EP2102394A1 - Electrospinning process - Google Patents
Electrospinning processInfo
- Publication number
- EP2102394A1 EP2102394A1 EP07864252A EP07864252A EP2102394A1 EP 2102394 A1 EP2102394 A1 EP 2102394A1 EP 07864252 A EP07864252 A EP 07864252A EP 07864252 A EP07864252 A EP 07864252A EP 2102394 A1 EP2102394 A1 EP 2102394A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- groups
- meth
- weight
- percent
- 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.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/0053—Electro-spinning characterised by the initial state of the material the material being a low molecular weight compound or an oligomer, and the fibres being formed by self-assembly
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
- D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/38—Formation of filaments, threads, or the like during polymerisation
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/36—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated carboxylic acids or unsaturated organic esters as the major constituent
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
Definitions
- the present invention relates to an electrospinning process, the resulting electrospun fiber and polymers used in the electrospinning process.
- the process of electrospinning uses an electrical charge to form fine fibers.
- the process consists of a spinneret with a dispensing needle, a syringe pump, a power supply and a grounded collection device.
- Polymers in solution or as melts are located in the syringe and driven to the needle tip by the syringe pump where they form a droplet.
- a droplet is stretched to an electrified liquid jet.
- the jet is elongated continuously until it is deposited on the collector as a mat of fine fibers usually of nanometer-sized dimensions.
- the resultant fibers are useful in a wide variety of applications such as protective clothing, wound dressing and as supports or carriers for catalyst.
- the polymeric melt or solution must have a sufficient viscosity otherwise a drop rather than a liquid jet will form.
- thickeners are included in the polymer solution or melt to provide the necessary viscosity.
- thickeners can adversely affect the properties of the resultant fibers and for this reason, their use should be minimized.
- the present invention provides for a process of electrospinning a fiber from an electrically conductive solution of a polymer in the presence of an electric field between a spinneret and a ground source.
- the polymer undergoes a crosslinking reaction prior to and during the electrospinning process resulting in a viscosity buildup of the polymer solution enabling fiber formation and minimizing the use of thickeners.
- the invention also provides for the resultant eiectrospun fiber that contains silane, preferably carboxyl and hydroxyl groups and optionally a nitrogen-containing group such as amine or amide groups.
- silane groups provide for crosslinking and viscosity build-up.
- carboxyl, hydroxyl, amine and amide groups provide for a hydrogen bonding and viscosity build-up.
- the carboxyl group, in the form of carboxylic acid, and the nitrogen-containing groups are good electrical charge carrying groups.
- FIG. 1 depicts a basic electrospinning system
- FIG. 2 simulates a scanning electron microscopic (SCM) image of a non-woven mat.
- each numerical parameter shouid at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements. [0008] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein.
- a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
- the electrospinning system consists of three major components, a power supply 1 , a spinneret 3 and an electrically grounded collector 4. Direct current or alternating current may be used in the electrospinning process.
- the polymer solution 5 is contained in a syringe 7.
- a syringe pump 9 forces the solution through the spinneret 3 at a controlled rate.
- a drop of the solution forms at the tip of the needle 1 1.
- a voltage typically from 5 to 30 kilovolts (kV)
- kV kilovolts
- the polymers of the present invention can be acrylic polymers.
- acrylic polymer refers to those polymers that are well known to those skilled in the art which results in the polymerization of one or more ethylenically unsaturated polymerizable materials.
- (Meth)acrylic polymers suitable for use in the present invention can be made by any of a wide variety of methods as will be understood by those skilled in the art.
- the (meth)acrylic polymers can be made by addition polymerization of unsaturated polymerizable materials that contain silane groups, carboxyl groups, hydroxyl groups and optionally a nitrogen-containing group.
- silane groups include, without limitation, groups that have the structure Si-X n (wherein n is an integer having a value ranging from 1 to 3 and X is selected from chlorine, alkoxy esters, and/or acyloxy esters). Such groups hydroiyze in the presence of water including moisture in the air to form silanol groups that condense to form -Si-O-Si- groups.
- silane-containing ethylenically unsaturated polymerizable materials suitable for use in preparing such (meth)acrylic polymers include, without limitation, ethylenically unsaturated alkoxy siianes and ethylenically unsaturated acyloxy siianes, more specific examples of which include vinyf siianes such as vinyl trimethoxysilane, acrylatoalkoxysilanes, such as gamma-acryloxypropyl trimethoxysilane and gamma-acryloxypropyl triethoxysilane, and methacrylatoalkoxysilanes, such as gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl triethoxysilane and gamma-methacryloxypropy!
- vinyf siianes such as vinyl trimethoxysilane
- acrylatoalkoxysilanes such as gam
- acyloxysilanes including, for example, acryfato acetoxys ⁇ anes, methacrylato acetoxysilanes and ethylenically unsaturated acetoxysilanes, such as acrylatopropyl triacetoxysilane and methacrylatopropyi triacetoxysilane.
- monomers that, upon addition polymerization, will result in a (meth)acrylic polymer in which the Si atoms of the resulting hydrolyzable silyl groups are separated by at least two atoms from the backbone of the polymer.
- Preferred monomers are (meth)acryloxyaikylpolyalkoxy silane, particularly (meth)acryloxyalkyltrialkoxy silane in which the alkyl group contains from 2 to 3 carbon atoms and the alkoxy groups contain from 1 to 2 carbon atoms.
- the amount of the silane-containing ethylenically unsaturated polymerizable material used in the total monomer mixture is chosen so as to result in the production of a (meth)acrylic polymer comprising silane groups that contain from 0.2 to 20, preferably 5 to 10 percent by weight, silicon, based on the weight of the total monomer combination used in preparing the (meth)acryiic polymer.
- the (meth)acrylic polymer suitable for use in the present invention can be the reaction product of one or more of the aforementioned silane-containing ethylenically unsaturated polymerizable materials and preferably an ethylenically unsaturated poiymerizable material that comprises carboxyl such as carboxylic acid groups or an anhydride thereof.
- Suitable ethylenically unsaturated acids and/or anhydrides thereof include, without limitation, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, ethylenically unsaturated sulfonic acids and/or anhydrides such as sulfoethyl methacrylate, and half esters of maieic and fumaric acids, such as butyl hydrogen maleate and ethyl hydrogen fumarate in which one carboxyl group is esterified with an alcohol,
- Examples of other polymerizable ethylenically unsaturated monomers to introduce carboxyl functionality are alkyl including cycloalkyl and aryl (meth)acrylates containing from 1 to 12 carbon atoms in the alkyl group and from 6 to 12 carbon atoms in the aryf group.
- Specific examples of such monomers include methyl methacrylate, n-butyi methacryiate, n-butyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and phenyl methacrylate.
- the amount of the polymerizabie carboxyl-containing ethylenically unsaturated monomers is preferably sufficient to provide a carboxy) content of up to 55, preferably 15.0 to 45.0 percent by weight based on the weight of the total monomer combination used to prepare the (meth)acrylic polymer.
- Preferabiy at least a portion of the carboxyl groups are derived from a carboxylic acid such that the acid value of the polymer is within the range of 20 to 80, preferably 30 to 70, on a 100% resin solids basis.
- the (meth)acrylic polymer used in the invention also preferably contains hydroxyl functionality typically achieved by using a hydroxyl functional ethyfenically unsaturated poiymerizable monomer.
- hydroxyl functional ethyfenically unsaturated poiymerizable monomer examples include hydroxyalkyl esters of (meth)acrylic acids having from 2 to 4 carbon atoms in the hydroxyalkyl group. Specific examples include hydroxyethyl (meth)acrylate, hydroxypropyj (meth)acrylate and 4-hydroxybutyl (meth)acrylate.
- the amount of the hydroxy functional ethylenically unsaturated monomer is sufficient to provide a hydroxy!
- the (meth)acrylic polymer optionally contains nitrogen functionality introduced from a nitrogen-containing ethylenically unsaturated monomer. Examples of nitrogen functionality are amines, amides, ureas, imidazoles and pyrrolidones.
- N-containing ethylenically unsaturated monomers are: amino-functional ethylenically unsaturated poiymerizable materials that include, without limitation, p-dimethylamino ethyl styrene, t-butyiaminoethyl (meth)acrylate, dimethyiaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate and dimethylaminopropyl (meth)acrylamide; armido-functional ethylenically unsaturated materials that include acrylamide, methacrylamide, n-methyl acrylamide and n-ethyl (meth)acrylamide; urea functional ethylenically unsaturated monomers that include methacrylamidoethylethyJene urea.
- the amount of the nitrogen-containing ethylenically unsaturated monomer is sufficient to provide nitrogen content of up to 5 such as from 0.2 to 5.0 , preferably from 0.4 to 2.5 percent by weight based on weight of a total monomer combination used in preparing the (meth)acrylic poJymer.
- poiymerizable ethyfenically unsaturated monomers that may be used to prepare the (meth)acrylic polymer.
- examples of such monomers include poly(meth)acryiates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetraacrylate; aromatic vinyl monomers such as styrene, vinyl toluene and alpha- methylstyrene; monoolefinic and diolefinic hydrocarbons, unsaturated esters of organic and inorganic acids and esters of unsaturated acids and nitriles.
- Examples of such monomers include 1 ,3-butadiene, acrylonitrile, vinyl butyrate, vinyl acetate, allyl chloride, divinyl benzene, diallyl itaconate, triallyl cyanurate as well as mixtures thereof.
- the polyfunctionaf monomers, such as the polyacrylates, if present, are typically used in amounts up to 20 percent by weight.
- the monfunctionai monomers, if present, are used in amount up to 70 percent by weight; the percentage being based on weight of the total monomer combination used to prepare the (meth)acrylic polymer.
- the (meth)acrylic polymer is typically formed by solution polymerization of the ethylenically unsaturated polymerizable monomers in the presence of a polymerization initiator such as azo compounds, such as alpha, alpha'-azobis(isobutyronitrile), 2,2'-azobis (methylbutyronitrile) and 2,2'- azobis(2,4-dimethylvaleronitrile); peroxides, such as benzoyl peroxide, cumene hydroperoxide and t-amylperoxy-2-ethyfhexanoate; tertiary butyl peracetate; tertiary butyl perbenzoate; isopropyl percarbonate; butyl isopropyl peroxy carbonate; and similar compounds.
- a polymerization initiator such as azo compounds, such as alpha, alpha'-azobis(isobutyronitrile), 2,2'-azobis (methylbutyronitrile) and 2,2'
- the quantity of initiator employed can be varied considerably; however, in most instances, it is desirable to utilize from 0.1 to 10 percent by weight of initiator based on the total weight of copolymerizabfe monomers employed.
- a chain modifying agent or chain transfer agent may be added to the polymerization mixture.
- the mercaptans such as dodecyl mercaptan, tertiary dodecyl mercaptan, octyl mercaptan, hexyi mercaptan and the mercaptoalkyl trialkoxysilanes such as 3- mercaptopropyl trimethoxysilane may be used for this purpose as well as other chain transfer agents such as cyclopentadiene, allyl acetate, allyl carbamate, and mercaptoethanol.
- chain transfer agents such as cyclopentadiene, allyl acetate, allyl carbamate, and mercaptoethanol.
- the polymerization reaction for the mixture of monomers to prepare the acrylic polymer can be carried out in an organic solvent medium utilizing conventional solution polymerization procedures which are well known in the addition polymer art as illustrated with particularity in, for example, United States Patent Nos. 2,978,437; 3,079,434 and 3,307,963.
- Organic solvents that may be utilized in the polymerization of the monomers include virtually any of the organic solvents often employed in preparing acrylic or vinyl polymers such as, for example, alcohols, ketones, aromatic hydrocarbons or mixtures thereof, illustrative of organic solvents of the above type which may be employed are alcohols such as lower alkanols containing 2 to 4 carbon atoms including ethanol, propanoJ, isopropanol, and butanol; ether alcohols such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; ketones such as methyl ethyl ketone, methyl N-butyl ketone, and methyl isobutyl ketone; esters such as butyl acetate; and aromatic hydrocarbons such as xylene, toluene, and naphtha.
- alcohols such as lower alkanols
- the polymerization of the ethylenicaily unsaturated components is conducted at from 0 0 C to 150 0 C, such as from 5O 0 C to 150 0 C, or, in some cases, from 8O 0 C to 120°C.
- the polymer prepared as described above is usually dissolved in solvent and typically has a resin solids content of about 15 to 80, preferably 20 to 60 percent by weight based on total solution weight.
- the molecular weight of the polymer typically ranges between 3,000 to 1 ,000,000, preferably 5,000 to 100,000 as determined by gel permeation chromatography using a polystyrene standard.
- the polymer solution such as described above can be mixed with water to initiate the crosslinking reaction and to build viscosity necessary for fiber formation.
- water typically about 5 to 20, preferably 10 to 15 percent by weight water is added to the polymer solution with the percentage by weight being based on total weight of the polymer solution and the water.
- a base such as a water-soluble organic amine is added to the water-polymer solution to catalyze the crosslinking reaction.
- a thickener such as polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyamides and/or a cellulosic thickener can be added to the electrospinning formulation to better control its viscoelastic behavior. If used, the thickener is present in amounts no greater than 20 percent by weight, typically from 1 to 6 percent by weight based on weight of the polymer solution.
- the electrospinning formulation prepared as described above is then stored to permit the viscosity to build to the crosslinking reaction.
- the viscosity is at least 5 and less than 2,000, usually less than 1 ,000, such as preferably within the range of 50 to 250 centistokes for the electrospinning process.
- a Bubble Viscometer according to ASTM D- 1544 determines the viscosity.
- the time for storing the electrospinning formulation will depend on a number of factors such as temperature, crosslinking functionality and catalyst. Typically, the electrospinning formulation will be stored for as low as one minute up to two hours.
- the formulations described above typically produce fibers having a diameter of up to 5,000, such as from 5 to 5,000 nanometers, more typically within the range of 50 to 1 ,200 nanometers, such as 50 to 700 nanometers.
- the fibers also can have a ribbon configuration and in this case diameter is intended to mean the largest dimension of the fiber.
- the width of the ribbon shaped fibers is up to 5000 such as 500 to 5000 nanometers and the thickness up to 200 such as 5 to 200 nanometers.
- the polymer is not completely soluble in tetrahydrofuran.
- Example B The acrylic-silane resin solution from Example B (8.5 grams) was blended with polyvinylpyrrolidone (0.1 grams) and water (1.5 grams). The formulation was stored at room temperature for 210 minutes. A portion of the resulting solution was loaded into a 10 ml syringe and delivered via a syringe pump at a rate of 0.2 milliliters per hour to the spinneret of Example 1 . The conditions for electrospinning were as described in Example 1 . Ribbon shaped nanofibers having a thickness of 100-200 nanometers and a width of 900-1200 nanometers were collected on grounded aluminum foil and were characterized by optical microscopy and scanning electron microscopy.
- Example A The acrylic-silane resin from Example A (8.5 grams) was blended with polyvinylpyrrolidone (0,1 grams) and water (1.5 grams). The formulation was stored at room temperature for 225 minutes. A portion of the resulting solution was loaded into a 10 ml syringe and delivered via a syringe pump at a rate of 1.6 milliliters per hour to the spinneret as described in Example 1. The conditions for electrospinning were as described in Example 1 . Ribbon shaped nanofibers having a thickness of 100-200 nanometers and a width of 1200-5000 nanometers were collected on grounded aluminum foil and were characterized by optical microscopy and scanning electron microscopy. A sample of the nanofibers was dried in an oven at 110 0 C for two hours. No measurable weight loss was observed. This indicates the nanofibers were completely crosslinked.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/610,726 US20080145655A1 (en) | 2006-12-14 | 2006-12-14 | Electrospinning Process |
PCT/US2007/084381 WO2008073662A1 (en) | 2006-12-14 | 2007-11-12 | Electrospinning process |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2102394A1 true EP2102394A1 (en) | 2009-09-23 |
EP2102394B1 EP2102394B1 (en) | 2010-09-15 |
Family
ID=39111761
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07864252A Not-in-force EP2102394B1 (en) | 2006-12-14 | 2007-11-12 | Electrospinning process |
Country Status (13)
Country | Link |
---|---|
US (1) | US20080145655A1 (en) |
EP (1) | EP2102394B1 (en) |
JP (1) | JP2010512472A (en) |
KR (1) | KR20090080124A (en) |
CN (1) | CN101558189B (en) |
AT (1) | ATE481513T1 (en) |
AU (1) | AU2007333369B2 (en) |
BR (1) | BRPI0719721A2 (en) |
CA (1) | CA2671499A1 (en) |
DE (1) | DE602007009320D1 (en) |
MX (1) | MX2009006204A (en) |
RU (1) | RU2435876C2 (en) |
WO (1) | WO2008073662A1 (en) |
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FR2911151B1 (en) * | 2007-01-05 | 2010-08-20 | Rhodia Poliamida E Especialidades Ltda | PROCESS FOR OBTAINING A PRODUCT CONTAINING NANOFIBERS AND PRODUCT COMPRISING NANOFIBRES |
AU2009263898B2 (en) * | 2008-06-24 | 2014-10-30 | Stellenbosch University | Method and apparatus for the production of fine fibres |
TW201016909A (en) * | 2008-08-29 | 2010-05-01 | Dow Corning | Article formed from electrospinning a dispersion |
US8715828B2 (en) | 2008-08-29 | 2014-05-06 | Dow Corning Corporation | Emulsion of metallized particles comprising a compound having a pendant Si-H group |
WO2010108124A2 (en) * | 2009-03-19 | 2010-09-23 | Nanostatics Corporation | Fluid formulations for electric-field-driven spinning of fibers |
KR20130069611A (en) | 2010-04-06 | 2013-06-26 | 엔디에스유 리서치 파운데이션 | Liquid silane-based compositions and methods for producing silicon-based materials |
WO2013103332A2 (en) * | 2011-10-03 | 2013-07-11 | Ndsu Research Foundation | Liquid silane-based compositions and methods of fabrication |
WO2011153111A2 (en) | 2010-05-29 | 2011-12-08 | Scott Ashley S | Apparatus, methods, and fluid compositions for electrostatically-driven solvent ejection or particle formation |
WO2014137095A1 (en) * | 2013-03-08 | 2014-09-12 | (주)에프티이앤이 | Filter medium having nanofibers on both sides of base and having improved heat resistance, and manufacturing method therefor |
US10870928B2 (en) | 2017-01-17 | 2020-12-22 | Ian McClure | Multi-phase, variable frequency electrospinner system |
EP3570821B1 (en) | 2017-01-23 | 2021-07-21 | AFYX Therapeutics A/S | Method for fabrication of a two-layered product based on electrospun fibres |
CN114541038B (en) * | 2020-11-24 | 2023-12-12 | 诺一迈尔(苏州)医学科技有限公司 | Preparation method of electrostatic spinning membrane for repairing tissue defect |
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-
2006
- 2006-12-14 US US11/610,726 patent/US20080145655A1/en not_active Abandoned
-
2007
- 2007-11-12 DE DE602007009320T patent/DE602007009320D1/en active Active
- 2007-11-12 EP EP07864252A patent/EP2102394B1/en not_active Not-in-force
- 2007-11-12 CA CA002671499A patent/CA2671499A1/en not_active Abandoned
- 2007-11-12 RU RU2009126755/05A patent/RU2435876C2/en not_active IP Right Cessation
- 2007-11-12 AU AU2007333369A patent/AU2007333369B2/en not_active Ceased
- 2007-11-12 BR BRPI0719721-7A patent/BRPI0719721A2/en not_active IP Right Cessation
- 2007-11-12 KR KR1020097012172A patent/KR20090080124A/en not_active Application Discontinuation
- 2007-11-12 CN CN200780046137.9A patent/CN101558189B/en not_active Expired - Fee Related
- 2007-11-12 MX MX2009006204A patent/MX2009006204A/en active IP Right Grant
- 2007-11-12 JP JP2009541448A patent/JP2010512472A/en active Pending
- 2007-11-12 AT AT07864252T patent/ATE481513T1/en not_active IP Right Cessation
- 2007-11-12 WO PCT/US2007/084381 patent/WO2008073662A1/en active Application Filing
Non-Patent Citations (1)
Title |
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See references of WO2008073662A1 * |
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EP2102394B1 (en) | 2010-09-15 |
US20080145655A1 (en) | 2008-06-19 |
RU2009126755A (en) | 2011-01-20 |
RU2435876C2 (en) | 2011-12-10 |
BRPI0719721A2 (en) | 2013-12-10 |
DE602007009320D1 (en) | 2010-10-28 |
JP2010512472A (en) | 2010-04-22 |
CN101558189A (en) | 2009-10-14 |
MX2009006204A (en) | 2009-06-22 |
KR20090080124A (en) | 2009-07-23 |
AU2007333369A1 (en) | 2008-06-19 |
CA2671499A1 (en) | 2008-06-19 |
AU2007333369B2 (en) | 2010-11-25 |
CN101558189B (en) | 2011-10-26 |
WO2008073662A1 (en) | 2008-06-19 |
ATE481513T1 (en) | 2010-10-15 |
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