackifying copolymer or a macromolecular surfactant for improving the oil recovery ratio.
Description
One, technical field
The present invention relates to a kind of preparation method of allyl surface-active macromonomer, this big monomer is used for synthetic water-soluble tackify copolymer of comb type and high molecular surfactant, also can belong to organic chemistry, macromolecular material and raising oil recovery field directly as surfactant.
Two, technical background
Entered world lead level at the successful polymer flooding of China and with chemical flooding raising recovery efficiency techniques such as the binary of surfactant, alkali or ternary composite drivings, but this technology only is suitable for I, the II class reserves of permeability height, high-quality at present, is difficult to be applied in strong and big III class, the IV class oil reservoir of reserves of high temperature and high salt, hyposmosis, viscous crude, anisotropism.Now, for in, low permeability pay, China mainly adopts the secondary oil recovery water injection technology, average recovery ratio can only reach about 23%, a large amount of residual oils is trapped in the reservoir, long-term water filling is washed away and is also made pore structure, porosity, permeability, rock surface wetability etc. that great change takes place, but the average recovery ratio of external low infiltration sandrock oil reservoir is 25%-50%.In addition, verify in the petroleum-in-place, also mainly based on difficulties such as low, ultra-low permeability oil layer, viscous crude exploitation oil reservoir newly-increased.In order to guarantee the sustainable development of China's economy, exploration can be used for, the novel high polymer oil displacement agent of low permeability pay comprises high-effective viscosity polymer and high molecular surfactant, have important economy and social effect, obtain the important prerequisite that novel high molecular functional monomer is these novel high polymer oil displacement agents of preparation and synthesize.
The polymer that has high-effective viscosity or high table/interfacial activity at present mainly is by the synthetic comb-typed amphiphilic water-soluble co-polymer of surface-active macromonomers, this copolymer is to be connected in the graft polymers that forms on the high polymer main chain by covalent bond by the big molecule side chain of a lot of bars, side chain is randomly dispersed within on the main chain, and all side chains (broach) are isometric and be shorter than main chain.Compare with linear polymer, the molecular structure of comb copolymer has better rigidity, the conformation of macromolecular main chain is stretched, in saline solution, be difficult to take place curl in the molecule, make polymer have good tackify, anti-salt property and high table/interfacial activity, aqueous copolymers solution has low surface tension and oil water interfacial tension.Comb copolymer is by surface-active macromonomers and acrylamide, ionic monomer or/and the hydrophobic monomer copolymerization obtains.Its thickening property or table/interfacial activity can be by the content decision of surface-active macromonomers in macromolecule, and when the surface-active macromonomers content in the macromolecule was low, copolymer was as Tackified polymeric; When the surface-active macromonomers content in the macromolecule was high, copolymer was as high molecular surfactant.The at present synthetic used surface-active macromonomers of comb-typed amphiphilic water-soluble co-polymer mainly is (methyl) acrylate and other ester class and the unsaturated big monomer of acrylic amide.Though these monomers have good reaction activity and surface-active, facile hydrolysis in high temperature and acid, alkaline media, thus make polymer lose the function of surface-active and tackify.And in tertiary oil recovery, oil reservoir is dark more, and the temperature of oil reservoir can be high more, and is also high more to the requirement of Tackified polymeric or surfactant heatproof, and therefore, oil reservoir environmental requirement surface-active macromonomers at high temperature has heat endurance.Liu Jixian etc., petrochemical industry, 2008,37 (2): 174-177, with AEO and butyl methacrylate is raw material, synthesized the AEO methacrylate by the azeotropic fractionation ester exchange method, this surface-active macromonomers is because of containing ester bond and do not contain not heatproof of phenyl ring in having divided, and strand easily curls in saline solution.Wang Fang equality, Acta PhySico-Chimica Sinica, 2008,24 (2): 350-354, synthesized interior olefin(e) acid/OPEO acrylate copolymer, studies show that, the surface tension of this copolymer in fresh water and salt solution is not very low, is respectively 39.8mN/m and 32.3mN/m.Qian Jinwen etc., the macromolecule journal, 2008 (10): 955-959, OPEO (10) (OP-10) is reacted down at 95 ℃ with maleic anhydride, synthesized OPEO maleic acid monoesters, synthesized high molecular surfactant acrylamide/OPEO maleic acid monoesters then, this surfactant has stronger thickening capabilities, but surface-active is not very high, and the surface of 1.5g/L aqueous copolymers solution and oil water interfacial tension are respectively 53.94mN/m and 5.41mN/m.For above-mentioned two kinds of copolymers, at high temperature, hydrolysis can take place in the ester bond in the surface-active macromonomers molecule, and copolymer has also just lost the function of thickening and table/interfacial activity.
Three, summary of the invention
The objective of the invention is to contain the molecule long-chain according to synthesizing present Research and the deficiency that comb type macromolecule oil-displacing agent comprises Tackified polymeric and the used surface-active macromonomers of high molecular surfactant at present, providing a kind of, have the preparation method of the allyl surface-active macromonomer of surface-active, heatproof, anti-salt.This big monomer contains the hydrophilic chain of benzene ring structure, length and has the hydrophobic carbochain of association, is characterized in APES (C
mH
2m+1-C
6H
4-O-(CH
2CH
2O)
nH, n=1～60, m=1～20) and allyl chloride as synthesis material, with sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), aluminium (Al), sodium hydride (NaH), hydrofining (KH), calcium hydride (CaH
2), NaOH (NaOH), potassium hydroxide (KOH), potash (K
2CO
3), sodium carbonate (Na
2CO
3), saleratus (KHCO
3) or/and sodium acid carbonate (NaHCO
3) at least a be catalyst, with oxolane (THF), N, N dimethyl formamide (DMF), methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the tert-butyl alcohol, acetone, benzene,toluene,xylene, carrene, chloroform, ether, ethyl acetate, pyridine have synthesized pi-allyl APES (CH or/and at least a in the water is solvent
2=CH-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20).
The present inventor finds in the synthetic reaction that various reaction conditions such as reactant total concentration, the mol ratio of allyl chloride/APES, reaction temperature, catalyst amount, the productive rate of reaction time to product pi-allyl APES have a significant impact.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
1. the recipe ingredient of pi-allyl APES is:
20 parts of APESs
0.5～20 part of allyl chloride
0.1～15 part of catalyst
10～900 parts of solvents
Wherein catalyst is sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), aluminium (Al), sodium hydride (NaH), hydrofining (KH), calcium hydride (CaH
2), NaOH (NaOH), potassium hydroxide (KOH), potash (K
2CO
3), sodium carbonate (Na
2CO
3), saleratus (KHCO
3) or/and sodium acid carbonate (NaHCO
3) at least a; Solvent is oxolane (THF), N, and dinethylformamide (DMF), methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the tert-butyl alcohol, acetone, benzene,toluene,xylene, carrene, chloroform, ether, ethyl acetate, pyridine are or/and at least a in the water.
2. the preparation of pi-allyl APES
With APES (C
mH
2m+1-C
6H
4-O-(CH
2CH
2O)
nH, n=1～60, m=1～20) 20 parts, 10～900 parts of solvents, 0.1～15 part of adding of catalyst are equipped with in three mouthfuls of reaction bulbs of reflux condensate device, at room temperature stirring reaction 1h, be warming up to 30～95 ℃ then, add 0.5～20 part of allyl chloride, continue reaction 6～48 hours.The product decompression distillation except that desolvating, is obtained crude product, carry out silica gel column chromatography then and separate, obtain the pi-allyl APES, productive rate is 70～95%.
Wherein catalyst is sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), aluminium (Al), sodium hydride (NaH), hydrofining (KH), calcium hydride (CaH
2), NaOH (NaOH), potassium hydroxide (KOH), potash (K
2CO
3), sodium carbonate (Na
2CO
3), saleratus (KHCO
3) or/and sodium acid carbonate (NaHCO
3) at least a; Solvent is oxolane (THF), N, and dinethylformamide (DMF), methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the tert-butyl alcohol, acetone, benzene,toluene,xylene, carrene, chloroform, ether, ethyl acetate, pyridine are or/and at least a in the water.
Pi-allyl APES of the present invention has following advantage:
Pi-allyl APES of the present invention itself just has the surface of good activity, can be directly as surfactant.With the pi-allyl APES is that the synthetic water solubility copolymer of surface-active macromonomers has the function of tackify or reduction solution surface tension and oil water interfacial tension, can be used as tackify copolymer or high molecular surfactant, be used to improve oil recovery.Pi-allyl APES copolymer molecule chain is the rigid structure of comb type, is difficult to take place in saline solution curl in the molecule, and the ethyoxyl in the strand is to Ca
2+, Mg
2+Bivalent cation has complexing, and therefore, this copolymer has the ability of good anti-one, bivalent cation salt.When the pi-allyl APES was introduced in the water solubility copolymer, the methylene APES molecular side chain that end contains phenyl ring had rigidity, was difficult for curling.Long side chain also can increase the rigidity of macromolecular main chain, and the conformation of macromolecular main chain is stretched, and improves tackify, anti-salt or the surface-active of copolymer.In addition, the phenyl ring that steric hindrance is bigger can also suppress the oxidative degradation of molecular side chain, main chain, significantly improves the heatproof and the thermal stability of copolymer.
Four, the specific embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the researcher in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
Embodiment 1
With 20 parts of OPEOs (the addition product EO of APEO is 10), 25 parts of solvent acetone, 0.3 part of adding of catalyst sodium is equipped with in three mouthfuls of reaction bulbs of reflux condensate device, stirring reaction 1h at room temperature, be warming up to 40 ℃ then, add 2 parts of allyl chlorides, continue reaction 6 hours.The product decompression distillation except that desolvating, is obtained crude product, carry out silica gel column chromatography then and separate, obtain the pi-allyl APES, productive rate is 73%.
Embodiment 2
With 20 parts of NPEs (the addition product EO of APEO is 20), solvent N, 80 parts of dinethylformamides, 1.8 parts of addings of catalyst sodium hydride are equipped with in three mouthfuls of reaction bulbs of reflux condensate device, stirring reaction 1h at room temperature, be warming up to 65 ℃ then, add 4.0 parts of allyl chlorides, continue reaction 24 hours.The product decompression distillation except that desolvating, is obtained crude product, carry out silica gel column chromatography then and separate, obtain the pi-allyl APES, productive rate is 79%.
Embodiment 3
With 20 parts of dodecyl phenol polyethenoxy ethers (the addition product EO of APEO is 15), 200 parts of solvents tetrahydrofurane, 4.2 parts of addings of catalyst carbonic acid sodium are equipped with in three mouthfuls of reaction bulbs of reflux condensate device, stirring reaction 1h at room temperature, be warming up to 60 ℃ then, add 17 parts of allyl chlorides, continue reaction 24 hours.The product decompression distillation except that desolvating, is obtained crude product, carry out silica gel column chromatography then and separate, obtain the pi-allyl APES, productive rate is 86%.
Embodiment 4
With 20 parts of cetyl phenol polyethenoxy ethers (the addition product EO of APEO is 30), 320 parts of solvent benzols, 6.0 parts of addings of catalyst NaOH are equipped with in three mouthfuls of reaction bulbs of reflux condensate device, stirring reaction 1h at room temperature, be warming up to 75 ℃ then, add 9.5 parts of allyl chlorides, continue reaction 36 hours.The product decompression distillation except that desolvating, is obtained crude product, carry out silica gel column chromatography then and separate, obtain the pi-allyl APES, productive rate is 90%.
Embodiment 5
With 20 parts of cetyl phenol polyethenoxy ethers (the addition product EO of APEO is 40), 600 parts of solvent xylenes, 11 parts of addings of catalyst carbonic acid sodium are equipped with in three mouthfuls of reaction bulbs of reflux condensate device, stirring reaction 1h at room temperature, be warming up to 95 ℃ then, add 12 parts of allyl chlorides, continue reaction 48 hours.The product decompression distillation except that desolvating, is obtained crude product, carry out silica gel column chromatography then and separate, obtain the pi-allyl APES, productive rate is 92%.
Embodiment 6
With 20 parts of octadecyl phenol polyethenoxy ethers (the addition product EO of APEO is 50), 900 parts of solvent tertiary butanol, 14 parts of addings of catalyst carbonic acid potassium are equipped with in three mouthfuls of reaction bulbs of reflux condensate device, stirring reaction 1h at room temperature, be warming up to 75 ℃ then, add 25 parts of allyl chlorides, continue reaction 48 hours.The product decompression distillation except that desolvating, is obtained crude product, carry out silica gel column chromatography then and separate, obtain the pi-allyl APES, productive rate is 81%.
Claims (2)
1. allyl surface-active macromonomer is characterized in that the recipe ingredient of this big monomer is by weight:
20 parts of APESs
0.5～20 part of allyl chloride
0.1～15 part of catalyst
10～900 parts of solvents
Wherein catalyst is sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), aluminium (Al), sodium hydride (NaH), hydrofining (KH), calcium hydride (CaH
2), NaOH (NaOH), potassium hydroxide (KOH), potash (K
2CO
3), sodium carbonate (Na
2CO
3), saleratus (KHCO
3) or/and sodium acid carbonate (NaHCO
3) at least a; Solvent is oxolane (THF), N, and dinethylformamide (DMF), methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the tert-butyl alcohol, acetone, benzene,toluene,xylene, carrene, chloroform, ether, ethyl acetate, pyridine are or/and at least a in the water.
2. the preparation method of allyl surface-active macromonomer according to claim 1 is characterized in that:
With APES (C
mH
2m+1-C
6H
4-O-(CH
2CH
2O)
nH, n=1～60, m=1～20) 20 parts, 10～900 parts of solvents, 0.1～15 part of adding of catalyst are equipped with in three mouthfuls of reaction bulbs of reflux condensate device, at room temperature stirring reaction 1h, be warming up to 30～95 ℃ then, add 0.5～20 part of allyl chloride, continue reaction 6～48 hours.The product decompression distillation except that desolvating, is obtained crude product, carry out silica gel column chromatography then and separate, obtain the pi-allyl APES, productive rate is 70～95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100587594A CN101543747B (en) | 2009-03-31 | 2009-03-31 | Method for preparing allyl surface-active macromonomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100587594A CN101543747B (en) | 2009-03-31 | 2009-03-31 | Method for preparing allyl surface-active macromonomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101543747A true CN101543747A (en) | 2009-09-30 |
| CN101543747B CN101543747B (en) | 2011-12-28 |
Family
ID=41191277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100587594A Expired - Fee Related CN101543747B (en) | 2009-03-31 | 2009-03-31 | Method for preparing allyl surface-active macromonomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101543747B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585194A (en) * | 2011-12-14 | 2012-07-18 | 中国日用化学工业研究院 | Method for synthesizing allyl fatty alcohol-polyoxyethylene ether or allyl alkylphenol ethoxylate |
| CN102627957A (en) * | 2012-03-22 | 2012-08-08 | 西南石油大学 | Pyridine ring-containing polymer oil displacement agent and preparation method thereof |
| CN103450869A (en) * | 2013-08-14 | 2013-12-18 | 陕西延长石油(集团)有限责任公司研究院 | Preparation method of novel surfactant composite system oil-displacing agent |
| CN103772626A (en) * | 2014-01-23 | 2014-05-07 | 焦作超达环保科技有限公司 | Preparation method of comb type high-molecular flotation agent |
| CN105175627A (en) * | 2015-07-27 | 2015-12-23 | 长江大学 | Foam-type surfactant polymer used for displacement of reservoir oil and preparation method therefor |
| CN108117868A (en) * | 2018-01-10 | 2018-06-05 | 成都理工大学 | A kind of preparation method of the modified xantham gum of long-chain branch containing surface-active |
| CN111777723A (en) * | 2020-07-30 | 2020-10-16 | 西南石油大学 | Physical-chemical double-crosslinking gel particles and preparation method thereof |
| CN113785839A (en) * | 2021-09-17 | 2021-12-14 | 黑龙江巨卓作物科学有限公司 | Nematicidal compositions containing fluoroalkene sulfones and organophosphorus |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284893B (en) * | 2008-06-06 | 2010-10-27 | 成都理工大学 | Comb-typed amphiphilic water-soluble co-polymer, method for preparing same and use |
-
2009
- 2009-03-31 CN CN2009100587594A patent/CN101543747B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585194A (en) * | 2011-12-14 | 2012-07-18 | 中国日用化学工业研究院 | Method for synthesizing allyl fatty alcohol-polyoxyethylene ether or allyl alkylphenol ethoxylate |
| CN102627957A (en) * | 2012-03-22 | 2012-08-08 | 西南石油大学 | Pyridine ring-containing polymer oil displacement agent and preparation method thereof |
| CN103450869A (en) * | 2013-08-14 | 2013-12-18 | 陕西延长石油(集团)有限责任公司研究院 | Preparation method of novel surfactant composite system oil-displacing agent |
| CN103450869B (en) * | 2013-08-14 | 2016-03-16 | 陕西延长石油(集团)有限责任公司研究院 | A kind of preparation method of Surfactant Mixing Systems oil-displacing agent |
| CN103772626A (en) * | 2014-01-23 | 2014-05-07 | 焦作超达环保科技有限公司 | Preparation method of comb type high-molecular flotation agent |
| CN105175627A (en) * | 2015-07-27 | 2015-12-23 | 长江大学 | Foam-type surfactant polymer used for displacement of reservoir oil and preparation method therefor |
| CN108117868A (en) * | 2018-01-10 | 2018-06-05 | 成都理工大学 | A kind of preparation method of the modified xantham gum of long-chain branch containing surface-active |
| CN111777723A (en) * | 2020-07-30 | 2020-10-16 | 西南石油大学 | Physical-chemical double-crosslinking gel particles and preparation method thereof |
| CN113785839A (en) * | 2021-09-17 | 2021-12-14 | 黑龙江巨卓作物科学有限公司 | Nematicidal compositions containing fluoroalkene sulfones and organophosphorus |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101543747B (en) | 2011-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101543747B (en) | Method for preparing allyl surface-active macromonomer | |
| CN101543748B (en) | Method for preparing 4-vinyl benzyl surface-active macromonomer | |
| CN104245791B (en) | Multi-arm polyethylene glycol derivative, its intermediate and their manufacture method | |
| CA2795104C (en) | Process for producing mineral oil using surfactants based on a mixture of c32 guerbet-, c34 guerbet-, c36 guerbet-containing alkyl alkoxylates | |
| CN104356318B (en) | A kind of starlike thermoplastic elastomer (TPE) of lignin-base and preparation method thereof | |
| CN101215364B (en) | Fluorine silicon tri-block copolymers and preparation method thereof | |
| CN103032055B (en) | Use the flooding method containing the cloudy non-surfactant composition of sulfonate | |
| CN113278143B (en) | Efficient unsaturated carbon dioxide-based polyol and preparation method thereof | |
| CN108034052B (en) | Preparation method of phenyltetraurea siloxane polymer supercritical carbon dioxide thickener | |
| CN103275270A (en) | Method for preparing fluorocarbon-modified polyacrylamide by using soap-free emulsion method | |
| CN105198892A (en) | Synthetic method for isosorbide acrylic ester and application of isosorbide acrylic ester in improving thermal performance of polymer | |
| CN102432861A (en) | Branching polyether macromonomer and preparation method thereof | |
| CN102029124B (en) | Polyacrylamide surfactant and preparation method thereof | |
| CN111548445B (en) | Optical activity AIE fluorescent material and preparation method of aqueous polymer thereof | |
| CN112358584B (en) | Sterically hindered mud-resistant polycarboxylate superplasticizer and preparation method thereof | |
| CN101016246A (en) | 2-Vinyl-terephthalic acid bis-(4-butoxy-phenyl) ester, its polymer, preparing method and application | |
| CN1314614C (en) | Concrete water reducing agent of polycarboxylic acid and its prepn process | |
| CN108276979A (en) | A kind of temperature-resistant and anti-salt type polyether sulfonate oil displacement agent and preparation method thereof | |
| CN111635476B (en) | Oil reservoir wettability improver and preparation method thereof | |
| CN110343242A (en) | Photochromic hyperbranched azopolyamide of one kind and preparation method thereof | |
| CN102627762B (en) | Allyl polyether graft polymer synthesis method | |
| CN112079968A (en) | Acrylate polymer containing polyether and long carbon chain ester structure and preparation method thereof | |
| CN113881418B (en) | Alkylaniline polyether benzene sulfonate oil displacement surfactant and preparation method and application thereof | |
| CN113603879A (en) | Novel fluorine-containing hyperbranched polyglycidyl glycerin and preparation method thereof | |
| CN104211850B (en) | A kind of comb-shaped polymer containing reversible hydrogen bond and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111228 Termination date: 20120331 |