EP1963012A1 - Procédé de fabrication de composés de cyanures multimétalliques - Google Patents

Procédé de fabrication de composés de cyanures multimétalliques

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Publication number
EP1963012A1
EP1963012A1 EP06819719A EP06819719A EP1963012A1 EP 1963012 A1 EP1963012 A1 EP 1963012A1 EP 06819719 A EP06819719 A EP 06819719A EP 06819719 A EP06819719 A EP 06819719A EP 1963012 A1 EP1963012 A1 EP 1963012A1
Authority
EP
European Patent Office
Prior art keywords
general formula
aqueous solution
salt
catalyst
multimetal cyanide
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Withdrawn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
EP06819719A
Other languages
German (de)
English (en)
Inventor
Michael Triller
Raimund Ruppel
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
Publication of EP1963012A1 publication Critical patent/EP1963012A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof

Definitions

  • the invention relates to a process for the preparation of multimetal cyanide compounds, which can be used in particular as catalysts for the ring-opening polymerization of alkylene oxides.
  • Multimetal cyanide catalysts also referred to as DMC catalysts, are effective catalysts for preparing polyetherols by ring-opening polymerization of alkylene oxides. Such products are used, for example, as starting materials for the preparation of polyurethanes by reaction with polyisocyanates, as surface-active compounds or as carrier oils in the art.
  • the DMC catalysts are usually prepared by reacting a metal salt with a cyanometalate compound. To improve the properties of the DMC catalysts, it is customary to add organic ligands during and / or after the reaction. A description of the preparation of DMC catalysts can be found, for example, in US-A 3,278,457.
  • the DMC catalysts also have disadvantages. Thus, it may come at the start of the reaction to a delayed start of the reaction. This delay is often referred to as the induction period.
  • Another disadvantage is the formation of very high molecular weight fractions in the polyether alcohol. These high molecular weight fractions can have a very disadvantageous effect on the further processing into polyurethanes.
  • DMC catalysts One way to overcome these disadvantages is to improve the DMC catalysts.
  • the prior art describes a large number of structures of DMC catalysts.
  • the variation of the DMC catalysts may consist of the morphology, the type of organic ligands used, or the use of additives.
  • EP 1 400 281 describes the addition of functional polymers to improve the selectivity of the DMC catalysts.
  • EP 090 444 describes a process for the preparation of polyether alcohols using DMC catalysts in which the DMC catalyst is used together with an acid for the preparation of polyether alcohols.
  • WO 01/64772 a process for the preparation of DMC catalysts is described in which first a DMC catalyst is prepared and this is then subjected to recrystallization.
  • the invention thus relates to a process for the preparation of multimetal cyanide compounds, comprising the steps
  • organic ligands optionally in the presence of organic ligands, organic additives and / or surface-active agents,
  • M 1 is a metal ion selected from the group consisting of Zn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ni 2+ , Mn 2+ , Sn 2+ , Sn 4+ , Pb 2+ , Al 3+ , Sr 2+ , Cr 3+ , Cd 2+ , Cu 2+ , La 3+ , Ce 3+ , Ce 4+ , Eu 3+ , Mg 2+ , Ti 4+ , Ag + , Rh 2 + , Ru 2+ , Ru 3+ , Pd 2+
  • M 2 is a metal ion selected from the group containing Fe 2+ , Fe 3+ , Co 2+ ,
  • X is an anion selected from the group consisting of halide, hydroxide,
  • L is a water-miscible ligand selected from the group comprising alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, nitriles, and sulfides or mixtures thereof,
  • P is an organic additive selected from the group comprising polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkylene acrylates , Polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, Polyalkyleneimines, maleic acid and maleic anhydride copolymer, hydroxyethylcellulose, polyacetates, ionic surfaces and surface-active compounds, gallic
  • a, b, d, g, n, r, s, j, k and t are whole or fractional numbers greater than zero, e, f, h and z are integers or fractions greater than or equal to zero,
  • a, b, d, g, n, j, k and r and s and t are selected to ensure electro-neutrality
  • M 3 is hydrogen or an alkali or alkaline earth metal, as well as
  • the invention also provides the DMC catalysts prepared by this process, their use for the preparation of polyether alcohols and a process for the preparation of polyether alcohols by addition of alkylene oxides to H-functional starter substances, characterized in that the catalysts prepared by the novel DMC -Catalysts are used.
  • M 1 is Zn 2+ and M 2 is Co 3+ or Co 2+ .
  • the metals M 1 and M 2 are especially the same if they are cobalt, manganese or iron.
  • steps a) and b) of the process according to the invention can be carried out directly behind one another or temporally and / or spatially separated from one another.
  • the salt (IV) may also be a mixture of at least two salts. However, this embodiment is less preferred.
  • multimetal cyanide compounds of the general formula (III) are prepared from a metal salt of the general formula (I) and a cyanometallate compound of the general formula (II).
  • the DMC catalysts of the general formula (IM) may be crystalline or amorphous. In the case where z is equal to zero, crystalline double metal cyanide compounds are preferred. In the case where z is greater than zero, both crystalline, partially crystalline, and substantially amorphous catalysts are preferred.
  • a preferred embodiment are catalysts of the formula (III) in which z is greater than zero.
  • the preferred catalyst then contains:
  • z is zero, optionally e is also zero and X is exclusively carboxylate, preferably formate, acetate and propionate.
  • X is exclusively carboxylate, preferably formate, acetate and propionate.
  • Such compounds are described, for example, in WO 99/16775.
  • crystalline multimetal cyanide catalysts are preferred.
  • DMC catalysts of the formula (III) are not equal to zero.
  • DMC catalysts containing a water-miscible organic ligand generally in amounts of from 0.5 to 30% by weight
  • an organic additive generally in amounts of from 5 to 80% by weight. contained (WO 98/06312).
  • the catalysts may e.g. with vigorous stirring (e.g.,> 20,000 rpm with an UltraTurrax®) or otherwise sheared.
  • DMC catalysts of the formula (III) are described in WO 01/03830. These DMC catalysts are prepared with organic sulfones of the general form R-S (O) 2-R or sulfoxides of the general form R-S (O) -R as an organic complexing agent.
  • DMC catalysts of the formula (III) of metal [hexacyanometallate-hexanitro-metallate] are mentioned in the application WO 01/04182.
  • the starting compounds mentioned there are less expensive than the zinc hexacyano cobaltates usually used.
  • the DMC catalysts thus prepared can also be supported, as described in the applications WO 01/04180 and WO 01/04177. As a result, a simple separation of the catalyst can be achieved. However, this can lead to abrasion in the supported catalysts.
  • a likewise suitable DMC catalyst of the formula (III) can be prepared according to WO 01/04181 based on hexacyanocobaltate-nitroferrocyanide. The catalysts can be separated off after step a) and optionally worked up and dried.
  • step b) they are then resuspended. This can be done, for example, by suspending them in water and adding to this suspension the salt of the formula (IV), either as a solid or, preferably, in the form of an aqueous solution. It is also possible to suspend the DMC catalyst of the formula (III) for carrying out step b) in the aqueous solution of the salt of the formula (IV).
  • the suspension may also contain ligands, surfactants or other compounds.
  • the solution of the salt (IV) can be prepared by dissolving the salt in water. It is also possible to form the salts in situ by adding the appropriate acids and bases.
  • the catalysts of the formula (III) are suspended in the aqueous solution of the salt of the formula (IV).
  • the concentration of the salt solution is preferably 0.1% to 30% by weight, preferably 0.5% to 15% by weight, particularly preferably 1% to 10% by weight, if the solubility of the salt of the formula ( IV) allows this.
  • the proportion of the DMC catalyst of the formula (III) in the suspension is from 1 to 30% by weight, preferably from 1 to 20% by weight, particularly preferably from 3 to 15% by weight.
  • the suspension and step b) is carried out in particular between room temperature and the boiling point of the aqueous salt solution and can be repeated several times. The last suspension operation can optionally be followed by several washes with demineralized water.
  • the treatment of the DMC catalysts of the formula (III) in the aqueous salt solution of the salt (IV) may also be carried out under reduced or elevated pressure, preferably at a pressure between 200 and 1200 hPa.
  • step b) is carried out by washing, that is, flowing through a filter cake of the catalyst of the formula (III) on a filter with an aqueous salt solution of a salt of the formula (IV).
  • the filter cake can be formed directly in the separation of the catalyst of the formula (III) and further treated on the filter, or an already finished DMC catalyst of the formula (III) can be converted into filter cake form by being suspended in demineralized water and so on the filtration apparatus is applied. This is followed by treatment with the saline solution.
  • the concentrations and the temperature are as described above.
  • the pH of the aqueous solution of salt (IV) is between 4 and 7. If the pure solution has a different pH, this can be adjusted by adding acid or base.
  • step b) The treatment of the DMC catalysts of the formula (III) in step b) may result in ion exchange in the catalyst and / or impregnation with the salt (IV).
  • the catalyst resulting from step b) has the general formula (V), wherein the symbols have the same meaning as in the formulas (I) to (IV).
  • the catalyst resulting from step b) has the general formula (VI), where the symbols have the same meaning as in the formulas (I) to (IV),
  • u, v, m o, q and w are integer or fractional numbers greater than zero and selected to ensure electroneutrality, and the remaining coefficients and indices have the meanings given in formulas (I) to (IV).
  • an ion exchange according to formula (V) takes place.
  • ion exchange according to formula (V) takes place.
  • the treated catalyst has undergone ion exchange.
  • DMC catalysts can be obtained with a significantly improved catalytic activity.
  • the induction period is greatly shortened.
  • the amount of catalyst can be reduced.
  • the DMC catalysts of the invention are used for the preparation of polyether alcohols by addition of alkylene oxides to H-functional starter substances.
  • alkylene oxides it is possible to use all known alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide.
  • the alkylene oxides used are ethylene oxide, propylene oxide and mixtures of the compounds mentioned.
  • polyether alcohols for use as raw materials for polyurethane production are used as starting substances, in particular polyfunctional alcohols and as alkylene oxides, preferably ethylene oxide and / or propylene oxide. It is also possible to incorporate carbon dioxide into the polyether chain in addition to the alkylene oxides.
  • H-functional starter substances mono- or polyfunctional compounds are used.
  • alcohols having a functionality of 1 to 8, preferably 2 to 8, are used.
  • polyether alcohols which are used for flexible polyurethane foams
  • examples are ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol.
  • alkylene oxides by means of DMC catalysts, it is advantageous to use together with or in place of the alcohols mentioned their reaction products with alkylene oxides, in particular propylene oxide.
  • Such compounds preferably have a molecular weight of up to 500 g / mol.
  • the addition of the alkylene oxides in the preparation of these reaction products can be carried out with any catalysts, for example with basic catalysts.
  • the polyether alcohols for the production of flexible polyurethane foams usually have a hydroxyl number in the range between 20 and 100 mg KOH / g.
  • the addition of the alkylene oxides in the preparation of the polyether alcohols used for the process according to the invention can take place by the known processes.
  • the polyether alcohols contain only one alkylene oxide.
  • a so-called block-wise addition in which the alkylene oxides are added one after the other in succession, or a so-called statistical addition, in which the alkylene oxides are added together, possible.
  • the addition of the alkylene oxides is carried out under customary conditions, such as temperatures in the range of 60 to 180 ° C, preferably between 90 to 140 ° C, in particular between 100 to 130 ° C and pressures in the range of 0 to 20 bar, preferably in the range from 0 to 10 bar and in particular in the range of 0 to 5 bar.
  • the mixture of starting substance and DMC catalyst can be pretreated by stripping before starting the alkoxylation according to the teaching of WO 98/52689.
  • the polyether alcohol is usually worked up by customary processes by removing the unreacted alkylene oxides and volatile constituents, usually by distillation, Steam or gas stripping and or other methods of deodorization. If necessary, filtration can also be carried out.
  • the catalyst can be separated from the reaction mixture after completion of the addition of the alkylene oxides.
  • the preparation of the polyether alcohols can also be carried out continuously.
  • Such a procedure is for example in WO
  • alkylene oxides and starting substance are continuously metered into a continuous reactor and the resulting polyether alcohol is taken off continuously.
  • the monofunctional polyether alcohols obtained are mostly used as surface-active compounds.
  • the polyfunctional polyether alcohols are usually reacted with polyisocyanates to give polyurethanes.
  • Catalyst B 50 g of Catalyst B were heated in 1 L of a 5% by weight aqueous solution of potassium sulfite, the pH of which was adjusted to 6 with sulfuric acid, while stirring and refluxing for 3 hours.
  • the DMC catalyst was filtered off with suction after cooling and washed with demineralized water.
  • catalyst A 50 g of catalyst A were suspended in 1 L of a 5 wt .-% aqueous solution of sodium thiocyanate for 2 hours with stirring.
  • the DMC catalyst was filtered off with suction and suspended once more in 1 l of a 5% strength by weight aqueous solution of sodium thiocyanate for 2 hours with stirring.
  • the DMC catalyst was then filtered off with suction and washed with demineralized water.
  • catalyst A 50 g of catalyst A were heated in 1 L of a 15 wt .-% aqueous solution of potassium thiocyanate for 3 hours with stirring and reflux.
  • the DMC catalyst was filtered off with suction after cooling and washed with demineralized water.
  • Catalyst 6 (according to the invention)
  • catalyst B 50 g were briefly slurried in 1 L of a 5 wt .-% aqueous solution of potassium bromide. The homogeneous suspension was hung in a round-bottomed flask to a rotary evaporator and rotary evaporated for 2 hours at 50 ° C and 75mbar, wherein distilled off liquid was replaced by deionized water, so that the suspension does not dry.
  • the DMC catalyst was filtered off with suction and the described treatment was repeated with fresh solution. The DMC catalyst was then filtered off with suction and washed with demineralized water.
  • catalyst B 50 g of catalyst B were heated in 1 L of a 5 wt .-% aqueous solution of potassium borate, prepared from aqueous boric acid solution by addition of potassium hydroxide to a pH of 6, 2 hours with stirring and reflux.
  • the DMC catalyst was filtered off with suction and the described treatment was repeated with fresh solution. Subsequently, the DMC catalyst was filtered off with suction and washed with demineralized water.
  • catalyst B 50 g were briefly slurried in 20OmL of deionized water and filtered with suction on a glass sintered frit. The moist filter cake was slowly washed on the glass sintered frit with 2 L of a 5 wt.% Aqueous solution of potassium thiocyanate within 3 hours. Subsequently, the DMC catalyst was washed with demineralized water.
  • a glycerol propoxylate of molecular weight about 900 g / mol (hereinafter called VP900) with the appropriate amount DMC catalyst, which had previously been dried for 16 hours at 40 ° C, finely dispersed by means of an Ultra-turrax device for 5 minutes.
  • the reactor was sealed and evacuated at a temperature of 100 ° C for two hours at 3 mbar.
  • 36 g of propylene oxide were metered in within 2 minutes and the course of the pressure and temperature was recorded.
  • the reaction product was discharged from the autoclave at 100 ° C. after inerting with nitrogen and degassing at 10 mbar and the yield was determined. From the recorded curves, the time to the occurrence of the determined maximum (induction period), the maximum temperature and the maximum pressure were taken as a measure of the activity.
  • all catalysts according to the invention have either a shortened induction period, a higher exotherm or a higher pressure.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Polyethers (AREA)

Abstract

Procédé de fabrication de composés de cyanures multimétalliques comprenant les étapes suivantes : a) faire réagir la solution aqueuse d'un sel métallique de formule générale (I) M<SUP>1</SUP> <SUB>g</SUB>X
EP06819719A 2005-12-02 2006-11-23 Procédé de fabrication de composés de cyanures multimétalliques Withdrawn EP1963012A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005057895A DE102005057895A1 (de) 2005-12-02 2005-12-02 Verfahren zur Herstellung von Multimetallcyanidverbindungen
PCT/EP2006/068841 WO2007082596A1 (fr) 2005-12-02 2006-11-23 Procédé de fabrication de composes de cyanures multimétalliques

Publications (1)

Publication Number Publication Date
EP1963012A1 true EP1963012A1 (fr) 2008-09-03

Family

ID=38042473

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06819719A Withdrawn EP1963012A1 (fr) 2005-12-02 2006-11-23 Procédé de fabrication de composés de cyanures multimétalliques

Country Status (7)

Country Link
US (1) US8119825B2 (fr)
EP (1) EP1963012A1 (fr)
JP (1) JP5121718B2 (fr)
KR (1) KR20080075214A (fr)
CN (1) CN101336136B (fr)
DE (1) DE102005057895A1 (fr)
WO (1) WO2007082596A1 (fr)

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WO2011018471A1 (fr) * 2009-08-13 2011-02-17 Basf Se Procédé de production de composés de cyanure multimétalliques
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CN114276536A (zh) * 2022-01-13 2022-04-05 武汉全福茂新材料有限公司 一种硅烷改性聚醚及其直接制备硅烷改性聚醚的方法
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WO2007082596A1 (fr) 2007-07-26
KR20080075214A (ko) 2008-08-14
US20080300376A1 (en) 2008-12-04
CN101336136A (zh) 2008-12-31
CN101336136B (zh) 2012-02-08
JP2009517511A (ja) 2009-04-30
US8119825B2 (en) 2012-02-21
DE102005057895A1 (de) 2007-06-06
JP5121718B2 (ja) 2013-01-16

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