CN102675611A - Polylactic acid composition and copolymerization modification method thereof - Google Patents
Polylactic acid composition and copolymerization modification method thereof Download PDFInfo
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- CN102675611A CN102675611A CN2012101806707A CN201210180670A CN102675611A CN 102675611 A CN102675611 A CN 102675611A CN 2012101806707 A CN2012101806707 A CN 2012101806707A CN 201210180670 A CN201210180670 A CN 201210180670A CN 102675611 A CN102675611 A CN 102675611A
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Abstract
The invention discloses a polylactic acid composition and a copolymerization modification method thereof. The method comprises the following steps: mixing lactide with one or more of trimethylene carbonic ester, tetramethylene carbonic ester, pentamethylene carbonic ester and hexamethylene carbonic ester, and carrying out copolymerization to obtain the polylactic acid composition. The polylactic acid can be toughened and modified to overcome the fragility of polylactic acid. The polylactic acid composition can be used for preparing films, fibers and injection molding products according to a common polymer material processing method.
Description
Technical field
The present invention relates to a kind of poly (lactic acid) composition and modification by copolymerization method thereof, belong to polymeric material field.
Background technology
POLYACTIC ACID also is called polylactide; It is the linear macromolecular material of a kind of thermoplasticity; Because it can be degraded into carbonic acid gas and water fully; And be 100% recyclable materials from bio-based; Therefore present each field such as film (like food packaging film, packing bag, refuse bag, mulch film etc.), fiber and various injection-molded items (like cup, plate, cutter difference etc.) etc. in national economy begin to apply, and are human guard ring border, and the dependence that alleviates petroleum resources provides a kind of practicable thinking.Shortcomings such as it has the advantage of degradation property, biocompatibility, workability and production process save energy preferably, but enbrittles simultaneously, and snappiness is relatively poor; Its range of application (Rahul M. Rasala, Amol V. Janorkarc, Douglas E. Hirt have been limited; Poly (lactic acid) modifications, Progress in Polymer Science, 2010; 35, p338 – 356).In recent years; Numerous scientists carry out modification to its performance; Wherein main method is copolymerization and the blending and modifying that adopts macromolecular material commonly used; Its main innovation is the screening and the use of properties-correcting agent, and multipolymer and carbonic ether (trimethylene carbonate) and the rac-Lactide copolymerization system of having synthesized caprolactone and rac-Lactide through the method for ring-opening polymerization like Grijpma etc. found the flexibility to POLYACTIC ACID have clear improvement (Grijpma et al, High molecular weight copolymers of l-lactide and ε-caprolactone as biodegradable elastomeric implant materials; Polym.Bull.1991,25:327-333; Polymerization temperature effects on the properties of l-lactide and ε-caprolactone copolymers.Polym, Bull.1991,25:335-341; Rubber toughening of poly (lactide) by blending and block copolymerization.Polym. Eng. Sci. 1994,34:1674 – 1684).Aspect blending and modifying; People such as Yeh have studied and have gathered (hexanodioic acid-terephthalic acid) butanediol ester and polylactic acid blend modification; Result of study shows the fragility that can improve POLYACTIC ACID, increases toughness, improves elongation at break (Yeh et al; Compatible and Crystallization Properties of Poly (lactic acid)/Poly (butylene adipate-co-terephthalate) Blends. Journal of Applied Polymer Science; 2010,116,680-687; Compatible and Tearing Properties of Poly (lactic acid)/Poly (ethylene glutaric-co-terephthalate) Copolyester Blends. Journal of Polymer Science:Part B:Polymer Physics; 2010; 48,913 – 920.).Also have many in addition through adding organic and priceless small molecules to polylactic acid modified dose; Organic molecule as as: triethyl citrate (TEC), tributyl citrate (TBC), glycerol acetate etc.; Inorganic molecules is like (Chinese patent: CN101338068, CN102134381A, CN102241877A such as nano kaoline, Win 40350, clay nano materials; CN101235194, CN102002223A etc.).
Above-mentioned method of modifying and properties-correcting agent have certain effect to increase POLYACTIC ACID toughness, reduction fragility; What have begins to form commodity, but used properties-correcting agent is mainly from petroleum products, and the price that has is too high; And not the green properties-correcting agent in bio-based source; If the POLYACTIC ACID in bio-based source does not use the properties-correcting agent in bio-based source, promote polylactic acid article and just lost meaning, these properties-correcting agent do not solve the fragility problem of POLYACTIC ACID fully yet simultaneously; Polylactic acid modified toughness reinforcing problem remains a difficult problem, limits its Application Areas.
Summary of the invention
The purpose of this invention is to provide a kind of poly (lactic acid) composition and modification by copolymerization method thereof; Be through independent in rac-Lactide and trimethylene carbonate, tetramethylene carbonic ether, 5-methylene carbonate, the hexa-methylene carbonic ether any one or several kinds mix to use and carry out copolymerization and obtain poly (lactic acid) composition; POLYACTIC ACID is carried out toughening modifying; Solve the fragility problem of POLYACTIC ACID, poly (lactic acid) composition can prepare film, fiber and injection-molded item through the common high molecular materials method for processing.
The objective of the invention is to realize like this:
This poly (lactic acid) composition, be through independent in rac-Lactide and trimethylene carbonate, tetramethylene carbonic ether, 5-methylene carbonate, the hexa-methylene carbonic ether any one or several kinds mix to use and carry out copolymerization and obtain poly (lactic acid) composition.
The modification by copolymerization method of this poly (lactic acid) composition; Rac-Lactide and cyclic carbonates monomer proportional mixing, add catalyzer, under the 100-200 degree; (under protection of inert gas or the vacuum) carried out ring-opening copolymerization under the anhydrous and oxygen-free condition; Polymerization time is 1-24 hour, and polymerization unit is the common equipment of high molecular polymerization, can be also can be continuous device intermittently; Reach the polymerization degree that needs and require the back to remove unreacted monomer, be prepared into pellet with the method for plastic working then or sheet material just obtains poly (lactic acid) composition with the ordinary method purifying.
The modification by copolymerization method of this poly (lactic acid) composition; Rac-Lactide and cyclic carbonates monomer proportional mixing, add catalyzer, under the 100-200 degree; Be to carry out ring-opening copolymerization (can be that protection of inert gas also can be under the vacuum) under the anhydrous and oxygen-free condition
The modification by copolymerization method of this poly (lactic acid) composition; Said rac-Lactide specifically is in one in L-rac-Lactide, D-rac-Lactide and the DL-rac-Lactide or several kinds of mixing are used, and said cyclic carbonates monomer specifically is that a kind of independent or several kinds of mixing in trimethylene carbonate, tetramethylene carbonic ether, 5-methylene carbonate, the hexa-methylene carbonic ether are used.
The modification by copolymerization method of this poly (lactic acid) composition, said catalyzer generally is the oxide compound of tin, the oxide compound of organic acid salt, metallic tin, metallic zinc and zinc, weisspiessglanz, general consumption is 0.0001-0.5%.
The modification by copolymerization method of this poly (lactic acid) composition; The monomeric ratio of said rac-Lactide and cyclic carbonates can be between weight ratio 95:5-40-60 according to the requirement to material flexibility; Molecular weight of copolymer generally is controlled between the 10-40 ten thousand; Can when polymerization, add alcohol compound and regulate molecular weight, the consumption of alcohol compound is 0-1%.
The modification by copolymerization method of this poly (lactic acid) composition, said rac-Lactide are in one in L-rac-Lactide, D-rac-Lactide and the DL-rac-Lactide or several kinds of mixing are used, and said alcohol compound can be lauryl alcohol, terepthaloyl moietie, 1, ammediol.
The modification by copolymerization method of this poly (lactic acid) composition, representational copolymer reaction formula is represented as follows in the said modification by copolymerization method:
POLYACTIC ACID-polytetramethylene carbonate copolymer
POLYACTIC ACID-polytetramethylene carbonic ether-polyhexamethylene carbonate copolymer
Wherein m=10-5000, n=10-5000, x=10-5000, y=10-5000, z=10-5000 in the above-mentioned reaction formula.
Except as otherwise noted, molecular weight related among the present invention representes with weight-average molecular weight that all its value utilizes gel permeation chromatography (GPC) to measure.
Poly (lactic acid) composition provided by the invention and modification by copolymerization method thereof are that POLYACTIC ACID is carried out toughening modifying, solve the fragility problem of POLYACTIC ACID, and poly (lactic acid) composition can prepare film, fiber and injection-molded item through the common high molecular materials method for processing.These method characteristics are that properties-correcting agent is the Biodegradable material in bio-based source, working method such as the injection moulding that the poly (lactic acid) composition after the modification can be through common plastics, means processing film forming, fiber, injection-molded item etc. such as extrude.
Provide embodiments of the invention below, the present invention is specifically described through embodiment.Be necessary to be pointed out that at this; Embodiment only is used for the present invention is further explained; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment
In following examples, except that specifying, related molecular weight is all represented with weight-average molecular weight.
Embodiment 1
In 1 liter of vial, add 300 gram L-rac-Lactides, 200 gram tetramethylene carbonic ethers; After high pure nitrogen displacement three times, nitrogen protection adds 0.05 gram stannous octoate down, is heated to 110 degree; Treat that monomer all melts the back stirring and is warmed up to 6 hours postcooling of 140-160 degree reaction to room temperature,, obtain poly (lactic acid) composition 480 grams with 5000 milliliters of ethanol sedimentations with 2000 milliliters of dissolved in chloroform products; Measure weight-average molecular weight 350,000 through GPC; MWD 2.3 is used the method for processing plastics to be processed into and measured elongation at break behind the standard batten is 160% (pure POLYACTIC ACID bibliographical information is usually less than 10%), explain that toughness increases greatly, can be as processing various goods.
Embodiment 2
In the reactor drum that 20 liters of Stainless Steel Bands stir, add 10.5 kilograms of L-rac-Lactides, 3 kilograms of tetramethylene carbonic ethers, 1.5 kilograms of trimethylene carbonates; Inflated with nitrogen and displaced air three times in the fusion of 100-110 degree, add stannous octoate 5 grams under the nitrogen protection then; In 130-150 degree polyreaction 5 hours; Vacuum (vacuum tightness 1-10mmHg) is removed unreacted monomer under this temperature then,, carries out underwater cutpellet and obtains 14.5 kilograms of poly (lactic acid) compositions mass transport discharging in single spiral shell screw extrusion press of 35mm with Melt Pump; Measure weight-average molecular weight 300,000 through GPC; MWD 2.3 is used the method for processing plastics to be processed into and measured elongation at break behind the standard batten is 110%, explain that toughness increases greatly, can be as processing various goods.
Embodiment 3
In the reactor drum that 20 liters of Stainless Steel Bands stir, add 8 kilograms of DL-rac-Lactides, 8 kilograms of trimethylene carbonates, inflated with nitrogen and displaced air three times; Under the nitrogen protection in the fusion of 130-140 degree; Add stannous octoate 16 gram then, in 150-170 degree polyreaction 6 hours, vacuum (vacuum tightness 1-10mmHg) was removed unreacted monomer under this temperature then; With Melt Pump mass transport discharging in the twin screw extruder of 35mm; Carry out underwater cutpellet and obtain 14.5 kilograms of poly (lactic acid) compositions, measure weight-average molecular weight 250,000 through GPC, MWD 2.3 is used the method for processing plastics to be processed into and measured elongation at break behind the standard batten is 190%; Explain that toughness increases greatly, can be as the various goods of processing.
Embodiment 4
In the reactor drum that 20 liters of Stainless Steel Bands stir, add 9.75 kilograms of DL-rac-Lactides, 5.25 kilograms of tetramethylene carbonic ethers, inflated with nitrogen and displaced air three times; Under the nitrogen protection in the fusion of 130-140 degree; Add stannous octoate 8 gram then, in 150-170 degree polyreaction 8 hours, vacuum (vacuum tightness 1-10mmHg) was removed unreacted monomer under this temperature then; With Melt Pump mass transport discharging in the twin screw extruder of 35mm; Carry out underwater cutpellet and obtain 14.5 kilograms of poly (lactic acid) compositions, measure weight-average molecular weight 280,000 through GPC, MWD 2.3 is used the method for processing plastics to be processed into and measured elongation at break behind the standard batten is 105%; Explain that toughness increases greatly, can be as the various goods of processing.
Embodiment 5
In the reactor drum that 20 liters of Stainless Steel Bands stir, add 11.25 kilograms of L-rac-Lactides, 3.75 kilograms of hexa-methylene carbonic ethers add terepthaloyl moietie 1.5 grams; Inflated with nitrogen and displaced air three times in the fusion of 100-120 degree, add stannous octoate 16 grams under the nitrogen protection then; In 140-150 degree polyreaction 5 hours; Vacuum (vacuum tightness 1-10mmHg) is removed unreacted monomer under this temperature then,, carries out underwater cutpellet and obtains 14.5 kilograms of poly (lactic acid) compositions mass transport discharging in the twin screw extruder of 35mm with Melt Pump; Measure weight-average molecular weight 150,000 through GPC; MWD 2.3 is used the method for processing plastics to be processed into and measured elongation at break behind the standard batten is 78%, explain that toughness increases greatly, can be as processing various goods.
Embodiment 6
In the reactor drum that 20 liters of Stainless Steel Bands stir, add 13.5 kilograms of D-rac-Lactides, 1.5 kilograms of tetramethylene carbonic ethers add terepthaloyl moietie 3 grams; Inflated with nitrogen and displaced air three times in the fusion of 100-120 degree, add stannous octoate 16 grams under the nitrogen protection then; In 140-150 degree polyreaction 5 hours; Vacuum (vacuum tightness 1-10mmHg) is removed unreacted monomer under this temperature then,, carries out underwater cutpellet and obtains 14.5 kilograms of poly (lactic acid) compositions mass transport discharging in the twin screw extruder of 35mm with Melt Pump; Measure weight-average molecular weight 80,000 through GPC; MWD 2.3 is used the method for processing plastics to be processed into and measured elongation at break behind the standard batten is 43%, explain that toughness increases greatly, can be as processing various goods.
Embodiment 7
In the reactor drum that 20 liters of Stainless Steel Bands stir, add 10.5 kilograms of D-rac-Lactides, 3 kilograms of tetramethylene carbonic ethers, 1.5 kilograms of trimethylene carbonates; Inflated with nitrogen and displaced air three times in the fusion of 100-110 degree, add stannous octoate 5 grams under the nitrogen protection then; 1, ammediol was in 130-150 degree polyreaction 5 hours; Vacuum (vacuum tightness 1-10mmHg) is removed unreacted monomer under this temperature then,, carries out underwater cutpellet and obtains 14.5 kilograms of poly (lactic acid) compositions mass transport discharging in single spiral shell screw extrusion press of 35mm with Melt Pump; Measure weight-average molecular weight 150,000 through GPC; MWD 2.3 is used the method for processing plastics to be processed into and measured elongation at break behind the standard batten is 210%, explain that toughness increases greatly, can be as processing various goods.
Claims (7)
1. poly (lactic acid) composition, it is characterized in that through independent in rac-Lactide and trimethylene carbonate, tetramethylene carbonic ether, 5-methylene carbonate, the hexa-methylene carbonic ether any one or several kinds mix to use and carry out copolymerization and obtain poly (lactic acid) composition.
2. the modification by copolymerization method of poly (lactic acid) composition according to claim 1; It is characterized in that:, add catalyzer, under the 100-200 degree rac-Lactide and cyclic carbonates monomer proportional mixing; Carry out ring-opening copolymerization; Polymerization time is 1-24 hour, and polymerization unit is the common equipment of high molecular polymerization, can be also can be continuous device intermittently; Remove unreacted monomer with the ordinary method purifying after the polymerization, be prepared into pellet with the method for plastic working then or sheet material just obtains poly (lactic acid) composition.
3. the modification by copolymerization method of poly (lactic acid) composition according to claim 2; It is characterized in that: said rac-Lactide specifically is in one in L-rac-Lactide, D-rac-Lactide and the DL-rac-Lactide or several kinds of mixing are used, and said cyclic carbonates monomer specifically is that a kind of independent or several kinds of mixing in trimethylene carbonate, tetramethylene carbonic ether, 5-methylene carbonate, the hexa-methylene carbonic ether are used.
4. the modification by copolymerization method of poly (lactic acid) composition according to claim 2, it is characterized in that: said catalyzer generally is the oxide compound of tin, the oxide compound of organic acid salt, metallic tin, metallic zinc and zinc, weisspiessglanz, general consumption is 0.0001-0.5%.
5. the modification by copolymerization method of poly (lactic acid) composition according to claim 2; It is characterized in that: the monomeric ratio of said rac-Lactide and cyclic carbonates can be between weight ratio 95:5-40:60 according to the requirement to material flexibility; Molecular weight of copolymer generally is controlled between the 10-40 ten thousand; Can when polymerization, add alcohol compound and regulate molecular weight, the consumption of alcohol compound is 0-1%.
6. the modification by copolymerization method of poly (lactic acid) composition according to claim 5; It is characterized in that: said rac-Lactide is in one in L-rac-Lactide, D-rac-Lactide and the DL-rac-Lactide or several kinds of mixing are used; Said alcohol compound can be lauryl alcohol, terepthaloyl moietie, 1, ammediol etc.
7. the modification by copolymerization method of poly (lactic acid) composition according to claim 2, it is characterized in that: representational copolymer reaction formula is represented as follows in the said modification by copolymerization method.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102935248A (en) * | 2012-10-19 | 2013-02-20 | 东华大学 | PLA absorbable bone screw with PBC as toughening agent, and preparation method thereof |
| CN104119486A (en) * | 2014-06-27 | 2014-10-29 | 苏州市盛百威包装设备有限公司 | Polycarbonate composite material and preparation method thereof |
| CN105999433A (en) * | 2016-05-11 | 2016-10-12 | 山东省药学科学院 | Polyglycolic acid particle doped polylactic acid-trimethylene carbonate film and preparation method and application thereof |
| CN113185678A (en) * | 2021-04-28 | 2021-07-30 | 武汉大学 | Preparation method of aliphatic polycarbonate polyester copolymer with zero catalyst addition |
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| US20100305300A1 (en) * | 2009-06-01 | 2010-12-02 | International Business Machines Corporation | Method of Ring-Opening Polymerization, and Related Compositions and Articles |
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| CHIKARA TSUTSUMI等: "Incorporation of L-lactide random copolymers with Japanese cypress oil (α-pinene) using supercritical carbon dioxide", 《GREEN CHEMISTRY》, vol. 14, 7 March 2012 (2012-03-07), pages 1211 - 1219 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102935248A (en) * | 2012-10-19 | 2013-02-20 | 东华大学 | PLA absorbable bone screw with PBC as toughening agent, and preparation method thereof |
| CN104119486A (en) * | 2014-06-27 | 2014-10-29 | 苏州市盛百威包装设备有限公司 | Polycarbonate composite material and preparation method thereof |
| CN105999433A (en) * | 2016-05-11 | 2016-10-12 | 山东省药学科学院 | Polyglycolic acid particle doped polylactic acid-trimethylene carbonate film and preparation method and application thereof |
| CN105999433B (en) * | 2016-05-11 | 2019-03-19 | 山东省药学科学院 | A kind of polylactic acid-trimethylene carbonate film and its preparation method and application adulterating polyglycolic acid particle |
| CN113185678A (en) * | 2021-04-28 | 2021-07-30 | 武汉大学 | Preparation method of aliphatic polycarbonate polyester copolymer with zero catalyst addition |
| CN113185678B (en) * | 2021-04-28 | 2022-04-29 | 武汉大学 | Preparation method of aliphatic polycarbonate polyester copolymer with zero catalyst addition |
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Application publication date: 20120919 |