EP2225296A1 - Procédé de production d'homopolymères et de copolymères de polyoxyméthylène par homopolymérisation ou copolymérisation de trioxane, à partir de méthanol - Google Patents

Procédé de production d'homopolymères et de copolymères de polyoxyméthylène par homopolymérisation ou copolymérisation de trioxane, à partir de méthanol

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Publication number
EP2225296A1
EP2225296A1 EP08861536A EP08861536A EP2225296A1 EP 2225296 A1 EP2225296 A1 EP 2225296A1 EP 08861536 A EP08861536 A EP 08861536A EP 08861536 A EP08861536 A EP 08861536A EP 2225296 A1 EP2225296 A1 EP 2225296A1
Authority
EP
European Patent Office
Prior art keywords
trioxane
formaldehyde
stream
production plant
column
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.)
Withdrawn
Application number
EP08861536A
Other languages
German (de)
English (en)
Inventor
Markus Siegert
Tobias Kortekamp
Eckhard Stroefer
Christoph Sigwart
Neven Lang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP08861536A priority Critical patent/EP2225296A1/fr
Publication of EP2225296A1 publication Critical patent/EP2225296A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
    • C07D323/04—Six-membered rings
    • C07D323/06—Trioxane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/10—Polymerisation of cyclic oligomers of formaldehyde

Definitions

  • the invention relates to a process for the preparation of Polyoxymethylenhomo- or copolymers by homo- or copolymerization of trioxane, starting from methanol.
  • Trioxane is obtained predominantly by trimerization of formaldehyde from aqueous formaldehyde solutions in homogeneous or heterogeneous catalysis in the presence of acidic catalysts.
  • the problem here is that formaldehyde tends to solid precipitate, with the formation of paraformaldehyde, with increasing formaldehyde content in an aqueous solution, the temperature at which solid begins to precipitate decreases. It is approximately, at least for formaldehyde concentrations in the range of 30 to 70 wt .-%, that aqueous formaldehyde solutions must be heated to a temperature which is higher by about 10 0 C than the concentration of formaldehyde in wt .-%, to to avoid a solid precipitation.
  • a 50% aqueous solution of formaldehyde must be heated to about 60 to 70 0 C and a 60% formaldehyde solution to about 70 to 80 0 C to keep the formaldehyde in solution.
  • Formaldehyde is mainly obtained by oxidation of methanol.
  • trioxane obtained by trimerization of the formaldehyde is used, optionally together with other monomers, predominantly as a monomer for the preparation of polyoxymethylene homopolymers or copolymers.
  • Polymerizable trioxane must meet certain specification requirements and is referred to below as pure trioxane. This is a stream with a minimum content of 97.5% by weight of trioxane, or else 99% by weight of trioxane or 99.5% by weight of trioxane. A stream with a minimum content of 99.9% by weight of trioxane can be described as ultrapure trioxane.
  • trioxane is therefore preferably obtained by pressure swing rectification, as described for example in the earlier priority, not prepublished DE-A 07 101 198 or EP 07 1 18 103.6.
  • the solution consists in a process for the preparation of Polyoxymethylenhomo- or copolymers by homo- or copolymerization of trioxane, starting from methanol, the
  • the formaldehyde is trimerized to trioxane in the presence of an acidic catalyst in a second reactor and from which a trioxane / formaldehyde / water mixture is withdrawn,
  • trioxane / formaldehyde / water mixture is separated by distillation in a first column to give crude trioxane as overhead stream,
  • a partial flow of the condensate is again applied to the first column and the remaining part stream of a further workup to pure trioxane in one or more further process steps, wherein one of these further process steps a distillative removal of low boilers selected from the group comprising methyl formate, methylal, dimethoxydimethyl ether and methanol, in a low boiler separation column and -
  • the pure trioxane is fed to a third production plant in which it homo or copolymerized to Polyoxymethylenhomo- or copolymers, which is characterized in that the low boiler stream is recycled from the low boiler separation column in the first production plant in the feed of the first reactor .
  • the production of formaldehyde by oxidation of methanol in a first production plant, in a first reactor, is known per se.
  • an aqueous formaldehyde-containing stream is obtained, which is fed to a second production plant in which the formaldehyde is trimerized in the presence of an acidic catalyst in a second reactor to trioxane.
  • trioxane / formaldehyde / water mixture obtained is separated by distillation in a first column to give crude trioxane as the top stream.
  • the trioxane / formaldehyde / water mixture fed to the first column generally contains from 40 to 80% by weight of formaldehyde, from 20 to 59% by weight of water and from 1.0 to 30% by weight of trioxane.
  • the top stream of the first column generally contains more than 60% by weight, preferably more than 63% by weight, more preferably more than 65% by weight, of trioxane.
  • the crude trioxane overhead stream of the first column is composed as follows: 3 to 20% by weight of formaldehyde, 10 to 30% by weight of water and 60 to 75% by weight of trioxane.
  • the top stream of the first distillation column is condensed in a condenser at the top of the column to obtain a condensate, a partial stream of the condensate is again fed as reflux to the first column and the remaining part stream is in a further preparation to pure trioxane in one or more further process. led.
  • pure trioxane is understood as meaning a stream having a minimum content of 97.5% by weight of trioxane, or else 99% by weight of trioxane or else 99.5% by weight of trioxane.
  • One of these further process stages for working up crude trioxane to pure trioxane involves a distillative removal of low-boiling components.
  • low-boiling components which can be formed in the trioxane synthesis and the subsequent distillative separation are methyl formate, methylal, dimethoxydimethyl ether, methanol, formic acid and further hemiacetals and acetals.
  • the low-boiling components are preferably separated off via the top of a low-boiler separation column, which is generally operated at a pressure of 0.1 to 5 bar, preferably at a pressure of 1, 0 to 2.5 bar.
  • the stream fed to the low boiler distillation column may still contain up to 15% by weight of low boilers.
  • the low boiler separation column has at least 2 theoretical stages, preferably 15 to 50 theoretical stages.
  • the drive part of this column comprises 25 to 90%, preferably 50 to 75% of the theoretical stages of this column.
  • the bottom product of the low boiler separation column generally remain less than 5 wt .-%, preferably less than 2.5 wt .-%, more preferably less than 1, 5 wt .-% of trioxane lower boiling components
  • the pure trioxane is fed to a third production plant in which it is homo- or copolymerized to form polyoxymethylene homopolymers or copolymers.
  • the low-boiler stream which is withdrawn as top stream from the low-boiler separation column, is recycled into the first production plant, into the feed of the first reactor.
  • the low boiler stream preferably has the following main components:
  • Methanol up to 50 wt .-%, methyl formate up to 40 wt .-%, methylal up to 30% by weight and trioxane less than 10 wt .-%.
  • trioxane production plant In addition to the production plants A and B, d. H. to the formaldehyde production plant and the trioxane production plant, also the trioxane production plant with the production plant C of the plant for the polymerization of pure trioxane to polyoxymethylene homo- or copolymers coupled.
  • Polyoxymethylene homopolymers or copolymers generally have at least 50 mole percent of recurring units - CH 2 O - in the polymer backbone.
  • Polyoxymethylene copolymers are preferred, in particular those which, in addition to the repeating units -CH 2 O-, also contain up to 50, preferably 0.01 to 20, in particular 0.1 to 10, mol% and very particularly preferably 0.5 to 6 mol -% of recurring units.
  • R 1 to R 4 independently of one another are a hydrogen atom, a C 1 - to C 4 -alkyl group or a halogen-substituted alkyl group having 1 to 4 C atoms and R 5 is a - CH 2 -, -CH 2 O-, a d- to C 4 alkyl or C 1 to C 4 haloalkyl substituted methylene group or a corresponding oxymethylene group and n has a value in the range of 0 to 3.
  • these ring opening groups of cyclic ethers can be introduced into the copolymers.
  • Preferred cyclic ethers are those of the formula
  • R 1 to R 5 and n have the abovementioned meaning.
  • Oxymethylenterpolymerisate for example, by reacting trioxane, one of the cyclic ethers described above with a third monomer, preferably bifunctional compounds of the formula
  • Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in the molar ratio 2: 1 and diether from 2 mol glycidyl compound and 1 mol of an aliphatic diol having 2 to 8 carbon atoms such as the diglycidyl ethers of ethylene glycol, 1 , 4-butanediol, 1, 3-butanediol, cyclobutane-1, 3-diol, 1, 2-propanediol and cyclohexane-1, 4-diol, to name just a few examples.
  • End-group-stabilized polyoxymethylene polymers which have predominantly C-C or -O-CHs bonds at the chain ends are particularly preferred.
  • the preferred polyoxymethylene copolymers have melting points of at least 150 ° C. and weight average molecular weights M.sub.w in the range from 5,000 to 300,000, preferably from 7,000 to 250,000, g / mol. Particular preference is given to POM copolymers having a non-uniformity (MJM n ) of from 2 to 15, preferably from 2.5 to 12, more preferably 3 to 9.
  • the measurements are generally carried out by gel permeation chromatography (GPC) SEC (size exclusion chromatography).
  • the M n value number average molecular weight
  • GPC-SEC number average molecular weight
  • the molecular weights of the polymer can be adjusted to the desired values by the regulators customary in the trioxane polymerization and by the reaction temperature and residence time.
  • Suitable regulators are acetals or formals of monohydric alcohols, the alcohols themselves and the small amounts of water which act as chain transfer agents and whose presence can generally never be completely avoided.
  • the regulators are used in amounts of from 10 to 10,000 ppm, preferably from 20 to 5,000 ppm.
  • Initiators are the cationic initiators customary in the trioxane polymerization.
  • Proton acids are suitable, such as fluorinated or chlorinated alkyl- and arylsulfonic acids, for example perchloric acid, trifluoromethanesulfonic acid or Lewis acids, for example tin tetrachloride, arsenic pentafluoride, phosphoric pentafluoride and boron trifluoride, and their complex compounds and salt-like compounds, for example boron trifluoride etherates and triphenylmethylene hexafluorophosphate.
  • fluorinated or chlorinated alkyl- and arylsulfonic acids for example perchloric acid, trifluoromethanesulfonic acid or Lewis acids, for example tin tetrachloride, arsenic pentafluoride, phosphoric pentafluoride and boron trifluoride, and their complex compounds and salt
  • the initiators are used in amounts of about 0.01 to 1000 ppm, preferably 0.01 to 500 ppm and in particular from 0.01 to 200 ppm. In general, it is advisable to add the initiator in dilute form, preferably in concentrations of 0.005 to 5 wt .-%.
  • Suitable solvents for this purpose are inert compounds such as aliphatic, cycloaliphatic hydrocarbons For example, cyclohexane, halogenated aliphatic hydrocarbons, glycol ethers, etc. may be used. Particular preference is given to triglyme (triethylene glycol dimethyl ether) as solvent and 1,4-dioxane.
  • cocatalysts can be included.
  • alcohols of any kind e.g. aliphatic alcohols having 2 to 20 C atoms, such as t-amyl alcohol, methanol, ethanol, propanol, butanol, pentanol, hexanol; aromatic alcohols having 2 to 30 C atoms, such as hydroquinone; halogenated alcohols having 2 to 20 C atoms, such as hexafluoroisopropanol;
  • glycols of any type in particular diethylene glycol and triethylene glycol
  • aliphatic dihydroxy compounds, in particular diols having 2 to 6 carbon atoms such as 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanediol, 1, 4-cyclo
  • Monomers, initiators, cocatalyst and, if appropriate, regulators may be premixed in any way or may also be added to the polymerization reactor separately from one another.
  • the stabilizing components may contain sterically hindered phenols as described in EP-A 129369 or EP-A 128739.
  • the polymerization mixture is preferably deactivated directly after the polymerization, preferably without a phase change taking place.
  • the deactivation of the initiator residues is generally carried out by adding deactivators (terminating agents) to the polymerization melt.
  • deactivators are e.g. Ammonia and primary, secondary or tertiary, aliphatic and aromatic amines, e.g. Trialkylamines such as triethylamine, or triacetonediamine.
  • basic-reacting salts such as soda and borax, furthermore the carbonates and hydroxides of the alkali metals and alkaline earth metals, and also alkoxides, such as sodium ethanolate.
  • the deactivators are usually added to the polymers in amounts of preferably 0.01 ppmw (parts per million by weight) up to 2 wt .-%.
  • alkali metal or alkaline earth metal alkyls are preferred as deactivators which have 2 to 30 C atoms in the alkyl radical.
  • Particularly preferred metals are Li, Mg and Na, with n-butyllithium being particularly preferred.
  • Trioxane POMs are typically obtained by bulk polymerization using any reactors with high mixing efficiency.
  • the reaction can be carried out homogeneously, for example in a melt, or heterogeneously, for example as polymerization to a solid or solid granules.
  • the melted polymer produces a so-called melt seal, whereby volatile constituents remain in the extruder.
  • the above monomers are metered into the polymer melt present in the extruder, taken together or separately from the initiators (catalysts), at a preferred temperature of the reaction mixture of 62 to 114 ° C.
  • the monomers (trioxane) are vorzugt loading metered into a molten state, for example at 60 to 120 0 Due to the exothermic nature of the process, the polymer must C. usually be melted in the extruder, only at the start of the process; Subsequently, the amount of heat released is sufficient to melt the molten POM polymer or to keep it molten.
  • the melt polymerization is usually carried out at 1, 5 to 500 bar and 130 to 300 0 C, and the residence time of the polymerization mixture in the reactor is usually 0.1 to 20, preferably 0.4 to 5 min.
  • the polymerization is preferably carried out to a conversion of more than 30%, for example 60 to 90%.
  • a crude POM which, as mentioned, contains considerable proportions, for example up to 40%, of unconverted residual monomers, in particular trioxane and formaldeyde.
  • Formaldehyde can also be present in the crude POM if only trioxane was used as the monomer since it can be formed as a degradation product of the trioxane.
  • other oligomers of formaldehyde may also be present, e.g. the tetrameric tetroxane.
  • This crude POM is degassed in one or more stages in known degassing devices, for example in degassing pots (flash pots), degassing extruders with one or more screws, thin film evaporators, spray dryers or other conventional degassing devices. Particularly preferred are degassing pots (flash pots).
  • the degassing of the raw POM is operated in such a way that is degassed in a first flash to below 6 bar absolute, to obtain a gaseous stream and a liquid stream, which is fed to a second flash, which is operated at below 2 bar absolute , obtaining a vapor stream, which is recycled into the monomer plant.
  • the pressure in the first stage is preferably 2 to 18, in particular 2 to 15 and particularly preferably 2 to 10 bar, and in the second stage preferably 1, 05 to 4, in particular 1, 05 to 3.05 and especially preferably 1.05 to 3 bar amount.
  • the residual monomers liberated during degassing are optionally withdrawn as one or more vapor streams and fed to a condenser.
  • the condenser is preferably operated in such a way that the condensate stream obtained in this case has a higher proportion of trioxane in comparison with the uncondensed vapor stream.
  • additives include, for example, lubricants or mold release agents, colorants, e.g. Pigments or dyes, flame retardants, antioxidants, light stabilizers, formaldehyde scavengers, polyamides, nucleating agents, fibrous and powdery fillers or reinforcing agents or antistatic agents and other additives or mixtures thereof.
  • the desired product POM is obtained as a melt.
  • gaseous, formaldehyde-containing secondary streams which are obtained in the single or multi-stage expansion of the polymer melt from the polymerization reactor and remain in the gaseous state of aggregation after condensation, are recycled into the production plant C according to the invention.
  • the gaseous formaldehyde-containing stream from the production plant C is recycled into the first column of the production plant B.
  • the operating conditions in the condenser are preferably set in such a way that the proportion of trioxane in the gaseous formaldehyde-containing stream from the production plant C, which is recycled to the production plant B, less than 80 wt .-%, preferably less than 60 wt. -%, more preferably less than 40% by weight.
  • This stream usually has a formaldehyde content of preferably at least 25% by weight, more preferably at least 50% by weight.
  • One or more further formaldehyde-containing secondary streams are produced at the extruder or kneader dome, and the extruder or kneader exhaust gas, which is also present in accordance with the invention, ie. H. is recycled without any chemical or physical change to the production plant B.
  • a negative pressure is usually generated, often in a first stage in the range of less than 800 mbar and in a second stage at lower pressure, often in the range of less than 500 mbar.
  • the extruder or kneader exhaust gas is taken up in the liquid ring pump which is already present in the production plant B in order to produce a water-rich liquid stream, in particular the overhead stream from the evaporation of the formaldehyde feed stream upstream of the reactor for producing trioxane from a starting concentration of approximately 10 to 60 wt .-%, in particular from about 15 to 45 wt .-% to the pressure of the fourth column, for the separation of water, to compress.
  • the extruder exhaust gas taken up in the liquid ring pump is compressed to a pressure of 2 to 7 bar absolute, preferably to about 5 bar absolute.
  • methanol, methylal, methyl formate and other methanol derivatives from the low-boiler stream can be used to at least 90% in the first production plant as feedstock for the production of formaldehyde.
  • FIG. 1 shows a block flow diagram of the coupled operation according to the invention of a formaldehyde, a trioxane and a polyoxymethylene homopolymer or copolymer system,
  • FIG. 2 shows a preferred embodiment for a trioxane production plant.
  • the block flow diagram in FIG. 1 schematically shows a first production plant A (formaldehyde production plant), a second production plant B (trioxane production plant) and a third production plant C (polyoxymethylene homopolymer or copolymer plant).
  • a methanol stream 1 is supplied and deducted therefrom, an aqueous formaldehyde-containing stream 2, which is the second production plant B is supplied. From this, a low-boiler stream 5 is withdrawn, which is recycled into the first production plant A.
  • a pure trioxane stream 6 is obtained, which is fed to the third production plant C for the production of polyoxymethylene homopolymers or copolymers. From the third production plant C Polyoxymethylenhomo- or copolymers 7 are deducted.
  • An unspecified return flow from the third production plant C in the second production plant B illustrates the material coupling of these two production plants.
  • FIG. 2 shows a preferred embodiment for a second production plant B:
  • a trioxane / formaldehyde / water mixture 3 is withdrawn, and separated by distillation in a first column K1 to obtain crude trioxane as overhead stream 4.
  • the top stream 4 is condensed at a condenser W at the top of the column.
  • Some of the condensate is fed back to the column K1 as reflux and, moreover, in the preferred embodiment shown in the figure, it is fed to a low boiler separation column K2.
  • the light-ends separation column K2 is a lightweight withdrawn boiler containing stream 5, which according to the invention in the first production plant A, which is not shown in Figure 2, recycled.
  • the bottom stream from the low boiler separation column K2 is in further, unspecified distillation separation stages, purified to pure trioxane, stream 6, cleaned. Pure trioxane, stream 6, is fed as feed stream to the third production plant C not shown in FIG. 2 for the preparation of polyoxymethylene homopolymers or copolymers.

Abstract

L'invention concerne un procédé de production d'homopolymères ou de copolymères de polyoxyméthylène (7) par homopolymérisation ou copolymérisation de trioxane, à partir de méthanol (1), le méthanol étant oxydé dans une première installation de production (A) dans un premier réacteur jusqu'à l'obtention d'un flux aqueux (2) à teneur en formaldéhyde, lequel flux est amené à une deuxième installation de production (B), dans laquelle du trioxane pur (6) est obtenu, des fractions à bas point d'ébullition (5) étant séparées par distillation et le trioxane pur (6) étant amené à une troisième installation de production (C), dans laquelle le trioxane pur est homopolymérisé ou copolymérisé en homopolymères ou copolymères de polyoxyméthylène (7). Le procédé se caractérise en ce que le flux de fractions à bas point d'ébullition (5) issu de la colonne de séparation de fractions à bas point d'ébullition (K2) est renvoyé à la première installation de production (A) à l'entrée du premier réacteur.
EP08861536A 2007-12-19 2008-12-11 Procédé de production d'homopolymères et de copolymères de polyoxyméthylène par homopolymérisation ou copolymérisation de trioxane, à partir de méthanol Withdrawn EP2225296A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08861536A EP2225296A1 (fr) 2007-12-19 2008-12-11 Procédé de production d'homopolymères et de copolymères de polyoxyméthylène par homopolymérisation ou copolymérisation de trioxane, à partir de méthanol

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07150113 2007-12-19
PCT/EP2008/067286 WO2009077415A1 (fr) 2007-12-19 2008-12-11 Procédé de production d'homopolymères et de copolymères de polyoxyméthylène par homopolymérisation ou copolymérisation de trioxane, à partir de méthanol
EP08861536A EP2225296A1 (fr) 2007-12-19 2008-12-11 Procédé de production d'homopolymères et de copolymères de polyoxyméthylène par homopolymérisation ou copolymérisation de trioxane, à partir de méthanol

Publications (1)

Publication Number Publication Date
EP2225296A1 true EP2225296A1 (fr) 2010-09-08

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EP08861536A Withdrawn EP2225296A1 (fr) 2007-12-19 2008-12-11 Procédé de production d'homopolymères et de copolymères de polyoxyméthylène par homopolymérisation ou copolymérisation de trioxane, à partir de méthanol

Country Status (11)

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US (1) US8378144B2 (fr)
EP (1) EP2225296A1 (fr)
JP (1) JP2011506720A (fr)
KR (1) KR20100105610A (fr)
CN (1) CN101903430B (fr)
AU (1) AU2008337624A1 (fr)
BR (1) BRPI0820853A2 (fr)
CA (1) CA2707613A1 (fr)
MX (1) MX2010005954A (fr)
MY (1) MY151105A (fr)
WO (1) WO2009077415A1 (fr)

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ES2763359T3 (es) 2009-08-20 2020-05-28 Basf Se Procedimiento para la preparación de polímeros de polibifenilsulfona bajos en halógenos
CN102666474A (zh) 2009-12-18 2012-09-12 巴斯夫欧洲公司 在mda合成中成本有效地分离均相催化剂的两步方法
WO2013113879A1 (fr) 2012-02-02 2013-08-08 Basf Se Copolymères de polyoxyméthyléne
RU2014135489A (ru) 2012-02-02 2016-03-27 Басф Се Термопластичная полиоксиметиллен (пом )- масса
TW201500443A (zh) 2013-04-18 2015-01-01 Basf Se 聚甲醛共聚物及熱塑性ｐｏｍ組成物
KR101532623B1 (ko) * 2013-08-29 2015-06-30 한국엔지니어링플라스틱 주식회사 폴리옥시메틸렌 중합체의 제조방법 및 이로부터 제조되는 폴리옥시메틸렌 중합체

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BRPI0818078A2 (pt) * 2007-10-09 2015-03-31 Basf Se Processos para separar trioxano a partir de uma corrente de alimentação, e para preparar trioxano a partir de uma solução aquosa de formaldeído

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KR20100105610A (ko) 2010-09-29
BRPI0820853A2 (pt) 2015-06-16
US20100280195A1 (en) 2010-11-04
MX2010005954A (es) 2010-06-11
CA2707613A1 (fr) 2009-06-25
US8378144B2 (en) 2013-02-19
WO2009077415A1 (fr) 2009-06-25
JP2011506720A (ja) 2011-03-03
CN101903430B (zh) 2013-04-24
AU2008337624A1 (en) 2009-06-25
MY151105A (en) 2014-04-15
CN101903430A (zh) 2010-12-01

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