Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties

Definitions

• the present invention relates to a terpolymer
• the present invention relates to the use of this terpolymer to improve the cold flow properties of middle distillate fuels, to lower the lower mixing temperature of cold flow improver additives in middle distillate fuels and to improve the filterability of Kaltf togetherverêter- additives containing middle distillate fuels.
• the present invention also relates to middle distillate fuels containing such a terpolymer.
• Middle distillate fuels of fossil origin especially gas oils, diesel oils or light fuel oils derived from petroleum, have different levels of paraffins depending on the source of the crude oil.
• cloudy point or Cloud Point (“CP") precipitates solid paraffins.
• the platy n-paraffin crystals form a kind of "house of cards structure” and the middle distillate fuel stagnates, although its predominant part is still liquid.
• the precipitated n-paraffins in the temperature range between cloud point (cloud point) and pour point (“PP”) significantly affect the flowability of middle distillate fuels;
• the paraffins clog filters and cause uneven or completely interrupted fuel supply to the combustion units. Similar disturbances occur with light fuel oils.
• n-paraffins can be modified in middle distillate fuels.
• Good effective additives prevent middle distillate fuels from becoming solid at temperatures a few degrees Celsius below the temperature at which the first paraffin crystals crystallize out. Instead, fine, well crystallizing, separate paraffin crystals are formed, which also pass on further lowering of the temperature filter in motor vehicles and heating systems or at least form a permeable for the liquid part of the middle distillates filter cake, so that trouble-free operation is ensured.
• the effectiveness of the flow improvers is usually expressed in accordance with the European standard EN 1 16 indirectly by measuring the Cold Filter Plugging Point ("CFPP").
• ethylene-vinyl carboxylate copolymers such as ethylene-vinyl acetate copolymers (“EVA”) have long been used as such cold flow improvers or middle distillate flow improvers (“MDFI").
• EVA ethylene-vinyl carboxylate copolymers
• MDFI middle distillate flow improvers
• a disadvantage of these additives is that the paraffin crystals thus modified, due to their higher density compared to the liquid part, tend to settle more and more at the bottom of the container when storing the middle distillate fuel. This forms in the upper container part a homogeneous paraffine phase and at the bottom a two-phase paraffin-rich layer.
• Additives for improving the low-temperature behavior of middle distillate fuels of the newer generation are, for example, the terpolymers of ethylene, the vinyl ester of one or more aliphatic C 2 to C 20 monocarboxylic acids and bicyclo known from DE 196 20 1 19 C1 (1) [2.2.1 ] hept-2-ene (norbornene) or norbornene derivatives whose composition generally the wt .-% of vinyl ester at 5 to 40 wt .-% and the weight percent of norbornene or norbornene derivatives at 0 , 5 to 30 wt .-% is.
• EP 1 391 498 A1 (2) describes vinylic polymers which contain certain amounts of fractions insoluble in hexane at certain temperatures as flow improvers for fuel oils. These vinylic polymers are especially composed of ethylene and at least one vinylic monomer. As such, see monomers can serve unsaturated esters, ⁇ -olefins or "other vinylic monomers". Examples of unsaturated esters include vinyl acetate, vinyl propionate and methyl (meth) acrylate.
• Examples of ⁇ -olefins include propylene, 1-butene and higher homologs, and examples of "other vinylic monomers” include alicyclic hydrocarbon vinyl monomers such as cyclohexene, (di) cyclopentadiene, norbornene, pinene, indene or vinylcyclohexene.
• Japanese Laid-Open Patent Application 63-1,13097A (3) discloses fuel oil compositions containing certain copolymers as cold flow improvers.
• Example B-1 an ethylene-vinyl acetate copolymer having a vinyl acetate content of 33.1% by weight and a number average molecular weight of 2260 is used, which was prepared in the presence of the molecular weight regulator methylcyclohexane. It was the object to provide products available, which cause a very good cold behavior in middle distillate fuels. In particular, the CFPP value for these fuels should be effectively lowered. At the same time, these products should lower the lower blending temperature of cold flow improver additives into middle distillate fuels and improve the filterability of middle distillate fuels containing cold flow improver additives.
• the object is achieved by the above-mentioned terpolymer of components (A), (B) and (C).
• the terpolymer of the invention is
• component (C) 0.05 to 1 mol%, in particular 0.07 to 0.4 mol% of the component (C) constructed.
• the olefinically unsaturated hydrocarbon of component (C) is either the cylcoalkene mentioned under (iii) or the long-chain ⁇ -olefin mentioned under (iv).
• the component (C) usually contains only one olefinic double bond. aromatic Structural elements or a plurality of olefinically unsaturated double bonds are usually not present in component (C).
• the five-, six- or seven-membered cycloalkene used as component (C) of embodiment (iii) is monocyclic; bi- or polycyclic representatives are not suitable. In general, this Cylcoalkene contains a polymerizable olefinic double bond.
• Typical representatives of such cycloalkenes are cyclopentene, 1-methylcyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 1, 2-dimethylcyclopentene, 1, 3-dimethylcyclopentene, 1, 4-dimethylcyclopentene, cyclohexene, 1-methylcyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 1, 2-dimethylcyclohexene, 1, 3-dimethylcyclohexene, 1, 4-dimethyl-cyclohexene, Cylcohepten, 1 -Methylcyclohepten, 3-methylcycloheptene, 4-methylcycloheptene and 5-methylcyclohepten, of which, however, cyclohexene preferred becomes.
• the ⁇ -olefin used as component (C) of embodiment (iv) is usually linear, ie unbranched.
• this ⁇ -olefin contains no further unsaturations besides the one terminally polymerizable olefinic double bond.
• this ⁇ -olefin has 8 to 19, preferably 10 to 18, especially 12 to 16 carbon atoms.
• Typical representatives of such ⁇ -olefins are 1-hexene, 1-heptane, 1-octene, 1 -none, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1 - Hexadecene, 1-heptadecene, 1-octadecene, 1-nonodecene and 1-eicosene, of which, however, 1-dodecene, 1-tetradecene and 1-hexadecene are preferred.
• C2 to C-alkenyl esters of one or more aliphatic Cr to C2i monocarboxylic acids for the embodiment (i) of component (B) are in particular the vinyl and propenyl esters of aliphatic monocarboxylic acids having 2 to 18 carbon atoms, the hydrocarbon radical linear or can be branched. Preferred among these are the vinyl esters. Irrespective of the alkenyl radical, monocarboxylic acids which are particularly preferred for this purpose are those having 2 to 16, in particular 2 to 10, carbon atoms.
• carboxylic acids with a branched hydrocarbon radical preference is given to those whose branching is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie the carboxylic acid being a so-called neocarboxylic acid.
• the hydrocarbon radical of the carboxylic acid is linear.
• carboxylic alkenyl esters (i) are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, the vinyl esters being preferred.
• Suitable as Cr to C24-alkyl esters of acrylic acid or methacrylic acid for the embodiment (ii) of component (B) are in particular the esters of acrylic and methacrylic acid with Cr to Cu-alkanols, especially Cr to C4-alkanols, especially with methanol, Ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butyl nol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, 2-propylheptanol, decanol and isotridecanol.
• the terpolymer according to the invention can also contain two or more monomer species (i) and / or (ii) of component (B), ie two or more different carboxylic acid alkenyl esters (i) or two or more different acrylic or methacrylic acid esters (ii) or at least one Carboxylic alkenyl ester (i) and at least one acrylic or methacrylic acid ester (ii) in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group and / or in the alcohol radical.
• component (B) vinyl acetate is particularly preferred.
• the terpolymer of the invention is composed of ethylene, vinyl acetate as component (B) and cyclohexene, 1-dodecene, 1-tetradecene or 1-hexadecene as component (C).
• the terpolymer of (A) according to the invention is very particularly preferably 85 to 89.93 mol%, in particular 85 to 89.92 mol% of ethylene,
• the terpolymer according to the invention can be prepared by known and customary polymerization techniques.
• the mixture of the three monomer components (A), (B) and (C) can be polymerized in solution, in suspension or preferably in bulk. In general, this is done using a high-pressure polymerization process, as described for example in EP-A 007 590, in DE-A 31 41 507 and in the publications cited therein, and operates at pressures of 50 to 5000 bar, in particular 500 to 2500 bar, especially 1000 to 2300 bar, typically 1600 to 2000 bar, and at temperatures of 50 to 450 ° C, in particular 100 to 350 ° C, especially 150 to 250 ° C, typically 200 to 240 ° C.
• a continuously operated tubular reactor is suitable.
• the polymerization is initiated by radically decomposing initiators, this is air or oxygen, optionally in the presence of additional metered organic peroxides and / or hydroperoxides.
• suitable organic peroxides or hydroperoxides are diisopropylbenzene hydroperoxide, cumene hydroperoxide, methyl isobutyl ketone peroxide, di-tert-butyl peroxide and tert-butyl perisononate.
• suitable regulators such as aliphatic aldehydes or ketones or hydrogen can be used in the polymerization.
• the terpolymer according to the invention preferably has a number-average molecular weight (M n ) in the range from 1000 to 5000, in particular from 1500 to 2500, or alternatively a weight-average molecular weight from 2000 to 10 000, in particular from 3500 to 5000 (determined in each case by gel permeation chromatography).
• M n number-average molecular weight
• middle distillate fuels are understood to mean boiling middle distillate fuels in the range from 120 to 450 ° C.
• middle distillate fuels are used in particular as diesel fuel, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.
• Middle distillate fuels are fuels which are obtained by distillation of crude oil as the first process step and boil in the range from 120 to 450 ° C.
• low sulfur middle distillates are used, i. those containing less than 350 ppm of sulfur, in particular less than 200 ppm of sulfur, especially less than 50 ppm of sulfur. In special cases they contain less than 10 ppm sulfur, these middle distillates are also called “sulfur-free”.
• These are generally crude oil distillates, which have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds.
• middle distillates which have 90% distillation points below 370.degree. C., in particular below 360.degree. C. and in special cases below 330.degree.
• Low-sulfur and sulfur-free middle distillates can also be obtained from heavier petroleum fractions, which can no longer be distilled under atmospheric pressure.
• Hydrocarbon cracking, thermal cracking, catalytic cracking, coker processes and / or visbreaking may be mentioned as typical conversion processes for the preparation of middle distillates from heavy petroleum fractions. Depending on how the process is carried out, these middle distillates are produced with little or no sulfur or are subjected to hydrogenating refining.
• the middle distillates preferably have aromatics contents of less than 28% by weight, in particular less than 20% by weight.
• the content of normal paraffins is between 5% and 50% by weight, preferably between 10 and 35% by weight.
• middle distillate fuels are also to be understood as meaning those fuels which can be derived either indirectly from fossil sources such as crude oil or natural gas or else from biomass Gasification and subsequent hydrogenation are produced.
• a typical example of a middle distillate fuel derived indirectly from fossil sources is GTL (gas-to-liquid) diesel fuel produced by Fischer-Tropsch synthesis.
• GTL gas-to-liquid diesel fuel produced by Fischer-Tropsch synthesis.
• BTL biomass-to-liquid
• the middle distillates also include hydrocarbons obtained by hydrogenation of fats and fatty oils. They contain mostly n-paraffins.
• the qualities of fuel oils and diesel fuels are specified in greater detail in, for example, DIN 51603 and EN 590 (cf., also, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A12, page 617 et seq.).
• the terpolymer according to the invention in addition to its use in the said middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, can also be used in mixtures of such middle distillates with biofuel oils (biodiesel) to improve the cold flow behavior.
• middle distillate fuel such mixtures are also encompassed by the term "middle distillate fuel”.
• biofuel oils biodiesel
• middle distillate fuel are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel.
• Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats.
• Alkyl esters are usually lower alkyl esters, especially C 1 to C 4 alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, in particular triglycerides, by means of lower alcohols, for example ethanol or especially methanol (“ FAME ”) are available.
• Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biofuel oil or components thereof include, for example, sunflower methyl ester, palm oil methyl ester (“PME”), soybean oil methyl ester (“SME”) and in particular rapeseed oil methyl ester (“RME”).
• PME palm oil methyl ester
• SME soybean oil methyl ester
• RME rapeseed oil methyl ester
• the terpolymer according to the invention causes a significant improvement in the cold flow behavior of the middle distillate fuel or the middle distillate biofuel mixture, ie a reduction in particular the CFPP values, but also the CP values and / or the PP values, largely independent of the origin or the composition of the fuel or fuel.
• the precipitated paraffin crystals are generally held more effectively in suspension, so that it does not come to blockages of filters and pipes by such sediments.
• the invention Permitted terpolymer has in most cases a good broad effect and thus causes the precipitated paraffin crystals in the most different Kraft vers. Fuels are dispersed very well.
• the terpolymer according to the invention further causes a lowering of the lower mixing temperature of cold flow improvers additives in middle distillate fuels.
• cold flow improver additives must often be added to the refinery streams at a certain elevated minimum temperature to facilitate pumping and complete dissolution in the middle distillate fuel and its homogenization.
• This size also defined as the lower mixing temperature, should be as low as possible in order to avoid expensive heating of the cold flow improving storage tanks in the refineries.
• the terpolymer according to the invention furthermore effects an improvement in the filterability of middle distillate fuels containing cold flow improver additives.
• the presence of additives of the prior art often leads to a deterioration of the filterability of middle distillates, which is expressed in longer Fitrati- ons profession, whereby the applicability and the maximum dosing rate of the additives is limited.
• terpolymer according to the invention in addition to improving the cold flow properties of middle distillate fuels and handling cold flow improver additives or middle distillates containing cold flow improver additives, a number of other fuel or fuel shafts can be improved.
• a number of other fuel or fuel shafts can be improved.
• only the additional effect of protecting against corrosion or improving the stability to oxidation should be mentioned here.
• the present invention also provides middle distillate fuels which contain 10 to 5000 ppm by weight, in particular 25 to 1500 ppm by weight, especially 50 to 750 ppm by weight, of the terpolymer according to the invention.
• the middle distillate fuels mentioned may also contain further cold flow improvers, paraffin dispersants, conductivity improvers, corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, detergents, cetane number improvers, solvents or diluents, dyes or other additives Fragrances or mixtures thereof.
• Other cold flow improvers are described, for example, in WO 2008/1 13757 A1. Otherwise, the other additives mentioned above are familiar to the person skilled in the art and therefore need not be further explained here.
• the terpolymers or copolymers used can be characterized as follows, T-1, T-2, T-3 and T-4 being used according to the invention and C-5 being used for comparison:
• T-1 Composition: 70.1 wt% (87.88 mol%) of ethylene
• T-2 Composition: 69.9 wt% (87.81 mol%) of ethylene
• Dynamic viscosity 70 mPas prepared by high-pressure polymerization at 219 ° C and 1704 bar
• Composition 70.0 wt% (87.74 mol%) of ethylene
• Composition 70.4 wt% (87.94 mol%) of ethylene
• Composition 70% by weight of ethylene (87.74% by mol)
• Example 1 Determination of the Cold Behavior Table 1 below with the Cold Filter Plugging Points ("CFPP") determined according to the European standard EN 1 16 shows that the effect of the terpolymer according to the invention (T-1, T-2, T-3 and T-4) - depending on the test oil used - slightly better or at least as good as the comparable polymers of the prior art.
• CFPP Cold Filter Plugging Point
• Blank value (without additive) 68 s 74 s

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Emergency Medicine (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Citations (10)

• 2011
  • 2011-05-05 CN CN2011800228864A patent/CN102884095A/zh active Pending
  • 2011-05-05 RU RU2012152519/04A patent/RU2012152519A/ru not_active Application Discontinuation
  • 2011-05-05 EP EP11716967A patent/EP2566899A1/de not_active Withdrawn
  • 2011-05-05 WO PCT/EP2011/057214 patent/WO2011138400A1/de active Application Filing
  • 2011-05-05 CA CA2795843A patent/CA2795843A1/en not_active Abandoned
  • 2011-05-05 KR KR1020127031093A patent/KR20130062285A/ko not_active Application Discontinuation

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