CN102586921A - Method for producing polyacrylonitrile-based carbon fiber precursor - Google Patents
Method for producing polyacrylonitrile-based carbon fiber precursor Download PDFInfo
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- CN102586921A CN102586921A CN2011100015484A CN201110001548A CN102586921A CN 102586921 A CN102586921 A CN 102586921A CN 2011100015484 A CN2011100015484 A CN 2011100015484A CN 201110001548 A CN201110001548 A CN 201110001548A CN 102586921 A CN102586921 A CN 102586921A
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Abstract
The invention relates to a method for producing a polyacrylonitrile-based carbon fiber precursor by using dimethylformamide as a solvent. The polyacrylonitrile-based carbon fiber precursor finished product is prepared by the following steps of preparation of stock solution, monomer removal, filtration, coagulating bath, pre-drawing, washing, rear drawing, oiling and drying drawing. According to the invention, due to the utilization of the dimethylformamide with the chain transfer effect, a polymer has moderate molecular weight and the molecular weight distribution is narrowed down; by reducing the concentration of a reactant, reducing the polymerization reaction temperature, prolonging the reaction time and controlling the polymerization reaction conversion rate, the polymerization heat release in unit time is reduced and the reaction can be performed at a balanced temperature, so that the quality of the stock solution is improved; by improving the concentration of the coagulating bath and reducing the double diffusion speed, the forming of a sheath-core structure is avoided; and by increasing the number of hot rolls, prolonging the retention time and carrying out drawing at the same time, the bridging of holes is further promoted and fibers have uniform property.
Description
Technical field:
The present invention relates to a kind of production method of polyacrylonitrile base carbon fiber precursors, particularly relate to and use the production method of dimethyl formamide as the polyacrylonitrile base carbon fiber precursors of solvent.
Technical background: carbon fiber is as a kind of new and high technology material, has high-strength, Gao Mo, low-density, advantage such as high temperature resistant, is widely used in fields such as aviation, automobile, style.Polyacrylonitrile base carbon fiber precursors is the important source material of preparation carbon fiber, and the article confrontation carbon fiber quality of precursor plays decisive role.
The acrylonitrile polymerization reaction speed is fast, and thermal discharge is big, and implode takes place easily.For suitability for industrialized production, react uncontrollable.Cause inhomogeneous this of polymer molecular weight will cause the quality of precursor to descend, influence the quality of carbon fiber.
It is extremely important that coagulating bath concentration is solidified the formation precursor to polymer, and the concentration of coagulating bath is being controlled double diffused speed.The concentration of present domestic coagulating bath is lower, and the double diffusion excessive velocities makes precursor form skin-core structure, causes former yarn quality to descend.
Dry run can promote the precursor inside holes to make up, reduces the precursor defective.The general form that adopts heating hot-rolling drying, but drying time is all shorter, has seriously undermined the effect of compacting by drying, has caused the defective of precursor.
Summary of the invention:
The object of the invention provides a kind of production method of polyacrylonitrile carbon fiber precursor, in the method, and through reducing reaction temperature; Prolong the reaction time, make unit interval thermal discharge minimizing in the course of reaction, thereby make polymerization process controlled; The resulting polymers molecular weight is moderate, narrow molecular weight distribution.Through reducing coagulation bath temperature, improve coagulating bath concentration, reduce double diffusion speed and avoid taking place skin-core structure.Simultaneously in the process of coagulation forming, add cleaning agent, remove the impurity in precursor and the coagulating bath solvent, make the precursor impurity content low, defective is few.Through prolonging the dry drawing-off time, impel the hole in the fiber to make up.
Method of the present invention may further comprise the steps:
1, stoste preparation: in the quality proportioning is the reactant of comonomer composition of acrylonitrile and 1-5% of 95-99%, add initator; The addition of initator is the 0.01-0.1% of above-mentioned reactant quality, in the solvent dimethyl formamide, reacts the generation polyacrylonitrile polymer then.The mass ratio of solvent and above-mentioned substance total amount is 60-80%.Reaction temperature is controlled at 40-70 ℃, preferred 40-55 ℃; Reaction time 25-50 hour, preferred 30-45 hour; The polyacrylonitrile polymer molecular weight that generates is 7-11 ten thousand.Wherein, said comonomer is itaconic acid or methyl methacrylate; Initator is an azodiisobutyronitrile.
2, take off list: stoste gets into and to take off Dan Ta and remove unreacted acrylonitrile and comonomer after polymerization, takes off that temperature is 50-90 ℃ in single tower, pressure 0.001-0.05MPaG.Make at last that polyacrylonitrile copolymer quality mass number is 20-25%. in the stoste
3, filter: take off single back stoste and remove the gel that produces in the course of reaction through three-stage filtration, filtering accuracy is respectively: one-level 20-30um, secondary 5-15um, three grades of 2-5um.
4, coagulating bath: stoste gets into the coagulating bath coagulation forming through the measuring pump metering through spinnerets.Coagulation bath temperature 15-30 ℃, time of staying 25-50 second.Solvent dimethyl formamide mass concentration 55-80% in the coagulating bath, preferred 60-75%; Cleaning agent mass concentration 0.01-10%.Said cleaning agent is selected from the combination of one or more materials in benzoic acid, itaconic acid, formic acid, acetate, triethylamine, pyridine, ammoniacal liquor, monoethanolamine, the bicyclic amidine.Between combination proportion relation needn't be arranged.
5, preliminary draft: solidifying in the tow entering preliminary draft machine of gained carried out preliminary draft, 60-80 ℃ of preliminary draft temperature, solvent dimethyl formamide mass concentration 10-60% in the preliminary draft, preferred 10-50% in the coagulating bath; Time of staying 30-75 second, drafting multiple 2-5 doubly.
6, washing: tow gets into washing step behind the preliminary draft, and washing temperature 70-85 ℃, time of staying 30-50 second.
7, first break draft: washing back tow carries out first break draft, 85-100 ℃ of first break draft temperature, and time of staying 15-40 second, drafting multiple 2-6 is doubly.
8, oil: the tow through first break draft oils, and the rate of oiling is the 0.5-1% of tow weight.
9, dry drawing-off: dry drawing-off is carried out on 20-50 hot-rolling, and the hot-rolling number is preferably 20-35; Except that last hot-rolling, heat roller temperature is controlled at 160-210 ℃, preferred 160-190 ℃; Last heat roller temperature is 50-120 ℃, final drafting multiple 1-5, and tow contains quality less than 2%, the remaining quality 1.0-1.8% of finish.Make the polyacrylonitrile base carbon fiber precursors finished product at last.
The present invention has the following advantages:
Utilize dimethyl formamide to have chain transfer, make polymer molecular weight moderate, molecular weight distribution narrows down; Through reducing reactant concentration, reduce polymeric reaction temperature, prolong the reaction time, the control polymerization conversion, thus reduced the unit interval polymerization exotherm, reaction can be reacted under the temperature of equilibrium, thereby improve the quality of stoste; Through improving the concentration of coagulating bath, reduce double diffusion speed, avoid forming skin-core structure; Through increasing hot-rolling quantity, increase the time of staying, carry out drawing-off simultaneously, promote that further hole makes up, make the fibre property homogeneous.
The specific embodiment:
Embodiment one
1, stoste preparation: the quality proportioning in the reactant is an acrylonitrile 96%, and comonomer 4% adds initator and in the solvent dimethyl formamide, reacts.Reaction temperature is controlled at 60 ℃, and in 38 hours reaction time, polymer molecular weight is 10.5 ten thousand.
2, take off list: stoste gets into and to take off Dan Ta and deviate from unreacted acrylonitrile and comonomer after polymerization, and the mass fraction that makes polyacrylonitrile copolymer in the stoste is 23%.
3, filter: take off single back stoste and remove the gel that produces in the course of reaction through three-stage filtration, filtering accuracy is respectively: one-level 30um, secondary 12um, three grades of 3um.
4, coagulating bath: stoste gets into the coagulating bath coagulation forming through the measuring pump metering through spinnerets.28 ℃ of coagulation bath temperatures, solvent quality concentration 68% in the coagulating bath, detergent concentration 5%.40 seconds time of staying.
5, preliminary draft: solidifying in the tow entering preliminary draft machine of gained carried out preliminary draft, 77 ℃ of preliminary draft temperature, solvent quality concentration 20% in the preliminary draft, 75 seconds time of staying, 3 times of drafting multiples in the coagulating bath.
6, washing: tow gets into washing step, 85 ℃ of washing temperature, 50 seconds time of staying behind the preliminary draft.
7, first break draft: washing back tow carries out first break draft, 90 ℃ of first break draft temperature, 30 seconds time of staying, 6 times of drafting multiples.
8, oil: the tow through first break draft oils, and the rate of oiling is 1% of a tow weight.
9, drying: drying is carried out on 40 hot-rollings, and 200 ℃ of heat roller temperatures, last heat roller temperature are controlled at 100 ℃, drafting multiple 2.Final tow moisture 2%, finish residual volume 1.5%.
Fiber number: 0.95d intensity: 6.7g/d extension at break: 12%
Embodiment two
1, stoste preparation: the quality proportioning in the reactant is an acrylonitrile 98%, and comonomer 2% adds initator and in the solvent dimethyl formamide, reacts.Reaction temperature is controlled at 60 ℃, and in 35 hours reaction time, polymer molecular weight is 90,000.
2, take off list: stoste gets into and to take off Dan Ta and deviate from unreacted acrylonitrile and comonomer after polymerization, and the mass fraction that makes polyacrylonitrile copolymer in the stoste is 21%.
3, filter: take off single back stoste and remove the gel that produces in the course of reaction through three-stage filtration, filtering accuracy is respectively: one-level 30um, secondary 12um, three grades of 2um.
4, coagulating bath: stoste gets into the coagulating bath coagulation forming through the measuring pump metering through spinnerets.30 ℃ of coagulation bath temperatures, solvent quality concentration 80% in the coagulating bath, detergent concentration 7%.50 seconds time of staying.
5, preliminary draft: solidifying in the tow entering preliminary draft machine of gained drawn 70 ℃ of preliminary draft temperature, solvent quality concentration 30% in the preliminary draft, 60 seconds time of staying, 4 times of drafting multiples in advance in the coagulating bath.
6, washing: tow gets into washing step, 80 ℃ of washing temperature, 40 seconds time of staying behind the preliminary draft.
7, first break draft: washing back tow carries out first break draft, 95 ℃ of first break draft temperature, 40 seconds time of staying, 4 times of drafting multiples.
8, oil: the tow through first break draft oils, and the rate of oiling is 0.8% of a tow weight.
9, dry drawing-off: drying is carried out on 50 hot-rollings, 190 ℃ of heat roller temperatures, and last heat roller temperature is controlled at 120 ℃, and multiple 2 protracts.Final tow moisture is less than 1.8%, finish residual volume 1.2%.Fiber number: 1.05d intensity: 6.5g/d extension at break: 15%.
Claims (10)
1. the production method of a polyacrylonitrile base carbon fiber precursors makes the polyacrylonitrile base carbon fiber precursors finished product by following steps:
The stoste preparation; Take off list; Filter; Coagulating bath; Preliminary draft; Washing; First break draft; Oil; Dry drawing-off.
2. production method according to claim 1 is characterized in that, makes the polyacrylonitrile base carbon fiber precursors finished product by following steps:
(1), stoste preparation: in the quality proportioning is the reactant of comonomer composition of acrylonitrile and 1-5% of 95-99%, add initator; The addition of initator is the 0.01-0.1% of above-mentioned reactant quality, in the solvent dimethyl formamide, reacts the generation polyacrylonitrile polymer then; The mass ratio of solvent and above-mentioned substance total amount is 60-80%, and reaction temperature is controlled at 40-70 ℃, reaction time 25-50 hour, generates polyacrylonitrile polymer;
(2), take off list: stoste gets into and to take off Dan Ta and remove unreacted acrylonitrile and comonomer after polymerization, takes off that temperature is 50-90 ℃ in single tower, and pressure 0.001-0.05MPaG makes at last that polyacrylonitrile copolymer quality number is 20-25% in the stoste;
(3), filter: take off single back stoste and remove the gel that produces in the course of reaction through three-stage filtration;
(4), coagulating bath: stoste gets into the coagulating bath coagulation forming through the measuring pump metering through spinnerets; Coagulation bath temperature 15-30 ℃, time of staying 25-50 second; Solvent dimethyl formamide mass concentration 55-80% in the coagulating bath, cleaning agent mass concentration 0.01-10%;
(5), preliminary draft: the tow that solidifies of gained gets in the preliminary draft machine and carries out preliminary draft in the coagulating bath, 60-80 ℃ of preliminary draft temperature, solvent dimethyl formamide mass concentration 10-60% in the preliminary draft, time of staying 30-75 second, drafting multiple 2-5 doubly;
(6), washing: tow gets into washing step behind the preliminary draft, washing temperature 70-85 ℃, time of staying 30-50 second;
(7), first break draft: washing back tow carries out first break draft, 85-100 ℃ of first break draft temperature, time of staying 15-40 second, drafting multiple 2-6 is doubly;
(8), oil: the tow through first break draft oils, and the rate of oiling is the 0.5-1% of tow weight;
(9), dry drawing-off: dry drawing-off is carried out on 20-50 hot-rolling, and except that last group hot-rolling, heat roller temperature is controlled at 160-210 ℃; Last group heat roller temperature is 30-120 ℃; Final drafting multiple 1-3, the tow moisture is less than 2%, finish residual volume 1.0-1.8%.
3. according to claim 2,3 production method, in step (1), the polyacrylonitrile polymer molecular weight of generation is 7-11 ten thousand.
4. according to claim 2,3 production method, in step (1), reaction generates the preferred 40-55 of reaction temperature ℃ of polyacrylonitrile polymer; Preferred 30-45 of reaction time hour.
5. according to the production method of claim 2, in step (3), the filtering accuracy of three-stage filtration is respectively: one-level 20-30um, secondary 5-15um, three grades of 2-5um.
6. according to the production method of claim 2, in step (4), said cleaning agent is selected from the one or more combination in benzoic acid, itaconic acid, formic acid, acetate, triethylamine, pyridine, ammoniacal liquor, monoethanolamine, the bicyclic amidine.
7. according to the production method of claim 2, in step (4), the preferred 60-75% of solvent dimethyl formamide mass concentration in the coagulating bath.
8. according to the production method of claim 2, in step (5), the preferred 10-50% of solvent dimethyl formamide mass concentration in the preliminary draft.
9. according to the production method of claim 2, in step (9), except that last group hot-rolling, the preferred 160-190 of heat roller temperature ℃.
10. according to the production method of claim 2, in step (1), said comonomer is itaconic acid or methyl methacrylate; Initator is an azodiisobutyronitrile.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103399490A (en) * | 2013-08-01 | 2013-11-20 | 东华大学 | Immune memory learning control based wet coagulation bath temperature control process for carbon fiber precursor |
| CN103614801A (en) * | 2013-12-03 | 2014-03-05 | 国家电网公司 | Method for preparing high-crystallinity polyacrylonitrile nascent fiber |
| CN103668524A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of low-viscosity high-performance binary acrylonitrile polymer spinning liquor |
| CN103952797A (en) * | 2014-04-23 | 2014-07-30 | 北京化工大学 | Preparation method of wet-process high-strength polyacrylonitrile-based carbon fiber |
| CN105986328A (en) * | 2015-03-04 | 2016-10-05 | 吉林碳谷碳纤维有限公司 | Method for preparing high-strength acrylic industrial yarns |
| CN110685041A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber |
| CN113072658A (en) * | 2021-04-02 | 2021-07-06 | 长春工业大学 | High-solid-content low-viscosity polyacrylonitrile turbid liquid, preparation method and application thereof, and preparation method of polyacrylonitrile-based carbon fiber |
| CN113373540A (en) * | 2021-07-07 | 2021-09-10 | 山西钢科碳材料有限公司 | Polyacrylonitrile fiber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401675A (en) * | 2002-08-13 | 2003-03-12 | 中国科学院山西煤炭化学研究所 | Method for preparing polyacrylonitrile based carbon fibre spinning solution |
| CN101260172A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing super-high molecular weight polyacrylonitrile-base carbon fiber spinning primary fluid |
| CN101643943A (en) * | 2009-07-10 | 2010-02-10 | 东华大学 | Preparation method for polyacrylonitrile-based carbon fiber protofilament |
| CN101831729A (en) * | 2010-05-10 | 2010-09-15 | 北京化工大学 | High-hydrophilic and exothermal spinning solution for polyacrylonitrile-based carbon fibers and preparation method thereof |
| CN101864028A (en) * | 2010-05-28 | 2010-10-20 | 金发科技股份有限公司 | Preparation method of polyacrylonitrile spinning solution |
-
2011
- 2011-01-06 CN CN2011100015484A patent/CN102586921A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401675A (en) * | 2002-08-13 | 2003-03-12 | 中国科学院山西煤炭化学研究所 | Method for preparing polyacrylonitrile based carbon fibre spinning solution |
| CN101260172A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing super-high molecular weight polyacrylonitrile-base carbon fiber spinning primary fluid |
| CN101643943A (en) * | 2009-07-10 | 2010-02-10 | 东华大学 | Preparation method for polyacrylonitrile-based carbon fiber protofilament |
| CN101831729A (en) * | 2010-05-10 | 2010-09-15 | 北京化工大学 | High-hydrophilic and exothermal spinning solution for polyacrylonitrile-based carbon fibers and preparation method thereof |
| CN101864028A (en) * | 2010-05-28 | 2010-10-20 | 金发科技股份有限公司 | Preparation method of polyacrylonitrile spinning solution |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103668524A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of low-viscosity high-performance binary acrylonitrile polymer spinning liquor |
| CN103668524B (en) * | 2012-09-05 | 2016-07-13 | 中国石油化工股份有限公司 | Low viscosity, high-performance binary acrylonitrile copolymer spinning solution preparation method |
| CN103399490A (en) * | 2013-08-01 | 2013-11-20 | 东华大学 | Immune memory learning control based wet coagulation bath temperature control process for carbon fiber precursor |
| CN103399490B (en) * | 2013-08-01 | 2016-05-18 | 东华大学 | A kind of carbon fibre precursor wet method coagulation bath temperature control technique that study is controlled based on immunological memory |
| CN103614801A (en) * | 2013-12-03 | 2014-03-05 | 国家电网公司 | Method for preparing high-crystallinity polyacrylonitrile nascent fiber |
| CN103952797A (en) * | 2014-04-23 | 2014-07-30 | 北京化工大学 | Preparation method of wet-process high-strength polyacrylonitrile-based carbon fiber |
| CN105986328A (en) * | 2015-03-04 | 2016-10-05 | 吉林碳谷碳纤维有限公司 | Method for preparing high-strength acrylic industrial yarns |
| CN110685041A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber |
| CN110685041B (en) * | 2018-07-06 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile-based carbon fiber |
| CN113072658A (en) * | 2021-04-02 | 2021-07-06 | 长春工业大学 | High-solid-content low-viscosity polyacrylonitrile turbid liquid, preparation method and application thereof, and preparation method of polyacrylonitrile-based carbon fiber |
| CN113072658B (en) * | 2021-04-02 | 2022-08-12 | 长春工业大学 | High-solid-content low-viscosity polyacrylonitrile turbid liquid, preparation method and application thereof, and preparation method of polyacrylonitrile-based carbon fiber |
| CN113373540A (en) * | 2021-07-07 | 2021-09-10 | 山西钢科碳材料有限公司 | Polyacrylonitrile fiber and preparation method thereof |
| CN113373540B (en) * | 2021-07-07 | 2022-10-14 | 山西钢科碳材料有限公司 | Polyacrylonitrile fiber and preparation method thereof |
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Application publication date: 20120718 |