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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/04—Hydrides of silicon
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G17/00—Compounds of germanium
• • 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
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
  • C08G79/14—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and silicon
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• This disclosure relates to chlorinated oligogermanes and mixtures of chlorinated oligogermanes which have a molar germanium:chlorine ratio of 1:2 to 1:3 and also to a method for producing such chlorinated oligogermanes and oligogermane mixtures.
• Germanium dichloride can more particularly be produced thermally from trichlorogermane (HGeCl 3 ) (cf. Holleman Wiberg, Lehrbuch der Anorganischen Chemie, Walter De Gruyter Verlag, 102 nd edition, p. 1013 or C. E. Rick, T. D. McKinley, J. N. Tully (PB No. 96945 [1944] 1/10)).
• HGeCl 3 trichlorogermane
• WO 08/110386 A1 discloses a method and apparatus for production of halogenated polygermanes from halogermanes in a plasma-chemical way.
• Halogenated oligogermanes are little known apart from hexachlorodigermane, which is described in the literature.
• a chlorinated oligogermane as a pure compound or mixture of compounds which each have at least one direct Ge—Ge bond, substituents of which include chlorine or chlorine and hydrogen and atom ratio for substituent:germanium is at least 2:1 in the composition thereof, wherein a) the mixture has on average a Ge:Cl ratio of 1:1 to 1:3, or the pure compound has a Ge:Cl ratio of 1:2 to 1:2.67, and b) the mixture has an average number of germanium atoms of 2 to 8.
• We also provide a method for producing a halogenated oligogermane including A) providing a chlorinated polygermane, and B) chlorinating the chlorinated polygermane with chlorine, a chlorine-releasing compound and/or a chlorine-containing gas.
• the chlorinated oligogermanes (as pure compound) and the mixture of such chlorinated oligogermanes have at least one direct germanium-germanium bond, the substituents of which comprise either chlorine or chlorine and hydrogen, or at least one direct germanium-germanium bond, the substituents of which consist of chlorine or of chlorine and hydrogen.
• the atom ratio therein for substituent:germanium is at least 2:1.
• the chlorinated oligogermanes as pure compound have a germanium:chlorine ratio of 1:2 to 1:2.67.
• the mixtures of chlorinated oligogermanes further have a germanium:chlorine ratio of 1:1 to 1:3 and more particularly 1:2 to 1:3 and also an average number of germanium atoms per molecule of 2 to not more than 8.
• the mixture of chlorinated oligogermanes is more particularly to be understood as meaning that only some of the compounds present therein need have at least one direct germanium-germanium bond with the abovementioned substituents.
• the general case is that at least two such compounds having a direct germanium-germanium bond will be present in the mixture, but frequently three or more. In the general case, moreover, it is exclusively compounds having such a defined germanium-germanium bond which will be present in such a mixture with or without any tetrachlorogermane.
• Chlorinated oligogermanes are more particularly compounds of the formula Ge n X 2n+2 where n is not more than 8, or mixtures of chlorinated oligogermanes having an average n of not more than 8, where X is more particularly chlorine or else chlorine and hydrogen. In the individual case, single chlorine atoms can be replaced by bromine atoms, but generally there will be no bromine. Chlorinated polygermanes are accordingly more particularly compounds of the formula Ge n X 2n+2 where n >8.
• the chlorine content of the pure compounds, or the average chlorine content of a mixture, is determined herein by completely digesting the sample and then titrating the chloride by the Mohr method.
• the hydrogen content is determined by integration of 1 H NMR spectrum using an internal standard and comparing the integrals obtained at known mixing ratio.
• the molar masses of halogenated oligogermanes and the average molar masses of mixtures thereof are determined via freezing point depression.
• the recited parameters of chlorine content, molar mass and, if appropriate, hydrogen content can be used to determine the chlorine:germanium ratio and also the average number of germanium atoms per molecule directly.
• the chlorinated oligogermanes are obtainable in one example by chlorinating chlorinated polygermanes. Chlorinated oligogermanes thus obtained then generally have a heightened kinetic stability, more particularly with regard to the further chlorination of the oligochlorogermanes since the most reactive molecules in the chlorinated polygermane mixture will have already reacted.
• the chlorinated oligogermanes are more particularly suitable for applications where the chlorinated germanes are further processed under oxidizing conditions.
• An example is the application of layers of the chlorinated oligogermanes onto substrates in oxidizing atmospheres such as atmospheres containing chlorine gas, for example.
• the oligogermanes are obtained by splitting chlorinated polygermanes (PCGs) using an oxidizing agent.
• Chlorine and/or HCl are more particularly useful here as oxidizing agent, in which case the splitting can also be performed such that either an excess of the oxidizing agent is present or that the oxidizing agent is always present at low concentration only.
• the chlorinated polygermanes used as starting material are more particularly obtainable thermally as per Holleman Wiberg, Lehrbuch der Anorganischen Chemie, Walter De Gruyter Verlag, 102 nd edition, p. 1013 or C. E. Rick, T. D. McKinley, J. N. Tully (PB No. 96945 [1944] 1/10).
• trichlorogermane HGeCl 3
• HCl HCl
• Plasma-chemically obtained chlorinated polygermanes can also be used as an alternative or additional starting material, more particularly chlorinated polygermanes as described in WO 2008/110386 A1, the subject matter of which is incorporated herein by reference.
• the chlorinated polygermanes can also be plasma-chemically produced similarly to chlorinated polysilanes, methods for production of which are described, for example, in WO 2006/125425 A1 and WO 2009/143823 A2.
• the corresponding germanium compounds are then used as starting material, while the concrete plasma-chemical production is essentially identical to that of the corresponding silanes except that the power density of the irradiation should be lower than for the corresponding silanes.
• the power density should correspond to about 50 to 67% of the power density (in watts per cm 3 ) which is described in the two above-mentioned publications.
• the subject matter of WO 2006/125425 A1 and WO 2009/143823 A2 is incorporated herein by reference.
• the mixture of oligogermanes has a higher solubility in inert solvents than at least one and typically two or more of the respective individual components of the mixture insofar as these individual components have more than 3 germanium atoms.
• Individual components are more particularly all the components that are present in the mixture at not less than 1 wt %.
• Individual components further more particularly include the respective perchlorinated compounds n-tetragermane, isotetragermane, n-pentagermane, isopentagermane and/or neopentagermane.
• the solubility of the mixture of oligogermanes is heightened compared with at least one of these compounds, usually compared with three or more than three of the recited compounds and frequently also compared with all recited compounds.
• Inert solvents here and hereinbelow are more particularly non-nucleophilic aprotic solvents, of which in turn the solvents toluene, benzene and cyclohexane must be mentioned more particularly.
• the above-mentioned mixture of oligogermanes preferably has a higher solubility than the individual components having more than 3 germanium atoms in one or more of the recited preferred solvents at least.
• any reference herein to a higher or better solubility in inert solvents is to be understood as meaning that the specific solvent is capable of dissolving at room temperature a larger amount of chemical compound or of the mixture of chemical compounds before saturation is reached, while not more than 5 wt % of the amount used may remain as solid material.
• the determinative amount here is not for instance the molar amount, but the amount used (in g) of the still just soluble oligogermane/polygermane as individual compound or as mixture.
• the mixture of oligogermanes has particularly good solubility because the various components appear to act as reciprocal solubilizers.
• the mixture of oligogermanes is also superior to the pure individual compounds since it is not just the case that the higher kinetic stability is advantageous, but it is generally also the case that when operating in solution more solvent is required for a specific further use.
• the chlorinated oligogermane mixtures have a higher solubility in inert solvents than the known thermally produced chlorinated polygermanes as described in Holleman Wiberg, Lehrbuch der Anorganischen Chemie, Walter De Gruyter Verlag, 102 nd edition, p. 1013 or C. E. Rick, T. D. McKinley, J. N. Tully (PB No. 96945 [1944] 1/10).
• a particularly interesting fraction of chlorinated oligogermane mixtures is the fraction with essentially no germanium tetrachloride, no Ge 2 Cl 6 and no Ge 3 Cl 8 left.
• This fraction can be isolated via fractional distillation from an as-obtained crude mixture of our chlorinated oligogermanes, and is hereinafter referred to as “fraction of compounds having more than three germanium atoms”.
• Germanium tetrachloride, Ge 2 Cl 6 and Ge 3 Cl 8 can be removed, for example, by distillation at 0.01 to 0.1 hPa (i.e., in an oil pump vacuum for example) and room temperature so that the fraction of compounds having more than three germanium atoms may be separated off.
• the fraction of compounds having more than three germanium atoms is obtained by distillation, as mentioned, or else by crystallization and, hence, has essentially no germanium tetrachloride, hexachlorodigermane and octachlorotrigermane left. Essentially it is to be understood as meaning that the compounds mentioned are present at not more than 10 wt % in that the proportion of these three compounds is typically less than 5 wt % and usually even less than 2 wt %. Ultrahigh-vacuum distillation can be used to effect a concrete determination of the remaining level of these compounds.
• the fraction of compounds having more than three germanium atoms generally has a heightened degree of branching (as can be evidenced using IR or Raman spectroscopy) and correspondingly has a particularly good kinetic stability.
• Branching occurs with germanium atoms having bonds leading to three further germanium atoms (that is, they are tertiary germanium atoms) and with germanium atoms having bonds leading to four further germanium atoms (that is, they are quaternary germanium atoms).
• the fraction of compounds having more than three germanium atoms has a more than 8 atom % fraction and more particularly more than 11 atom % fraction of branching sites.
• at least 8% and more particularly more than 11% of the germanium atoms in the mixture are tertiary or quaternary germanium atoms.
• the degree of branching here can be determined via Raman spectra from the significant bands for vibrations of germanium-germanium bonds involving tertiary or quaternary germanium atoms.
• the perchlorinated neopentagermane within the fraction of compounds having more than three germanium atoms has a share of at least 10 atom %, more particularly more than 18 atom % and more particularly more than 25 atom %.
• the proportion of this compound can be quantified via the signal for the quaternary germanium atom in 73 Ge NMR. The content can be determined versus a known internal reference substance of known quantity (for example, an ampoule with tetramethylgermanium) by integration.
• the fraction of chlorinated oligogermane mixtures having more than 3 germanium atoms has a germanium:chlorine ratio of 1:2.2 to 1:2.5 and more particularly of 1:2.25 to 1:2.4.
• appropriately chosen conditions of chlorination provide an oligochlorogermane mixture in which the Ge 2 Cl 6 content after step B) is particularly high.
• the Ge 2 Cl 6 content can then be at least 70 wt %, more particularly more than 85 wt % and preferably more than 95 wt %.
• HCl is used as chlorinating agent, it is more particularly also possible for a significant Ge 2 Cl 5 H content to also be present.
• the mixtures of chlorinated oligogermanes have an average number of germanium atoms per molecule in the range from 3 to 8.
• the chlorinated oligogermane has a hydrogen content of less than 2 atom % and more particularly less than 1 atom %. Frequently, the chlorinated oligogermane (mixture) will at most have a hydrogen content corresponding to the customary degrees of purity.
• the hydrogen substituents in the chlorinated oligogermane may more particularly come from the oxidation with HCl or be already present in the starting material since the chlorinated polygermanes can also have hydrogen substituents due to their method of production.
• the general rule applicable to all compounds mentioned herein is that they have customary degrees of purity. That is, the purity of a compound consisting of particular varieties of atoms, or of a mixture which consists of two or more such individual compounds (which may also include GeCl 4 ), is at least 99.5% and frequently is at least 99.95%, and that the proportion of impurities is more particularly less than 10 ppm (% by weight is always meant). In the individual case, chlorine atoms may be partly replaced by bromine substituents. These then do not count as impurity in the above sense.
• the chlorinated oligogermane when considered as individual compound includes more than 2 atom % and more particularly more than 2.8 atom % (in Ge 11 Cl 23 H for example) and even more particularly more than 6 atom % of hydrogen (in Ge 5 Cl 11 H for example).
• Even Si 2 Cl 5 H is capable of being produced by reaction with HCl and of being obtained as pure substance by distillation.
• the hydrogen contents recited herein can be determined as described above, via 1 H NMR spectroscopy.
• the signals observed therein are in the chemical shift range between 7.2 and 3.5 ppm and more particularly in the range between 5 and 3.8 ppm, and in the case of mixtures can be signals having very large full width at half maximum values.
• the chlorinated oligogermanes, and the mixtures thereof have significant bands in the Raman spectrum at below 600 wavenumbers, more particularly between 500 and 370 and even more particularly at ⁇ 320 wavenumbers.
• a significant band here and hereinbelow is generally any band whose intensity is greater than 10% of the highest intensity band in the Raman spectrum.
• the mixture of chlorinated oligogermanes may be more particularly colorless to slightly yellow or ivory white.
• the mixture is more particularly obtained as a mobile liquid or at least partly crystalline substance.
• the viscosity of the liquid proportion at room temperature is less than 1000 mPa s and more preferably less than 400 mPa s. Crystallinity can be determined using X-ray powder diffractometry, since crystalline compounds generate significant signals which naturally cannot occur in the case of liquid or viscid compounds.
• the chlorinated oligogermane is readily soluble in the inert solvent as defined above. Readily soluble here is to be understood as meaning that concentrations of at least 10 wt % can be put into solution.
• our chlorinated oligogermanes and our chlorinated oligogermane mixtures have the solubility properties of this example in at least one of the solvents benzene, toluene and cyclohexane, frequently even in all three solvents.
• “Readily” soluble further refers to chlorinated oligogermane mixtures where a nonsoluble residue of not more than 5 wt % of the amount used remains (this means in the case of a solution with 10 wt % of dissolved chlorinated oligosilane that at most 0.5 wt % can remain as nondissolved solid material). Frequently, however, complete dissolution of the chlorinated oligogermane mixture will take place.
• At least 20 wt % of the above soluble fraction is distillable under reduced pressure, especially under a pressure in the range from 0.01 to 1 hPa, without decomposing. This stipulation is satisfied more particularly by compounds having up to 4 germanium atoms.
• HCl is more particularly useful as chlorine-containing gas
• chlorine is more particularly in the form of Cl 2
• nonmetal chlorides are more particularly useful as chlorine-releasing compounds. Particular preference is given to using either Cl 2 or HCl as a chlorinating agent.
• Method step B) is generally subject to the following temperature conditions and/or pressure conditions, although in most cases not only the following pressure conditions, but also the following temperature conditions apply. It is accordingly more particularly the case that the temperature in method step B) is ⁇ 60° C. to 200° C. and especially ⁇ 30 to 40° C., for example, ⁇ 10 to 25° C.
• the pressure is more particularly 200 to 2000 hPa, for example, 800 to 1500 hPa.
• the chlorination as per method step B) is followed by a fractional distillation to separate comparatively volatile chlorinated germanes from germanes having at least 4 germanium atoms in the molecule. It is thus more particularly the case that GeCl 4 , Ge 2 Cl 6 and Ge 3 Cl 8 are separated off in the fractional distillation.
• This fractional distillation can take place for example at a pressure of 10 ⁇ 1 to 10 ⁇ 2 hPa and a temperature of up to 140° C., preferably up to 100° C., and will frequently be carried out at room temperature.
• the chlorinated polygermanes provided in step A) are diluted before step B) and more particularly GeCl 4 , Ge 2 Cl 6 and/or Ge 3 Cl 8 can be used as diluent (hereinafter also referred to as solvent).
• diluent hereinafter also referred to as solvent
• Such a dilution can provide a more efficient chlorination in step B).
• the diluents can subsequently also be distilled off again and optionally the distilled-off diluents can be reused afresh (i.e., recycled) as diluents.
• the method can be carried out such that an excess of the chlorinating agent, more particularly an excess of HCl, is present during step B).
• an excess can be present when free HCl is constantly present in the reaction mixture, for example, such that the solution is saturated with HCl.
• further chlorinating agent can be constantly replenished in step B). In general, however, no saturated HCl solutions are used.
• chlorinating agent When other chlorinating agents are used (but optionally also in the case of HCl) there will frequently be a molar deficiency of chlorinating agent and then further chlorinating agent will be replenished as appropriate (so that it is permanently in molar deficiency). Especially when Cl 2 is used as chlorinating agent, Cl 2 will frequently be used in that manner in molar deficiency relative to the chloropolygermane.
• the reaction with the chloropolygermane may advantageously be controlled via the rate of chlorine addition to thereby try to suppress the formation of GeCl 4 .
• the chlorination can be carried out by selecting a particularly long reaction time with Cl 2 which, as shown above, is always in molar deficiency. Should a significant proportion of Ge 2 Cl 5 H be formed, HCl must be used as a chlorinating agent instead of Cl 2 (or some other chlorinating agent that does not contain hydrogen). When a particularly low proportion of Ge 2 Cl 6 is desired, the reaction should be carried out at low temperatures and the Cl 2 should be added particularly carefully.
• the total molar quantity of chlorine added should be adjusted appropriately, for example, by choosing the added amount of chlorine in relation to the known chlorine:germanium ratio for the chloropolygermane used such that a certain chlorine:germanium ratio must automatically result for the chlorooligogermane mixture obtained.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Silicon Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Silicon Polymers (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Chemical Vapour Deposition (AREA)
• Catalysts (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=43499339

Family Applications (7)

Family Applications After (6)

Country Status (9)

Families Citing this family (20)

Citations (2)

Family Cites Families (107)

• 2009
  • 2009-12-04 DE DE102009056731A patent/DE102009056731A1/de not_active Withdrawn
• 2010
  • 2010-12-06 WO PCT/EP2010/068974 patent/WO2011067410A1/de not_active Ceased
  • 2010-12-06 JP JP2012541537A patent/JP5731531B2/ja not_active Expired - Fee Related
  • 2010-12-06 WO PCT/EP2010/068994 patent/WO2011067417A1/de not_active Ceased
  • 2010-12-06 JP JP2012541539A patent/JP2013512845A/ja active Pending
  • 2010-12-06 US US13/512,760 patent/US20130043429A1/en not_active Abandoned
  • 2010-12-06 WO PCT/EP2010/068986 patent/WO2011067413A2/de not_active Ceased
  • 2010-12-06 TW TW099142324A patent/TW201134764A/zh unknown
  • 2010-12-06 WO PCT/EP2010/068991 patent/WO2011067415A1/de not_active Ceased
  • 2010-12-06 EP EP10787448A patent/EP2507169A1/de not_active Withdrawn
  • 2010-12-06 EP EP10787124.6A patent/EP2507296B1/de not_active Revoked
  • 2010-12-06 TW TW099142320A patent/TW201132587A/zh unknown
  • 2010-12-06 US US13/513,217 patent/US20120315392A1/en not_active Abandoned
  • 2010-12-06 CA CA2782226A patent/CA2782226A1/en not_active Abandoned
  • 2010-12-06 US US13/513,018 patent/US9040009B2/en not_active Expired - Fee Related
  • 2010-12-06 US US13/513,384 patent/US20120321540A1/en not_active Abandoned
  • 2010-12-06 BR BR112012014106A patent/BR112012014106A2/pt not_active IP Right Cessation
  • 2010-12-06 CN CN201080054817.7A patent/CN102666381B/zh not_active Expired - Fee Related
  • 2010-12-06 JP JP2012541533A patent/JP6297778B2/ja not_active Expired - Fee Related
  • 2010-12-06 TW TW099142328A patent/TWI580710B/zh not_active IP Right Cessation
  • 2010-12-06 EP EP10792879.8A patent/EP2507172B1/de not_active Not-in-force
  • 2010-12-06 WO PCT/EP2010/068993 patent/WO2011067416A1/de not_active Ceased
  • 2010-12-06 CN CN201080055163.XA patent/CN102639609B/zh not_active Expired - Fee Related
  • 2010-12-06 JP JP2012541538A patent/JP2013512844A/ja not_active Ceased
  • 2010-12-06 TW TW099142326A patent/TW201139283A/zh unknown
  • 2010-12-06 CA CA2782247A patent/CA2782247A1/en not_active Abandoned
  • 2010-12-06 TW TW099142321A patent/TW201132708A/zh unknown
  • 2010-12-06 EP EP10787123A patent/EP2507317A1/de not_active Withdrawn
  • 2010-12-06 US US13/512,999 patent/US9139702B2/en not_active Expired - Fee Related
  • 2010-12-06 WO PCT/EP2010/068995 patent/WO2011067418A1/de not_active Ceased
  • 2010-12-06 TW TW099142323A patent/TWI561559B/zh not_active IP Right Cessation
  • 2010-12-06 TW TW099142322A patent/TWI589527B/zh not_active IP Right Cessation
  • 2010-12-06 EP EP10788316A patent/EP2507171A1/de not_active Withdrawn
  • 2010-12-06 EP EP10793199.0A patent/EP2507174B1/de not_active Revoked
  • 2010-12-06 WO PCT/EP2010/068979 patent/WO2011067411A1/de not_active Ceased
  • 2010-12-06 US US13/513,036 patent/US20130004666A1/en not_active Abandoned
  • 2010-12-06 BR BR112012013500A patent/BR112012013500A2/pt not_active IP Right Cessation
  • 2010-12-06 CN CN2010800551644A patent/CN102639644A/zh active Pending
  • 2010-12-06 EP EP10787451A patent/EP2507299A2/de not_active Withdrawn
  • 2010-12-06 US US13/513,611 patent/US9458294B2/en not_active Expired - Fee Related
  • 2010-12-06 JP JP2012541535A patent/JP2013512842A/ja active Pending
• 2016
  • 2016-04-28 JP JP2016090381A patent/JP2016179935A/ja active Pending

Patent Citations (2)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events