WO2006056366A1 - Verfahren zur kontinuierlichen herstellung von alkylaminoacrylamiden - Google Patents
Verfahren zur kontinuierlichen herstellung von alkylaminoacrylamiden Download PDFInfo
- Publication number
- WO2006056366A1 WO2006056366A1 PCT/EP2005/012362 EP2005012362W WO2006056366A1 WO 2006056366 A1 WO2006056366 A1 WO 2006056366A1 EP 2005012362 W EP2005012362 W EP 2005012362W WO 2006056366 A1 WO2006056366 A1 WO 2006056366A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- distillation column
- acrylate
- reaction
- mixture
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
Definitions
- R 1 linear or branched alkyl radical having 3 to 10
- R 2 is a linear, branched or cyclic
- Alkyl radical an aryl radical which may also be substituted by one or more alkyl groups
- the linear, cyclic or branched alkyl radical may have a length of 1-12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. Butyl, pentyl, Hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl and may optionally be replaced by
- R 3 or R 4 may assume the meaning of hydrogen and furthermore:
- R 3 , R 4 or R 5 may be either the same or different and represent an alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. Butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl or hydrogen.
- R 6 may be a Ci-C 4 alkyl group, which may also be branched, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert. Butyl.
- R 7 may be the methyl group or the ethyl group.
- amines for example, the following compounds are suitable: Dimethylaminoethylamine, diethylaminoethylamine, Dipropylaminoethylamin, diisopropylaminoethylamine, dibutylaminoethylamine, Disobutylaminoehtylamin, dimethylaminopropylamine, diethylamino, dipropylaminopropylamine, Diisopropylaminopropylamin, dibutylaminopropylamine, Disobutylaminopropylamin, dimethylaminobutylamine, diethylaminobutylamine, Dipropylaminobutylamin, Diisopropylaminobutylamin, Dibutylaminobutylamin, Disobutylaminobutylamin, methylamine, cyclohexylamine, Dimethyla
- dimethylaminopropylamine dimethylaminoethylamine, dimethylaminobutylamine, dimethylaminopentylamine and dimethylaminohexylamine is particularly preferred.
- the continuous transesterification processes have the following advantages over the batch transesterification processes: The process is easier to automate and can be operated with reduced personnel requirements, the product quality is more reproducible and less variable, the plant capacity increases due to the omission of the sequential processing of the individual production steps (filling, reaction, low boiler removal, product separation, emptying).
- the process has a higher space-time yield than a batch process.
- EP 0 960 877 (Elf Atochem S.A.) describes a continuous process for the preparation of methacrylate esters of dialkylaminoalcohols. Dialkylamino alcohols are reacted with in general methyl (meth) acrylate and the dialkylaminoalkyl (meth) acrylate is obtained by the following process:
- the mixture of the starting materials (methyl (meth) acrylate and dialkylaminoalcohol) is used together with a tetraalkyl titanate as catalyst (for example tetrabutyl, tetraethyl or tetra (2-ethylhexyl) titanate) and at least one polymerization inhibitor (for example phenothiazine, tert-butylcatechol, hydroquinone monomethyl ether or hydroquinone) fed continuously to a stirred reactor, where at a temperature of 90 to 120 0 C, the conversion to the dialkylamino (meth) acrylate with simultaneous continuous withdrawal of the azeotropic methyl (meth) acrylate / methanol mixture.
- a tetraalkyl titanate for example tetrabutyl, tetraethyl or tetra (2-ethylhexyl) titanate
- at least one polymerization inhibitor for example phenothiazin
- the crude reaction mixture (crude ester) is fed to a first distillation column, wherein at reduced pressure at the top of the distillation column a substantially catalyst-free stream is withdrawn and withdrawn at the bottom of the distillation column of the catalyst and a little dialkylaminoalkyl (meth) acrylate.
- the top stream of the first distillation column is then fed to a second distillation column which comprises a stream of low-boiling products containing a little dialkylaminoalkyl (meth) acrylate under reduced pressure and a stream comprising mainly dialkylaminoalkyl (meth) acrylate and polymerization inhibitor (s) in the bottom.
- withdrawn which is fed to a third distillation column.
- a rectification carried out in which one withdraws the desired pure dialkylaminoalkyl (meth) acrylate ester at the top and in the bottom substantially the polymerization inhibitor or the polymerization inhibitors.
- the bottom stream of the first distillation column is recycled after further purification using a film evaporator as well as the top stream from the second distillation column.
- This process dispenses with dehydration of the alcohols before use, which can lead to increased deactivation of the tetraalkyl titanate used as a result of hydrolysis up to the formation of undesired precipitation of solids. Furthermore, the process has the disadvantage that in the first distillation column, the catalyst in the sump is thermally stressed at relatively high temperatures. This can easily lead to decomposition of the catalyst.
- EP 0 968 995 (Mitsubishi Gas Chemical Comp.) Describes a continuous process for the preparation of alkyl (meth) acrylic acid esters using a reaction column.
- the transesterification reaction is carried out directly in a distillation column (ie reactor and distillation column to remove the methyl (meth) acrylate / methanol azeotrope form an apparatus) to which the starting materials (methyl (meth) acrylate and alcohol) are fed continuously.
- the necessary catalyst here likewise preferably a titanium compound, is located in the distillation column. In the case of a homogeneous catalyst, the catalyst is continuously metered into the distillation column.
- the object of the present invention is to provide a continuous process for the aminolysis of acrylic acid esters which avoids the disadvantages of the two processes described above. Furthermore, the new process should provide a product that is better in quality than the one currently on the market. A better quality is understood to mean a lower crosslinker content or a lower content of addition products of the amines to the double bond of the starting ester or to the double bond of the product amide. Furthermore, with the new method aminoacrylates with as little effort and energetically cheaper (ie cheaper) are produced. The personnel costs for operating the system should be reduced.
- the method is shown schematically in FIG.
- FIG. 1 Explanations of the reference numbers FIG. 1:
- the Acrylatfeed starting material (11) is continuously fed to a suitable reactor (1), wherein both a single reaction vessel and a cascade of a plurality of successively connected reaction vessels can be used.
- a cascade may consist, for example, of 2, 3, 4, 5, 6 or optionally a plurality of individual reaction vessels.
- a cascade of 3 consecutively operated stirred kettles is used.
- the Acrylatfeed starting material (11) can be done in various ways. It is possible, for example, to supply the reactant stream (11) only to the first reaction vessel of the cascade or else to divide the reactant stream (11) into substreams and to supply these substreams to all or only some of the reaction vessels connected in series to the cascade. Exactly so it is possible to make the supply of the reactant stream (11) via the apparatus (2) and / or the reaction apparatuses (1). It may be advantageous to feed the educt stream (11) only into the apparatus (2) or, in another embodiment, to divide the educt stream (11) into partial streams which then both the apparatus (2) and the first or optionally a plurality of reaction vessels of the cascade be supplied.
- the flow guidance to and from the reactors does not necessarily have to be as shown in the flow chart. It has proved advantageous in particular embodiments to introduce the discharge of a boiler of the cascade into the respective subsequent boiler of the cascade from below.
- the amine (12) is continuously fed to the distillation column (2) for dehydration.
- the tetraalkoxititanate required as catalyst (the tetraalkoxititanate content with respect to acrylic ester A used is preferably 0.2-4% by weight) is likewise preferably metered continuously into the reactor (1) as is the polymerization inhibitor (s).
- aminolysis catalysts it is also possible to use all transesterification catalysts known from the prior art.
- Suitable catalysts are zirconium acetylacetonate and further 1,3-diketonates of zirconium; furthermore, mixtures of alkali metal cyanates or alkali metal thiocyanates and alkali metal halides, tin compounds, for example dioctyltin oxide, alkaline earth metal oxides or alkaline earth metal hydroxides, such as, for example, CaO, Ca (OH) 2 , MgO, Mg (OH) 2 or mixtures of the abovementioned compounds, furthermore alkali metal hydroxides, alkali metal alkoxides and lithium chloride and lithium hydroxide, it is also possible to use mixtures of the abovementioned compounds with the abovementioned alkaline earth compounds and the Li salts, dialkyltin oxides, such as, for example, dioctyltin oxide, alkali metal carbonates , Alkali metal carbonates together with quaternary ammonium salts such as te
- a catalyst mixture of dialkyltin oxide and alkyl titanate for example dioctyltin oxide and isopropyl titanate in a ratio of about 2.5: 1 (wt .-% / wt .-%).
- the catalyst or the catalyst mixture is used in amounts of 0.1-10% by weight, preferably 0.2-7% by weight, in each case based on the acrylate used.
- Suitable alkyl acrylates are all acrylates having a linear or branched alkyl radical having 3 to 10, preferably 3 to 6 and particularly preferably 3 or 4 carbon atoms. Typical examples thereof are propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 3-methylbutyl acrylate, amyl acrylate, neopentyl acrylate, hexyl acrylate, cyclohexyl acrylate, heptyl acrylate, n-octyl acrylate, ethylhexyl acrylate or decyl acrylate.
- the choice of starting materials is particularly advantageously such that as the alcohol is removed from the reaction mixture, the equilibrium can be shifted to the side of the products.
- the removal of the alcohol can be carried out by distillation by its lower boiling point compared to the amine used and / or by the formation of an azeotrope.
- Suitable polymerization inhibitors are, for example, hydroquinone, 4-hydroxy-2,2,6,6-tetra-methylpiperidinooxyl or else bis (2-methoxycarbonylpropyl) sulfide or hydroquinone monomethyl ether in combination with oxygen.
- the amine used may contain water.
- the amount of water in the amine used is in the case of amine between 50 and 500 ppm (0.05 - 0.005% by weight).
- the amine is preferably dewatered by distillation before entering the reactor, via the distillation column (2).
- the water contained in the amine is removed overhead.
- the task of the amine is preferably carried out in the lower part of the distillation column (2).
- the amine used can also be dehydrated in other ways:
- a dehydrating agent such as a molecular sieve, or
- Dewatering is therefore important because the water in the amine can cause irreversible damage to the catalyst (e.g., tetraalkyl titanate) in the reactor.
- the water contained in the amine leads to the formation of by-products and should therefore be strictly avoided.
- This dewatering step avoids the hydrolysis of the catalyst and the associated costs due to increased catalyst use and problems with solid precipitates.
- the purity of the product is increased by a reduced proportion of by-products.
- the reaction takes place in the reactor (1) at a temperature in the range between 80 and 180 0 C depending on the material system and operating pressure.
- the temperature range between 110 and 160 ° C. is preferred.
- the alcohol released in the reaction is withdrawn from the reaction mixture via the distillation column (2), optionally also as an azeotrope with the alcohol (13). This can both at atmospheric pressure, at overpressure or under reduced pressure.
- the reaction mixture which consists largely of the product alkyl acrylate, unreacted acrylate and amine and small amounts of alcohol, the catalyst, the polymerization inhibitors and a proportion of by-products is after about 0.5 to 3 hours reactor residence time (preferably, a residence time of 1 - 2 hours) fed to a continuously operated falling-film evaporator (5).
- the vapors of the falling film evaporator (5) are fed to a low boiler distillation column (3).
- These are withdrawn via the top of the distillation column (3) and returned to the reactor area or into the distillation column (2) (14). This circulation stream results in a high conversion based on the reactants and the entire process.
- the in the course of the falling film evaporator (5) obtained with catalyst, polymerization and high-boiling by-products still contaminated crude amide (15) preferably contains> 80 wt .-% product amide and is used to work up a further vacuum distillation stage, which in the preferred pressure range between 0.1 and 200 mbar works, fed.
- the distillative separation of the high-purity product amide takes place as top product.
- the by-products formed in the process are high-boiling components with respect to the educt amine and the starting acrylate and thus enter the product amide as an impurity, thereby significantly lowering product quality.
- This problem can be solved by separating the product amide from the catalyst and the polymerization inhibitors and the high-boiling by-products Apparatus with gentle film evaporation, such as (5). Suitable apparatuses for this fall film, thin film and short path evaporator are known.
- the preparation of the alkylaminoacrylamides may optionally be followed by a purifying distillation unit which can also be operated under reduced pressure, for example at 500-0.1 mbar.
- the first reaction vessel was charged with 200 kg / h of butyl acrylate / catalyst feed containing 2.0% by weight of isopropyl titanate 5.0% by weight of dioctyltin oxide from the distillation column (2) and 144 kg / h of N-dimethylaminopropylamine (DMAPA).
- DMAPA N-dimethylaminopropylamine
- the 1st reaction vessel via the distillation column (2) continuously recirculated from the top of the low boiler distillation column (400 kg / h with the composition 70 wt .-% Eduktacrylat and butyl alcohol, DMAPA and byproducts.)
- the molar butyl acrylate: DMAPA ratio in the reactor feed was 1.8. 1.
- the reaction temperature in the second and third reaction vessels was 143 and 155 ° C.
- the distillate removal of the distillation column (2) was 110 kg / h.
- Reaction vessel and the effluent of the second reaction vessel ran into the third reaction vessel Residence time of a total of about 150 minutes, the following proportions of the components were determined at the end of the third reaction vessel:
- the course of the third reaction vessel was continuously fed to the thin-film evaporator of a low-boiling column in which unreacted DMAPA 1 butyl acrylate and butanol were withdrawn as distillate (400 kg / h) and recycled as recycle stream to the distillation column (2).
- the bottom outlet of the low-boiling column thin-film evaporator was 240 kg / h and had the composition: about 90% of product amide, 0.1% of DMAPA, a larger proportion of high-boiling components and traces of the reactants.
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2581312A CA2581312C (en) | 2004-11-23 | 2005-11-18 | Method for the continuous production of alkyl amino acryl amides |
AT05803766T ATE443040T1 (de) | 2004-11-23 | 2005-11-18 | Verfahren zur kontinuierlichen herstellung von alkylaminoacrylamiden |
DE502005008156T DE502005008156D1 (de) | 2004-11-23 | 2005-11-18 | Verfahren zur kontinuierlichen herstellung von alkylaminoacrylamiden |
US11/719,564 US7723543B2 (en) | 2004-11-23 | 2005-11-18 | Method for the continuous production of alkyl amino acryl amides |
CN2005800320263A CN101027276B (zh) | 2004-11-23 | 2005-11-18 | 连续制备烷基氨基丙烯酰胺的方法 |
EP05803766A EP1814844B1 (de) | 2004-11-23 | 2005-11-18 | Verfahren zur kontinuierlichen herstellung von alkylaminoacrylamiden |
KR1020077011612A KR101246421B1 (ko) | 2004-11-23 | 2005-11-18 | 알킬 아미노 아크릴 아미드의 연속 제조 방법 |
HK08102061.2A HK1111405A1 (en) | 2004-11-23 | 2008-02-25 | Method for the continuous production of alkyl amino acryl amides |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004056629.1 | 2004-11-23 | ||
DE102004056629 | 2004-11-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006056366A1 true WO2006056366A1 (de) | 2006-06-01 |
Family
ID=35501171
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/012362 WO2006056366A1 (de) | 2004-11-23 | 2005-11-18 | Verfahren zur kontinuierlichen herstellung von alkylaminoacrylamiden |
Country Status (12)
Country | Link |
---|---|
US (1) | US7723543B2 (de) |
EP (1) | EP1814844B1 (de) |
KR (1) | KR101246421B1 (de) |
CN (1) | CN101027276B (de) |
AT (1) | ATE443040T1 (de) |
CA (1) | CA2581312C (de) |
DE (1) | DE502005008156D1 (de) |
ES (1) | ES2333536T3 (de) |
HK (1) | HK1111405A1 (de) |
MY (1) | MY142742A (de) |
TW (1) | TWI362375B (de) |
WO (1) | WO2006056366A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010115666A1 (de) * | 2009-04-07 | 2010-10-14 | Evonik Röhm Gmbh | Verfahren zur kontinuierlichen herstellung von alkylamino(meth)acrylamiden |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005023976A1 (de) * | 2005-05-20 | 2006-11-23 | Röhm Gmbh | Verfahren zur Umesterung |
DE102005023975A1 (de) | 2005-05-20 | 2006-11-23 | Röhm Gmbh | Verfahren zur Herstellung von Alkyl(meth)acrylaten |
DE102006034273A1 (de) * | 2006-07-21 | 2008-01-24 | Röhm Gmbh | Verfahren zur Herstellung von Alpha-Hydroxycarbonsäuren |
DE102006058250A1 (de) * | 2006-12-08 | 2008-06-12 | Evonik Röhm Gmbh | Integriertes Verfahren und Vorrichtung zur Herstellung von Methacrylsäureestern aus Aceton und Blausäure |
DE102006058249A1 (de) * | 2006-12-08 | 2008-06-12 | Evonik Röhm Gmbh | Verfahren zur Herstellung von Cyanhydrinen sowie deren Verwendung bei der Herstellung von Methacrylsäurealkylestern |
DE102006058251A1 (de) * | 2006-12-08 | 2008-06-12 | Evonik Röhm Gmbh | Verfahren und Vorrichtung zur Herstellung von Methacrylsäurealkylestern |
DE102006059511A1 (de) * | 2006-12-14 | 2008-06-19 | Evonik Röhm Gmbh | Verfahren zur Herstellung von Acetoncyanhydrin und dessen Folgeprodukten durch gezielte Kühlung |
DE102006059513A1 (de) * | 2006-12-14 | 2008-06-19 | Evonik Röhm Gmbh | Verfahren zur Herstellung von Methacrylsäure alkylestern mittels azeotroper Destillation |
DE102006059512A1 (de) * | 2006-12-14 | 2008-06-19 | Evonik Röhm Gmbh | Destillative Aufarbeitung von Acetoncyanhydrin und Verfahren zur Herstellung von Metharcylsäureesther und Nachfolgeprodukten |
DE102006060161A1 (de) * | 2006-12-18 | 2008-06-26 | Evonik Röhm Gmbh | Verfahren zur adsorptiven Aufreinigung von Methacrylsäurealkylestern |
CN105001110B (zh) * | 2015-07-10 | 2017-01-18 | 青岛科技大学 | 一种气相反应制备衣康酰胺的方法 |
CN105439890A (zh) * | 2015-12-31 | 2016-03-30 | 沈阳化工研究院有限公司 | 一种催化酰胺化制备n-(3-二甲氨基丙基)丙烯酰胺的方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4027843A1 (de) * | 1990-09-03 | 1992-03-05 | Roehm Gmbh | Kontinuierliches verfahren zur herstellung von n-substituierten acryl- und methacrylamiden |
DE10323699A1 (de) * | 2003-05-22 | 2004-12-09 | Röhm GmbH & Co. KG | Verfahren zur kontinuierlichen Herstellung von Alkylamino(meth)acrylamiden |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3123970A1 (de) * | 1981-06-19 | 1983-01-05 | Röhm GmbH, 6100 Darmstadt | "verfahren zur herstellung von methacrylamiden" |
BR8904728A (pt) * | 1988-09-26 | 1990-05-01 | Goodyear Tire & Rubber | Processo para a sintese catalisada de acrilamidas n-substituidas |
DE102005023976A1 (de) * | 2005-05-20 | 2006-11-23 | Röhm Gmbh | Verfahren zur Umesterung |
DE102005023975A1 (de) * | 2005-05-20 | 2006-11-23 | Röhm Gmbh | Verfahren zur Herstellung von Alkyl(meth)acrylaten |
-
2005
- 2005-11-18 CA CA2581312A patent/CA2581312C/en not_active Expired - Fee Related
- 2005-11-18 DE DE502005008156T patent/DE502005008156D1/de active Active
- 2005-11-18 WO PCT/EP2005/012362 patent/WO2006056366A1/de active Application Filing
- 2005-11-18 EP EP05803766A patent/EP1814844B1/de active Active
- 2005-11-18 KR KR1020077011612A patent/KR101246421B1/ko not_active IP Right Cessation
- 2005-11-18 ES ES05803766T patent/ES2333536T3/es active Active
- 2005-11-18 AT AT05803766T patent/ATE443040T1/de not_active IP Right Cessation
- 2005-11-18 US US11/719,564 patent/US7723543B2/en active Active
- 2005-11-18 CN CN2005800320263A patent/CN101027276B/zh active Active
- 2005-11-22 TW TW094140990A patent/TWI362375B/zh not_active IP Right Cessation
- 2005-11-22 MY MYPI20055442A patent/MY142742A/en unknown
-
2008
- 2008-02-25 HK HK08102061.2A patent/HK1111405A1/xx not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4027843A1 (de) * | 1990-09-03 | 1992-03-05 | Roehm Gmbh | Kontinuierliches verfahren zur herstellung von n-substituierten acryl- und methacrylamiden |
DE10323699A1 (de) * | 2003-05-22 | 2004-12-09 | Röhm GmbH & Co. KG | Verfahren zur kontinuierlichen Herstellung von Alkylamino(meth)acrylamiden |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010115666A1 (de) * | 2009-04-07 | 2010-10-14 | Evonik Röhm Gmbh | Verfahren zur kontinuierlichen herstellung von alkylamino(meth)acrylamiden |
AU2010234280B2 (en) * | 2009-04-07 | 2014-02-13 | Evonik Rohm Gmbh | Method for continuously producing alkylamino(meth)acrylamides |
US8674133B2 (en) | 2009-04-07 | 2014-03-18 | Evonik Röhm Gmbh | Method for continuously producing alkylamino(meth)acrylamides |
Also Published As
Publication number | Publication date |
---|---|
ATE443040T1 (de) | 2009-10-15 |
ES2333536T3 (es) | 2010-02-23 |
TWI362375B (en) | 2012-04-21 |
US7723543B2 (en) | 2010-05-25 |
CA2581312C (en) | 2013-07-16 |
CN101027276B (zh) | 2011-08-17 |
EP1814844B1 (de) | 2009-09-16 |
HK1111405A1 (en) | 2008-08-08 |
DE502005008156D1 (de) | 2009-10-29 |
CN101027276A (zh) | 2007-08-29 |
US20090149674A1 (en) | 2009-06-11 |
EP1814844A1 (de) | 2007-08-08 |
CA2581312A1 (en) | 2006-06-01 |
MY142742A (en) | 2010-12-31 |
KR20070084462A (ko) | 2007-08-24 |
TW200630323A (en) | 2006-09-01 |
KR101246421B1 (ko) | 2013-03-21 |
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