CN103193930A - Method for preparing amphoteric polyacrylamide emulsion capable of improving waste paper fine fiber strength - Google Patents
Method for preparing amphoteric polyacrylamide emulsion capable of improving waste paper fine fiber strength Download PDFInfo
- Publication number
- CN103193930A CN103193930A CN2013100756033A CN201310075603A CN103193930A CN 103193930 A CN103193930 A CN 103193930A CN 2013100756033 A CN2013100756033 A CN 2013100756033A CN 201310075603 A CN201310075603 A CN 201310075603A CN 103193930 A CN103193930 A CN 103193930A
- Authority
- CN
- China
- Prior art keywords
- monomer
- waste paper
- emulsion
- preparation
- polyacrylamide emulsion
- 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
Abstract
The invention discloses a method for preparing amphoteric polyacrylamide emulsion capable of improving waste paper fine fiber strength, comprising the following steps: weighing a monomer, sodium bisulfite, potassium persulfate, polyvinylpyrrolidone and hydroquinone, wherein the monomer is composed of AM, AMPS and DMC; preparing the monomer into a monomer aqueous solution and adjusting the PH value to 3-4; adding an ammonium sulfate solution, polyvinylpyrrolidone, and sodium hydrogen sulfite in a reaction kettle, feeding nitrogen gas, stirring uniformly and adding potassium persulfate at 30-40 DEG C, then adding the monomer aqueous solution dropwise to the reaction kettle for polymerization reaction, controlling the reaction temperature at 35-40 DEG C after the monomer aqueous solution is added, adding hydroquinone for inhibition and stopping the test operations. The prepared emulsion can improve fine fiber strength, is good in stability, does not require dissolving, is easy to use, and is environment-friendly in products and preparation process.
Description
Technical field
The present invention relates to the papermaking residue and recycle field, particularly a kind of preparation method who improves the amphiprotic polyacrylamide emulsion of waste paper fiber fines intensity.
Background technology
It is that the raw pulp proportion increases year by year that China adopted waste paper in recent years, according to investigations, the regenerated papermaking proportion in 05 year to 10 years rises to 62.7% by 54.0%, particularly promulgated the raw material policy of " progressively forming based on xylon, waste paper; non-wood fiber is the raw material mix of assisting " in country after, this trend is obvious further.Waste paper is back to production as paper making raw material, can significantly reduces the usage quantity of thallophyta fibrous material.But the art breading of pulping making beating can produce a large amount of fiber fines in the waste paper fibre reuse process, can run off with paper waste at paper-making process, and its intensity difference, drainability are poor, are adsorbed with a large amount of anionic trash that paper-making process produces simultaneously.Can produce interference to paper making wet part at the total anionic trash of the process of copying paper, have a strong impact on manufacturing paper with pulp and quality of finished paper of paper.
The fiber fines cationic demand is than the height of waste paper pulp fiber, probably about 11 μ moL/g; Zeta potential is-65.13mv; Its specific surface area can reach 500m2g
-1, so fiber surface is ionizable goes out more carboxyl, causes fiber surface electric density to improve, this has just caused the high result of Zeta potential absolute value jointly with the anionic trash that is present in the slurry.Such fiber fines is used for reuse papermaking, at first to solve the low problem of its retention, also should satisfy its bigger cationic demand then, increase its interfibrous bonded area and bonding strength, also namely increase quantity and the intensity of hydrogen bonded between its fiber, and strengthen original hydrogen bonded, thereby increase the intensity of fiber fines.
Have in amphiprotic polyacrylamide (AmPAM) molecule of good water-solubility and contain positive and negative electric charge group simultaneously; its anionic group that contains shields to cation group; can repel " the impurity negatively charged ion " that in residue, exist, thereby cation group can not reacted or be neutralized prematurely.And the positively charged ion of anionic group in can absorption system, make cationic auxiliary avoid assorted cationic interference, can satisfy a large amount of cationic demand of fiber fines, and the hydrogen bond quantity on the surface of fiber fines is increased.Its retention aid and filter aid effect and enhancement are better than independent use CPAM or APAM, can satisfy the requirement of fiber fines reuse papermaking.
The paper making additive that is specifically applied to the recycling of papermaking residue at present is also few, and the someone adopts reverse microemulsion process to synthesize AmPAM, is used for the residue result and shows enhancing and retention and drainage effect.But, adopt the often many and poor stability of impurity of the synthetic amphiprotic polyacrylamide product of reverse microemulsion process; If make powder, just need to dissolve in advance more than the 1h, not only need large-scale dissolver but also expend the energy, if the insufficient insolubles that " flake " shape then can occur of dissolving not only causes the waste of product, also can cause the decline of application performance.And synthetic employing emulsifying agent and the varsol of needing of reverse microemulsion process, can cause secondary pollution to environment.Given this, develop a kind of economical green, strong strengthen and the paper making additive of retention and drainage effect is handled the papermaking residue and just seemed particularly important arranged.
Summary of the invention
The object of the invention is to provide double-aqueous phase polymerization to prepare the method for amphiprotic polyacrylamide emulsion, overcomes that impurity in products in the existing amphiprotic polyacrylamide technology of preparing is many, poor stability, powder need dissolve and expend the energy in advance and contain to understand and environment be caused shortcomings such as the emulsifying agent of secondary pollution and varsol.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method who improves the amphiprotic polyacrylamide emulsion of waste paper fiber fines intensity, may further comprise the steps: (1) presses following mass percent weighing material: monomer 30%～35%, sodium bisulfite 0.06%～0.09%, Potassium Persulphate 0.04%～0.06%, polyvinylpyrrolidone 0.8%～1.0%, Resorcinol 0.4%～0.6%; Described monomer is by the AM(acrylamide), AMPS(2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid) and DMC(methylacryoyloxyethyl trimethyl ammonium chloride) form;
(2) monomer is made into monomer solution, and regulates pH value to 3～4;
(3) in the temperature control reactor that condensation reflux unit, agitator and logical nitrogen pipe are housed, add ammoniumsulphate soln, polyvinylpyrrolidone, sodium bisulfite, feed nitrogen, add Potassium Persulphate after under 30 ℃～40 ℃ condition, stirring, then monomer solution is added dropwise to and carries out polyreaction in the reactor;
(4) treat that monomer solution all adds after, the control temperature of reaction adds Resorcinol inhibition and the heating of stopped reaction still, feeds nitrogen and stirring at 35 ℃～40 ℃ behind the reaction terminating, the emulsion room temperature sealing that generates is preserved.
The mol ratio of described AMPS and DMC is 1:1, and the AM molar mass is 0.7:1～0.8:1 with three kinds of total molar masss ratios of monomer.
The described stirring of step (2) is specially: the speed with 300～350rpm stirs.
Step (3) is described to be added dropwise to monomer solution in the reactor, is specially: the speed of monomer solution with 35mL/h～45mL/h is added dropwise in the reactor.
The time of described polyreaction is 6h～8h.
Compared with prior art, the present invention has the following advantages and beneficial effect: synthetic AmPAM emulsion as paper making additive is not to adopt the conversed phase micro emulsion copolymerization method among (1) the present invention, but adopts the synthetic amphiprotic polyacrylamide of double-aqueous phase polymerization method.Double-aqueous phase polymerization is diffuse-aggregate a kind of, the present invention adopts inorganic salt solution as dispersion medium, AM, AMPS and DMC are as monomer, PVP is as dispersion agent, peroxy acid potassium and sodium bisulfite are as redox initiator, and monomer slowly is added dropwise to react in the reactor obtains the AmPAM emulsion, the clarification of product emulsion is stable, can place to preserve more than 3 months and do not change.
(2) this emulsion combines the advantage of double-aqueous phase polymerization method and amphiprotic polyacrylamide, and the polyacrylamide emulsion of generation contains positive and negative electric charge group simultaneously owing to be both sexes in the molecule, have good water-solubility.The retention aid and filter aid effect of amphiprotic polyacrylamide and enhancement are better than independent use cationic polyacrylamide or anionic polyacrylamide; because anionic group shields to cation group; can repel " the impurity negatively charged ion " that in residue, exist, thereby cation group can not reacted or be neutralized prematurely.And the positively charged ion of anionic group in can absorption system, make cationic auxiliary avoid assorted cationic interference.And adopt the double-aqueous phase polymerization method, and product good emulsion stability and do not need dissolving, easy to use.Its synthesis technique can not produce secondary pollution, and energy consumption is low, and the nontoxic non-corrosiveness of product is environmentally friendly.
(3) the poly-propionic acid amide emulsion of the both sexes that the present invention synthesized can obviously improve drainability and the fibre strength of sediment in the paper waste as paper making additive, and consumption only is other usual auxiliaries half, and price is low.Product is milky white transparence, and median size is 68nm, and particle size range is 60-75nm, and the copolymer product intrinsic viscosity is 115.48mL/g, and molecular weight is 30.36 ten thousand, is suitable as paper making additive.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Three kinds of monomers are mixed with mol ratio AM:AMPS:DMC=70:15:15, and quality is 60g, accounts for 30% of total mass, adds suitable quantity of water dissolving and regulator solution pH value to 3, and adds 0.12g reductive agent sodium bisulfite.
Condensation reflux unit is being housed, add the aqueous solution and the 1.6g polyvinylpyrrolidone that contains 45g ammonium sulfate in the reactor of agitator, thermometer and logical nitrogen pipe, on one side the mixing solutions in the reactor is stirred with the speed of 300r/min and be heated to 35 ℃ on one side, add 0.08g oxidation initiator potassium persulfate, feed nitrogen.
The speed of monomer solution with 35mL/h is added dropwise in the reactor, reacts 6h under the air-proof condition, after reaction finishes, stop heating, logical nitrogen and stirring, will generate emulsion and take out.Adding the sealing of 0.008g hydroquinone of polymerization retarder room temperature preserves.
Adopt the amphiprotic polyacrylamide emulsion of present embodiment preparation to experimentize as paper making additive, the result who obtains is as shown in table 1.
The amphiprotic polyacrylamide emulsion of table 1. present embodiment preparation is joined the enhancement of copying the sediment mixed pulp to the OCC paper waste
Slurry is from the sediment of certain secondary corrugating material paper mill plain boiled water section and secondary corrugating material magma, its sediment is Dark grey mud shape, need to remove moisture through sludge tank earlier, remove partial impurities through jumping sieve then, by the taper sand cleaning machine papermaking sediment is removed part of ash again, obtain purer fiber by the separation and purification of inflation hydrocyclone again.The joining of the sediment fiber that OCC paper waste and purifying are crossed copying mass ratio is 7:3, as known from Table 1, and when the amphiprotic polyacrylamide consumption of present embodiment preparation is 0.3%, paper basis weight has improved 3.0%, tear index has improved 15.1%, and burst index has improved 17.2%, and tensile index has improved 7.7%.
Use same slurry, add amphiprotic polyacrylamide emulsion auxiliary agent and other several frequently seen auxiliary agents of present embodiment preparation, treatment effect sees Table 2.
The different paper making additives of table 2 are joined the enhancement of copying the sediment mixed pulp to the OCC paper waste
As known from Table 2, the amphiprotic polyacrylamide emulsion of present embodiment preparation is compared with existing paper making additive on the market, consumption is few and can reach better enhancing and retention and drainage effect, can effectively solve the problem that the sediment fiber is used for the paper strength difference of papermaking generation.
Embodiment 2
Three kinds of monomers are mixed with mol ratio AM:AMPS:DMC=80:10:10, and quality is 70g, accounts for 35% of total mass, adds suitable quantity of water dissolving and regulator solution pH value to 4, and adds 0.18g reductive agent sodium bisulfite.
Condensation reflux unit is being housed, add the aqueous solution and the 2g polyvinylpyrrolidone that contains 40g ammonium sulfate in the reactor of agitator, thermometer and logical nitrogen pipe, on one side the mixing solutions in the reactor is stirred with the speed of 350r/min and be heated to 40 ℃ on one side, add 0.12g oxidation initiator potassium persulfate, feed nitrogen.
The speed of monomer solution with 45mL/h is added dropwise in the reactor, reacts 8h under the air-proof condition, after reaction finishes, stop heating, logical nitrogen and stirring, will generate emulsion and take out.Adding the sealing of 0.012g hydroquinone of polymerization retarder room temperature preserves.
Embodiment 3
Three kinds of monomers are mixed with mol ratio AM:AMPS:DMC=78:11:11, and quality is 64g, accounts for 32% of total mass, adds suitable quantity of water dissolving and regulator solution pH value to 3, and adds 0.15g reductive agent sodium bisulfite.
Condensation reflux unit is being housed, add the aqueous solution and the 1.8g polyvinylpyrrolidone that contains 46g ammonium sulfate in the four-hole boiling flask of agitator, thermometer and logical nitrogen pipe, on one side the mixing solutions in the reactor is stirred with the speed of 320r/min and be heated to 38 ℃ on one side, add 0.1g oxidation initiator potassium persulfate, feed nitrogen.
The speed of monomer solution with 40mL/h is added dropwise in the reactor, reacts 7h under the air-proof condition, after reaction finishes, stop heating, logical nitrogen and stirring, will generate emulsion and take out.Adding the sealing of 0.01g hydroquinone of polymerization retarder room temperature preserves.
Cost analysis
The cost analysis that the amphiprotic polyacrylamide emulsion of the present invention's preparation is handled one ton of paper waste (OCC slurry and sediment fiber) as auxiliary agent sees Table 3.
The amphiprotic polyacrylamide emulsion of table 3 the present invention preparation is handled paper waste per ton (calculating with oven dry stock) cost analysis
The amphiprotic polyacrylamide emulsion auxiliary agent of employing the present invention preparation and other paper making additives commonly used see Table 4 for the treatment of the cost contrast of one ton of fiber fines.
The different paper making additives of table 4 are handled the cost analysis of one ton of fiber fines
By table 4 result as can be known, it is good that the amphiprotic polyacrylamide emulsion of the present invention preparation and paper making additive commonly used are in the market compared effect, is applied to the reuse of fiber fines, to the water filtering performance of fiber, resident performance, become the paper dry strength that significant lifting is arranged.And synthetic emulsion does not contain the composition of environmental pollution, can not cause secondary pollution to environment, meets present requirement for the paper making additive clean and effective.Consumption is few relatively, and cost is low, has good economy, environment and social benefit, has the vast market using value.
Above-described embodiment is preferred implementation of the present invention; but embodiments of the present invention are not limited by the examples; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. a preparation method who improves the amphiprotic polyacrylamide emulsion of waste paper fiber fines intensity is characterized in that, may further comprise the steps:
(1) by following mass percent weighing material: monomer 30%～35%, sodium bisulfite 0.06%～0.09%, Potassium Persulphate 0.04%～0.06%, polyvinylpyrrolidone 0.8%～1.0%, Resorcinol 0.4%～0.6%; Described monomer is made up of AM, AMPS and DMC;
(2) monomer is made into monomer solution, and regulates pH value to 3～4;
(3) in the temperature control reactor that condensation reflux unit, agitator and logical nitrogen pipe are housed, add ammoniumsulphate soln, polyvinylpyrrolidone, sodium bisulfite, feed nitrogen, add Potassium Persulphate after under 30～40 ℃ condition, stirring, then monomer solution is added dropwise to and carries out polyreaction in the reactor;
(4) treat that monomer solution all adds after, the control temperature of reaction adds Resorcinol inhibition and the heating of stopped reaction still, feeds nitrogen and stirring at 35 ℃～40 ℃ behind the reaction terminating, the emulsion room temperature sealing that generates is preserved.
2. the preparation method of the amphiprotic polyacrylamide emulsion of raising waste paper fiber fines intensity according to claim 1, it is characterized in that, the mol ratio of described AMPS and DMC is 1:1, and the AM molar mass is 0.7:1～0.8:1 with three kinds of total molar masss ratios of monomer.
3. the preparation method of the amphiprotic polyacrylamide emulsion of raising waste paper fiber fines intensity according to claim 1 is characterized in that, the described stirring of step (2) is specially: the speed with 300～350rpm stirs.
4. the preparation method of the amphiprotic polyacrylamide emulsion of raising waste paper fiber fines intensity according to claim 1 is characterized in that, step (3) is described to be added dropwise to monomer solution in the reactor, is specially:
The speed of monomer solution with 35mL/h～45mL/h is added dropwise in the reactor.
5. the preparation method of the amphiprotic polyacrylamide emulsion of raising waste paper fiber fines intensity according to claim 1 is characterized in that, the time of described polyreaction is 6h～8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310075603.3A CN103193930B (en) | 2013-03-08 | 2013-03-08 | A kind of preparation method improving the amphiprotic polyacrylamide emulsion of waste paper fine fiber strength |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310075603.3A CN103193930B (en) | 2013-03-08 | 2013-03-08 | A kind of preparation method improving the amphiprotic polyacrylamide emulsion of waste paper fine fiber strength |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103193930A true CN103193930A (en) | 2013-07-10 |
| CN103193930B CN103193930B (en) | 2016-01-06 |
Family
ID=48716758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310075603.3A Expired - Fee Related CN103193930B (en) | 2013-03-08 | 2013-03-08 | A kind of preparation method improving the amphiprotic polyacrylamide emulsion of waste paper fine fiber strength |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103193930B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107779183A (en) * | 2017-03-23 | 2018-03-09 | 西南石油大学 | Big temperature difference retarder of cementing slurry and preparation method thereof |
| CN108083614A (en) * | 2018-02-05 | 2018-05-29 | 中国科学院长春应用化学研究所 | A kind of water-dispersion type composite diatomite flocculation dewatering agent and its application |
| CN110407974A (en) * | 2019-08-15 | 2019-11-05 | 浙江传化华洋化工有限公司 | A kind of preparation method of cross-linking amphiprotic polyacrylamide polymer |
| CN113912771A (en) * | 2021-09-28 | 2022-01-11 | 苏州派凯姆新能源科技有限公司 | Preparation method and application of amphoteric polyacrylamide resin papermaking reinforcing agent |
| CN114108356A (en) * | 2021-10-21 | 2022-03-01 | 江苏理文造纸有限公司 | Papermaking white water anion garbage recycling process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005100423A1 (en) * | 2004-04-07 | 2005-10-27 | Snf Sas | Novel high molecular weight associative amphoteric polymers and uses thereof |
| CN101514239A (en) * | 2008-12-30 | 2009-08-26 | 上海东升新材料有限公司 | Amphoteric polyacrylamide and preparation method thereof |
-
2013
- 2013-03-08 CN CN201310075603.3A patent/CN103193930B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005100423A1 (en) * | 2004-04-07 | 2005-10-27 | Snf Sas | Novel high molecular weight associative amphoteric polymers and uses thereof |
| CN101514239A (en) * | 2008-12-30 | 2009-08-26 | 上海东升新材料有限公司 | Amphoteric polyacrylamide and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 安会勇等: "ＡＭ/ＡＭPＳ/ＤＭＣ聚两性电解质的合成、表征", 《应用化工》 * |
| 张其平: "分散共聚合制备离子型聚丙烯酰胺", 《中国优秀硕士论文全文数据库（工程科技Ⅰ辑）》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107779183A (en) * | 2017-03-23 | 2018-03-09 | 西南石油大学 | Big temperature difference retarder of cementing slurry and preparation method thereof |
| CN107779183B (en) * | 2017-03-23 | 2020-03-27 | 西南石油大学 | Well cementation cement slurry large temperature difference retarder and preparation method thereof |
| CN108083614A (en) * | 2018-02-05 | 2018-05-29 | 中国科学院长春应用化学研究所 | A kind of water-dispersion type composite diatomite flocculation dewatering agent and its application |
| CN108083614B (en) * | 2018-02-05 | 2020-12-08 | 中国科学院长春应用化学研究所 | Water-dispersible diatomite composite flocculation dehydrating agent and application thereof |
| CN110407974A (en) * | 2019-08-15 | 2019-11-05 | 浙江传化华洋化工有限公司 | A kind of preparation method of cross-linking amphiprotic polyacrylamide polymer |
| CN113912771A (en) * | 2021-09-28 | 2022-01-11 | 苏州派凯姆新能源科技有限公司 | Preparation method and application of amphoteric polyacrylamide resin papermaking reinforcing agent |
| CN114108356A (en) * | 2021-10-21 | 2022-03-01 | 江苏理文造纸有限公司 | Papermaking white water anion garbage recycling process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103193930B (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103193930B (en) | A kind of preparation method improving the amphiprotic polyacrylamide emulsion of waste paper fine fiber strength | |
| CN103232573B (en) | Preparation method of polyacrylamide emulsion | |
| CN105484094B (en) | Low-gram-weight kraft paper produced from reclaimed waste paper and production process | |
| CN105452565B (en) | Nanocrystalline cellulose and the nanocrystalline cellulose of polymer grafting are used in paper technology increase the purposes of retention rate | |
| JP6425725B2 (en) | Use of nanocrystalline cellulose and polymer grafted nanocrystalline cellulose to increase retention in papermaking process | |
| CN102121208B (en) | Method for preparing papermaking dry strengthening agent | |
| CN103468028B (en) | A kind of Efficient calcium slurry dispersant and preparation method thereof | |
| KR101617313B1 (en) | Polymer dispersion | |
| CN101885528B (en) | Powdery high-whiteness polyaluminium chloride complex and preparation method thereof | |
| CN104086709A (en) | High-branch-chain water-soluble cellulose-acrylamide grafted copolymer and preparation method and application thereof | |
| CN102020720B (en) | High branch cationic starch for papermaking wet end and preparation method thereof | |
| EP2449175A1 (en) | Papermaking and products made thereby with high solids glyoxalated-polyacrylamide and silicon-containing microparticle | |
| CN107603278A (en) | A kind of paper grade (stock) modified calcium carbonate and its processing technology | |
| CN104877080A (en) | Preparation method of chitosan-grafted and organosilicone-modified amphoteric polyacrylamide | |
| CN101514265B (en) | Mixed calcium carbonate, preparation method and application thereof | |
| CN102382263A (en) | Starch graft acrylate copolymer emulsion, preparation method and application thereof | |
| CN102154934B (en) | Novel retention and filtration aid system for light paper | |
| CN102154943A (en) | Retention and reinforcing agent for papermaking and paper strength retention and reinforcing method | |
| TW201739983A (en) | Use of an acrylate copolymer, a method of making a substrate comprising cellulosic fibres by using the same, and the corresponding substrate | |
| CN103897107A (en) | Method for preparing paper stiffness agent | |
| CN106866897A (en) | A kind of straw base compounded mix, its preparation method and the paper containing the compounded mix | |
| CN105237648B (en) | A kind of glyoxal cross-linked polymer is modified high amylopectin starch and its preparation method and application | |
| WO2017177349A1 (en) | Ternary filler system for paper/paperboard production and preparation method therefor | |
| CN101357966B (en) | Method for preparing nano amphoteric polyacrylamide additives | |
| CN101575113B (en) | Mixed calcium carbonate, preparation method and application 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160106 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |