EP2212364A1 - Élastomères polyuréthanne/polyurée à base de prépolymères de diisocyanate de 2,4'-diphénylméthane et leur fabrication - Google Patents
Élastomères polyuréthanne/polyurée à base de prépolymères de diisocyanate de 2,4'-diphénylméthane et leur fabricationInfo
- Publication number
- EP2212364A1 EP2212364A1 EP08851682A EP08851682A EP2212364A1 EP 2212364 A1 EP2212364 A1 EP 2212364A1 EP 08851682 A EP08851682 A EP 08851682A EP 08851682 A EP08851682 A EP 08851682A EP 2212364 A1 EP2212364 A1 EP 2212364A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- elastomer
- total amount
- weight
- diphenylmethane diisocyanate
- nco
- 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.)
- Ceased
Links
Classifications
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
Definitions
- the present invention relates to polyurethane / polyurea elastomers (PUR elastomers) having improved processing characteristics such as extended casting time and reduced brittleness, as well as occupational hygiene benefits, such elastomers being suitable for replacing elastomers based on TDI prepolymers in comparable applications, as well a process for their preparation and their use.
- PUR elastomers polyurethane / polyurea elastomers
- PUR elastomers aromatic diisocyanates are reacted with long chain polyols to form a prepolymer having terminal NCO groups.
- prepolymers may also contain free monomeric diisocyanates.
- prepolymers are then chain extended with a short chain polyol or an aromatic polyamine to form a PUR elastomer.
- the viscosity of the reaction melt starting from liquid NCO prepolymer and liquid chain extender continuously increases until a solid elastomer has formed.
- the loss of NCO groups should be kept as low as possible and an increase in viscosity to a minimum.
- 4,4'-MDI (NCO content 33.5 wt .-%) to an NCO content of 28.9 wt .-% carbodiimidized (CD) / uretonimidinstrument (UI).
- This modified 4,4'-MDI crystallizes gradually after 7 days of storage only at 15 ° C. If one modifies 4,4'-MDI to 27.8 wt.% NCO content, the crystallization even begins only between 5 and 10 0 C.
- the increase in functionality has a strongly negative effect on processing and material properties of the PUR elastomers prepared from these modified isocyanates.
- the molecular weight buildup of the PUR reaction mixture is greatly accelerated, i. the casting time is shortened, and the mechanical properties, in particular the tear propagation resistance and the flex life, are strongly negatively affected.
- This object has been achieved by using special isocyanate components in the preparation of the polyurethane and using aromatic amines as chain extenders.
- the invention therefore polyurethane / polyurea elastomers, which are obtainable by reacting the components consisting of
- G 0 to 2% by weight, based on the total amount of elastomer, of aging inhibitors,
- N 0 to 3 wt .-%, based on the total amount of elastomer, blowing agents and / or water.
- the CDfUI modified 2,4'-MDI can be added in liquid form, so that the NCO content of the prepolymers can be easily increased, without having to resort to solid MDI derivatives or on solid 2,4'-MDI, or 4 To use 4'-MDI-containing modifications that would increase the reactivity too much.
- Another object of the invention is a process for the preparation of the polyurethane-ZPolyharnstoff-elastomers according to the invention, wherein
- Polyester polyols having number average molecular weights of 250 to 6000 g / mol and functionalities of 1.95 to 2.20
- aromatic diaminic chain extenders having a molecular weight of less than 900 g / mol in the presence of
- G 0 to 2% by weight, based on the total amount of elastomer, of aging inhibitors,
- N 0 to 3 wt .-%, based on the total amount of elastomer, blowing agents and / or water
- CD / UI-modified 2,4'-MDI is obtained by reacting MDI with a 2,4'-isomer content of 90 to 100% by weight, preferably 95 to 100% by weight, particularly preferably 98 to 100 wt .-%, preferably using catalysts, eg Implements phospholine derivatives.
- catalysts eg Implements phospholine derivatives.
- the phospholine-type catalysts are described, for example, in EP-A 0 515 933 and US Pat. No. 6,120,699. Typical examples of these catalysts are the mixtures of the phospholine oxides known from the prior art
- the amount of catalyst used depends on the quality and / or the reactivity of the starting isocyanate. The amount of catalyst necessary in each case can therefore be determined most simply in a preliminary experiment.
- the carbodiimidization / uretonimidization reaction is usually carried out in a temperature range of 50 to 150 ° C, preferably from 60 to 100 0 C. However, significantly higher reaction temperatures are possible (up to about 28O 0 C). The optimum reaction temperature depends on the type of catalyst used and can also be determined in a preliminary experiment. - o -
- the carbodiimidization / Uretonimidmaschinesresure is terminated when an NCO content of 25 to 31.5 wt.%, Preferably 27 to 30.5 wt .-%, particularly preferably 28 to 30 wt.% By addition of a stopper.
- the NCO content is determined in the manner known to those skilled in the art either by titration or by on-line techniques (e.g., near-infrared analysis). Of course, the course of the reaction can also be determined by the amount of escaping carbon dioxide. This volumetrically determinable amount of carbon dioxide provides information about the achieved degree of conversion at any time.
- At least the equimolar amount of a stopper particularly preferably the molar excess of 1 to 20 times, very particularly preferably 1 to 10 times the molar excess, is used.
- stoppers are e.g. in DE-A 25 37 685, EP-A 515 933, EP-A 609 698 and US-A 6 120 699 and include e.g. Acids, acid chlorides, chloroformates, silylated acids and alkylating agents, e.g. Esters of trifluoromethanesulfonic acid, e.g. Ethyl trifluoromethanesulfonic acid (ETF).
- Silylated acids are e.g. Trimethylsilyl trifluoromethanesulfonate (TMST).
- the stopper can be added to the reaction mixture either in one portion or in two portions, the second portion after cooling e.g. to room temperature.
- reaction mixture can be completely freed from the formed carbon dioxide after completion of the reaction by applying a vacuum.
- This CD / UI-modified 2,4'-MDI has the advantage over the correspondingly modified 4,4'-MDI that it has the same NCO content, i. same degree of carbodiimidization crystallized only at lower temperatures. Of course, this is an important advantage in processing, as this product does not have to be stored warm. This advantageous property is also apparent from Table 1.
- the NCO prepolymers A2) are obtained by reacting a high molecular weight polyol with 2,4'-MDI.
- High molecular weight polyols are in particular hydroxyl-terminated polyether and polyester polyols having a number average molecular weight of from 250 to 6000 g / mol, preferably from 500 to 4000 g / mol.
- Polyether polyols can be described by the general formula HO (RO) n H where R is an alkylene radical and n takes values such that the molecular weight ranges from 250 to 6000 g / mol.
- polyether polyols are the polyols known to those skilled in the art, which are obtained by ring-opening polymerization of monomeric cyclic ethers or by acid condensation of diols or dihydroxyethers.
- polyether polyols are bifunctional, but can also have higher functionalities by choosing suitable higher-functional starters.
- Typical monomeric cyclic ethers are ethylene oxide, propylene oxide and tetrathydrofuran.
- Polyester polyols are obtained by reacting dicarboxylic acids with diols with elimination of water.
- Important dicarboxylic acids are adipic, glutaric, succinic, sebacic or phthalic acid, the latter usually being used in the form of the anhydride.
- Important diols are ethylene, 1, 2-propylene, 1,3-propylene, 1,4-butylene or diethylene glycol, but also 1,6-hexanediol, and its isomers.
- building blocks from the group glycerol, 1,1,1-trimethylolpropane, pentaerythritol and sorbitol can be used.
- polyester polyols can also be used.
- polycarbonate polyols can also be used.
- the 2,4'-MDI-based prepolymers are prepared by slowly adding the respective polyol to charged molten 2,4'-MDI. To complete the reaction is then stirred for 2 to 8 hours at elevated temperature, preferably 40 to 100 0 C, more preferably stirred at 50 to 90 0 C.
- the prepolymers are mixed before use with the CD / UI-modified 2,4'-MDI to vary the NCO content of the prepolymer.
- the advantage is that the processing can be carried out with two isocyanate raw materials which are liquid at ambient temperature and casting elastomers can be produced with a wide range of properties that would otherwise be accessible only with a large number of raw materials.
- the NCO prepolymer is thus supplemented with monomeric diisocyanate.
- these monomeric diisocyanates should also be storable and usable in liquid form at ambient temperature.
- the CD / UI-modified 2,4'-MDI used fulfills these requirements.
- component B exclusively aromatic diamines are used.
- the molecular weight of component B) is below 900 g / mol.
- the Jeffamine available on the market ® will not be used as a component.
- Other oligomeric or polymeric aliphatic diamines do not belong to the group of compounds used as component B).
- the chain extenders for producing the casting elastomers are the aromatic diamines known per se. Preferred are the aromatic diamines which have a low melting point or are liquid. Particularly preferred are diamines which melt below 12O 0 C.
- Aromatic aminic chain extenders are, for example, 4,4'-methylenebis (2-chloroaniline) (MBOCA), 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,5-dimethyl-3', 5'-diisopropyl-4,4'-diaminophenylmethane, 3,5-diethyl-2,4-toluenediamine, 3,5-diethyl-2,6-toluenediamine (DETDA), 4,4'-methylenebis (3 chloro-2,6-diethylaniline), 3,5-dimethylthio-2,4-toluenediamine, 3,5-dimethylthio-2,6-toluenediamine (Ethacure TM 300, Albemarle Corporation), methylenedianiline, trimethyleneglycol-di-p- amino-benzoate (Polacure TM 740, Air Products and Chemicals Inc.),
- the components C) to N) are the generally known additives and auxiliaries, which are described in detail in G. Oertel, Polyurethane Handbook, 2nd edition, C. Hanser Verlag 1993, pages 98 ff.
- auxiliaries and additives are, for example, acid stabilizers, eg chloropropionic, dialkyl, p-toluene sulfonic acid or acid chlorides such as benzoic acid, phthalic acid dichloride, and antioxidants, such as Ionol ®, phosphites and Stabaxol ® known as hydrolysis. Fillers such as carbon black, carbon nanotubes, chalk and glass fibers can be used as well as dyes.
- the casting elastomers are preferably prepared by first degassing the isocyanate component at elevated temperature under reduced pressure while stirring, then stirring it with the chain extender and pouring the reacting melt into preheated molds.
- Casting elastomers are used where good mechanical properties are required, for example as industrial rollers e.g. in the paper industry, as rollers and wheels, squeegees, hydrocyclones, for electrical encapsulation, for the production of screens, sports floor coverings and bumpers.
- Desmodur ® CD-S carbodiimide / uretonimine modified Desmodur ® 44M (isocyanate based on 4,4'-MDI) having an NCO content of 29.5 wt .-% of Bayer MaterialScience AG with a crystallization section. 15 to 20 0 C.
- Phopholine oxide Tvp catalyst technical mixture of 1-methyl-1-oxo-1-phosphacyclopent-2-ene and 1-methyl-1-oxo-1-phosphacyclopent-3-ene, 1% by weight in toluene.
- Stopper ethyl trifluoromethanesulfonate (stopper A) or trimethylsilyl trifluoromethanesulfonate (stopper B)
- Desmodur ® VP.PU ME 40TF04 Ether-based NCO prepolymer of 2,4'-MDI having an NCO content of 3.9 wt .-% from Bayer MaterialScience AG.
- Desmodur ® VP.PU ME 80TF04 Ether-based NCO prepolymer of 2,4'-MDI having an NCO content of about 8 wt .-% from Bayer MaterialScience AG.
- Desmodur ® VP.PU ME 60TF04 Ether-based NCO prepolymer of 2,4'-MDI having an NCO content of about 6 wt .-% from Bayer MaterialScience AG.
- Bavtec ® XL 1604 3,5-diamino-4-chlorobenzoic from Bayer Material Science AG.
- Table 1 shows that 2,4'-MDI having carbodiimide / uretonimine groups at stop amounts of 50 and 10 ppm and an NCO content of 29.1 to 29.5% in terms of the crystallization range and the viscosity provides virtually identical products.
- Examples A-3 and A-4 show that at nearly equal NCO contents, the product of the present invention is the more favorable, i. has lower crystallization range.
- Example A-4 (V) shows that even at a high degree of modification, i. At a low NCO value with 4,4'-MDI no good crystallization properties can be achieved.
- the carbodiimide / uretonimine modified 2,4'-MDI according to Example AI was homogenized with Desmodur® VP.PU ME 40TF04 for one hour at 8O 0 C under nitrogen. Subsequently, the NCO content and the viscosity were determined.
- the cast elastomers were (3,5-diamino-4-chloro- benzoeklareisobutylester) prepared using Baytec ® XL 1604 as crosslinking agent, wherein the mixtures with degassing at 90 0 C to 100 0 C with preheated Baytec ® XL 1604 stirred for 30 seconds were.
- the reacting melt was poured in to HO 0 C preheated molds and cured for 24 hours at 110 0 C. Then store at room temperature for 7 days and determine the mechanical values (see Table 3).
- Desmodur ® ME VP.PU 80TF04 Ether-based NCO-prepolymer of 2,4'-MDI having an NCO content of about 8 wt .-% of Bayer Material Science AG.
- Desmodur ® ME VP.PU 60TF04 Ether-based NCO-prepolymer of 2,4'-MDI having an NCO content of about 6 wt .-% of Bayer Material Science AG.
- Table 3 shows that with the use of the prepolymer / blends with the same NCO content, ie, the same amounts of added Baytec ® XL 1604 when using carbodiimidized / ure- tonimidis Aidm 4,4'-MDI, the casting time is shortened adversely as a blend component.
- the cast elastomers C-3 according to the invention have a casting time of 170 sec and C-5 a casting time of 210 sec.
- the comparative example CI (V) has a casting time of only 115 sec. Both systems according to the invention (C-3 and C-5) even achieve almost the casting time of the directly produced elastomer C-7 (V) and are easily processable without problems.
- elastomers (C-3 and C-5) are obtained from blends of low NCO-containing prepolymers with modified 2,4'-MDI, which have the same property level as elastomers which react directly with 2,4'-MDI.
- Prepolymers are prepared (C-7 (V)). That is, by blending a high NCO-containing isocyanate component and a low NCO-containing prepolymer, elastomers having properties that are normally obtained only by using specific isocyanate components can be prepared.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007055267 | 2007-11-20 | ||
DE102008045223A DE102008045223A1 (de) | 2007-11-20 | 2008-08-30 | Polyurethan-/Polyharnstoff-Elastomere auf Basis von 2,4'-Diphenylmethandiisocyanat-Prepolymeren und ihre Herstellung |
PCT/EP2008/009520 WO2009065513A1 (fr) | 2007-11-20 | 2008-11-12 | Élastomères polyuréthanne/polyurée à base de prépolymères de diisocyanate de 2,4'-diphénylméthane et leur fabrication |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2212364A1 true EP2212364A1 (fr) | 2010-08-04 |
Family
ID=40577256
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08851682A Ceased EP2212364A1 (fr) | 2007-11-20 | 2008-11-12 | Élastomères polyuréthanne/polyurée à base de prépolymères de diisocyanate de 2,4'-diphénylméthane et leur fabrication |
Country Status (6)
Country | Link |
---|---|
US (1) | US20090131606A1 (fr) |
EP (1) | EP2212364A1 (fr) |
CN (1) | CN101868484A (fr) |
DE (1) | DE102008045223A1 (fr) |
TW (1) | TW200946552A (fr) |
WO (1) | WO2009065513A1 (fr) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120202945A1 (en) * | 2009-07-07 | 2012-08-09 | Baulé S.A.S. | Polyurethanes and use thereof |
US9994672B2 (en) | 2011-12-20 | 2018-06-12 | Covestro Deutschland Ag | Hydroxy-aminopolymers and method for producing same |
CN102585688A (zh) * | 2012-02-29 | 2012-07-18 | 廖有为 | 一种单组分聚氨酯-脲弹性体车底涂层 |
CN104341576A (zh) * | 2013-08-05 | 2015-02-11 | 福建南光轻工有限公司 | 消防水带用tpu树脂 |
CN103483533A (zh) * | 2013-09-23 | 2014-01-01 | 句容市睿远科技有限公司 | 一种高铁减震垫板用弹性体及其制备方法 |
CN103740091B (zh) * | 2014-01-20 | 2015-11-04 | 苏州井上高分子新材料有限公司 | 一种发泡轮用聚醚型聚氨酯弹性体组合物及其制备方法 |
CN104194318B (zh) * | 2014-09-22 | 2017-01-11 | 东莞市雄林新材料科技股份有限公司 | 一种用于鞋材印刷的tpu薄膜及其制备方法 |
CN104231224A (zh) * | 2014-10-22 | 2014-12-24 | 苏州市景荣科技有限公司 | 一种导电的pu鞋材及其制造方法 |
CN104341579B (zh) * | 2014-10-27 | 2016-11-02 | 中国科学院长春应用化学研究所 | 一种低形变聚氨酯减震缓冲块的制备方法 |
EP3402670B1 (fr) * | 2016-01-15 | 2021-09-22 | Basf Se | Article composite |
WO2018094611A1 (fr) * | 2016-11-23 | 2018-05-31 | 广州艾科新材料股份有限公司 | Matériau moussant à base de polyuréthane souple |
CN111253550A (zh) * | 2020-01-16 | 2020-06-09 | 滁州市玉林聚氨酯有限公司 | 一种阻燃耐磨聚氨酯轮及其制备方法 |
Family Cites Families (17)
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DE1618380C3 (de) * | 1967-03-08 | 1975-09-11 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung eines bei Raumtemperatur flüssigen Diphenylmethan-diisocyanatpräparates |
DE2537685C2 (de) | 1975-08-23 | 1989-04-06 | Bayer Ag, 5090 Leverkusen | Verfahren zur teilweisen Carbodiimidisierung der Isocyanatgruppen von organischen Polyisocyanaten |
AU532047B2 (en) * | 1978-12-11 | 1983-09-15 | Ici Ltd. | Modified isocyanate |
DE2928182A1 (de) * | 1979-07-12 | 1981-01-29 | Bayer Ag | Verfahren zur herstellung von elastischen, gegebenenfalls zellfoermigen, polyurethanharnstoffen |
EP0288067A1 (fr) * | 1987-04-24 | 1988-10-26 | Asahi Glass Company Ltd. | Procédé de préparation d'élastomères de polyuréthane et composition pour la préparation de ceux-ci |
DE4117384A1 (de) * | 1991-05-28 | 1992-12-03 | Bayer Ag | Verfahren zur herstellung fluessiger, lagerstabiler carbodiimid- und/oder uretonimingruppen aufweisender organischer isocyanate und ihre verwendung zur herstellung von polyurethankunststoffen |
DE4126359A1 (de) * | 1991-08-09 | 1993-02-11 | Basf Ag | Oligomere carbodiimide |
KR100275076B1 (ko) * | 1992-12-07 | 2000-12-15 | 배리 제이. 사인맨 | 4,4'-메틸렌-비스-(3-클로로-2,6-디에틸아닐린)으로 경화된 폴리우레탄 |
DE4302697A1 (de) * | 1993-02-01 | 1994-08-04 | Bayer Ag | Verfahren zur Herstellung organischer Carbodiimide und ihre Verwendung als Kunststoff-Stabilisatoren |
US5731397A (en) * | 1996-04-16 | 1998-03-24 | Huntman Petrochemical Corporation | Polyurea spray railcar lining systems |
US6120699A (en) | 1998-09-21 | 2000-09-19 | Basf Corporation | Storage stable methylene bis(phenylisocyanate) compositions |
US6242556B1 (en) | 2000-02-07 | 2001-06-05 | Bayer Corporation | Liquid MDI adducts with improved freeze stability |
DE102004022683A1 (de) * | 2004-05-05 | 2005-11-24 | Basf Ag | Polyharnstoff-Sprühelastomere |
DE102004035764A1 (de) * | 2004-07-23 | 2006-03-16 | Bayer Materialscience Ag | Niedrigviskose Polyurethan-Prepolymere auf Basis von 2,4'-MDI |
DE102005012794A1 (de) * | 2005-03-19 | 2006-09-21 | Bayer Materialscience Ag | Poly(etherester)polyole und Verfahren zu ihrer Herstellung |
DE102006002158A1 (de) * | 2006-01-17 | 2007-07-19 | Bayer Materialscience Ag | Verfahren zur Herstellung flüssiger, lagerstabiler Carboddimid- und/oder Uretonimingruppen aufweisender organischer Isocyanate |
DE102006004527A1 (de) * | 2006-02-01 | 2007-08-09 | Bayer Materialscience Ag | Polyurethan-Gießelastomere aus NCO-Prepolymeren auf Basis von 2,4-MDI, ein Verfahren zu ihrer Herstellung und ihre Verwendung |
-
2008
- 2008-08-30 DE DE102008045223A patent/DE102008045223A1/de not_active Withdrawn
- 2008-11-12 CN CN200880117038A patent/CN101868484A/zh active Pending
- 2008-11-12 WO PCT/EP2008/009520 patent/WO2009065513A1/fr active Application Filing
- 2008-11-12 EP EP08851682A patent/EP2212364A1/fr not_active Ceased
- 2008-11-19 TW TW097144605A patent/TW200946552A/zh unknown
- 2008-11-19 US US12/273,986 patent/US20090131606A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO2009065513A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2009065513A1 (fr) | 2009-05-28 |
CN101868484A (zh) | 2010-10-20 |
DE102008045223A1 (de) | 2009-05-28 |
TW200946552A (en) | 2009-11-16 |
US20090131606A1 (en) | 2009-05-21 |
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