US20080145655A1 - Electrospinning Process - Google Patents
Electrospinning Process Download PDFInfo
- Publication number
- US20080145655A1 US20080145655A1 US11/610,726 US61072606A US2008145655A1 US 20080145655 A1 US20080145655 A1 US 20080145655A1 US 61072606 A US61072606 A US 61072606A US 2008145655 A1 US2008145655 A1 US 2008145655A1
- Authority
- US
- United States
- 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.)
- Abandoned
Links
Images
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 electrospun 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.
- 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.
- polymer is also meant to include copolymer and oligiomer.
- acrylic is meant to include methacrylic and is depicted by (meth)acrylic.
- 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 11 .
- a voltage typically from 5 to 30 kilovolts (kV)
- kV kilovolts
- the polymers of the present invention can be acrylic polymers.
- the term “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 hydrolyze 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 silanes and ethylenically unsaturated acyloxy silanes, more specific examples of which include vinyl silanes 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-methacryloxypropyl tris-(2-methoxyethoxy) silane; acyloxysilanes, including, for example, acrylato acetoxysi
- 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)acryloxyalkylpolyalkoxy 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)acrylic 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 polymerizable 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 maleic 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 aryl group.
- Specific examples of such monomers include methyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and phenyl methacrylate.
- the amount of the polymerizable carboxyl-containing ethylenically unsaturated monomers is preferably sufficient to provide a carboxyl 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.
- 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 ethylenically unsaturated polymerizable monomer.
- hydroxyl functional ethylenically unsaturated polymerizable 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, hydroxypropyl(meth)acrylate and 4-hydroxybutyl (meth)acrylate.
- the amount of the hydroxy functional ethylenically unsaturated monomer is sufficient to provide a hydroxyl content of up to 6.5 such as 0.5 to 6.5, preferably 1 to 4 percent by weight based on the weight of the total monomer combination used to prepare the (meth)acrylic polymer.
- the (meth)acrylic polymer optionally contains nitrogen functionality introduced from a nitrogen-containing ethylenically unsaturated monomer.
- nitrogen functionality are amines, amides, ureas, imidazoles and pyrrolidones.
- N-containing ethylenically unsaturated monomers are: amino-functional ethylenically unsaturated polymerizable materials that include, without limitation, p-dimethylamino ethyl styrene, t-butylaminoethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, dimethylaminopropyl(meth)acrylate and dimethylaminopropyl(meth)acrylamide; amido-functional ethylenically unsaturated materials that include acrylamide, methacrylamide, n-methyl acrylamide and n-ethyl(meth)acrylamide; urea functional ethylenically unsaturated monomers that include methacrylamidoethylethylene 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 polymer.
- polymerizable ethylenically unsaturated monomers that may be used to prepare the (meth)acrylic polymer.
- monomers include poly(meth)acrylates 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 nitrites.
- poly(meth)acrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetraacrylate
- aromatic vinyl monomers such as styrene, vinyl toluene and alpha-methylstyrene
- 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 polyfunctional monomers, such as the polyacrylates, if present, are typically used in amounts up to 20 percent by weight.
- the monfunctional 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-ethylhexanoate; 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 copolymerizable 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, hexyl 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, U.S. Pat. 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.
- organic solvents of the above type which may be employed are alcohols such as lower alkanols containing 2 to 4 carbon atoms including ethanol, propanol, 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 containing 2 to 4 carbon atoms including ethanol, propanol, isopropanol, and butanol
- ether alcohols such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, prop
- the polymerization of the ethylenically unsaturated components is conducted at from 0° C. to 150° C., such as from 50° C. to 150° C., or, in some cases, from 80° 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 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 formulation is subjected to the electrospinning process as described above.
- 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 When subject to the electrospinning process, 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 acrylic-silane resin solution from Example C (8.5 grams) was blended with polyvinylpyrrolidone (0.2 grams) and water (1.5 grams). The formulation was stored at room temperature for 215 minutes. A portion of the resulting formulation was loaded into a 10 ml syringe and delivered via a syringe pump at a rate of 1.6 milliliters per hour to a spinneret (stainless steel tube 1/16-inch outer diameter and 0.010-inch internal diameter). This tube was connected to a grounding aluminum collector via a high voltage source to which about 21 kV potential was applied. The delivery tube and collector were encased in a box that allowed nitrogen purging to maintain a relative humidity of less than 25%. Ribbon shaped nanofibers having a thickness of about 100-200 nanometers and a width of 500-700 nanometers were collected on the grounded aluminum panels and were characterized by optical microscopy and scanning electron microscopy.
- 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.
- 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° C. for two hours. No measurable weight loss was observed. This indicates the nanofibers were completely crosslinked.
Abstract
A method for electrospinning polymer fibers and the resultant electrospun fibers are disclosed. In the electrospinning method, the polymer undergoes a crosslinking reaction prior to and during the electrospinning process.
Description
- 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. When voltage is applied to the needle, 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. To form a fiber, the polymeric melt or solution must have a sufficient viscosity otherwise a drop rather than a liquid jet will form. Typically, thickeners are included in the polymer solution or melt to provide the necessary viscosity. However, 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 electrospun fiber that contains silane, preferably carboxyl and hydroxyl groups and optionally a nitrogen-containing group such as amine or amide groups. The silane groups provide for crosslinking and viscosity build-up. The 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. - For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should 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.
- Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, 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.
- In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. In addition, in this application, the use of “or” means “and/or” unless specifically stated otherwise, even though “and/or” may be explicitly used in certain instances.
- The term “polymer” is also meant to include copolymer and oligiomer. The term “acrylic” is meant to include methacrylic and is depicted by (meth)acrylic.
- With reference to
FIG. 1 , the electrospinning system consists of three major components, apower supply 1, a spinneret 3 and an electrically groundedcollector 4. Direct current or alternating current may be used in the electrospinning process. Thepolymer solution 5 is contained in asyringe 7. Asyringe pump 9 forces the solution through thespinneret 3 at a controlled rate. A drop of the solution forms at the tip of theneedle 11. Upon application of a voltage, typically from 5 to 30 kilovolts (kV), the drop becomes electrically charged. Consequently, the drop experiences electrostatic repulsion between the surface charges and the forces exerted by the external electric field. These electrical forces will distort the drop and will eventually overcome the surface tension of the polymer solution resulting in the ejection of aliquid jet 13 from the tip of theneedle 11. Because of its charge, the jet is drawn downward to thegrounded collector 4. During its travel towards thecollector 4, thejet 13 undergoes a stretching action leading to the formation of a thin fiber. The charged fiber is deposited on thecollector 4 as a random oriented non-woven mat as generally shown inFIG. 2 . - The polymers of the present invention can be acrylic polymers. As used herein, the term “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. Examples of silane groups include, without limitation, groups that have the structure Si—Xn (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 hydrolyze in the presence of water including moisture in the air to form silanol groups that condense to form —Si—O—Si— groups.
- Examples of silane-containing ethylenically unsaturated polymerizable materials, suitable for use in preparing such (meth)acrylic polymers include, without limitation, ethylenically unsaturated alkoxy silanes and ethylenically unsaturated acyloxy silanes, more specific examples of which include vinyl silanes 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-methacryloxypropyl tris-(2-methoxyethoxy) silane; acyloxysilanes, including, for example, acrylato acetoxysilanes, methacrylato acetoxysilanes and ethylenically unsaturated acetoxysilanes, such as acrylatopropyl triacetoxysilane and methacrylatopropyl triacetoxysilane. In certain embodiments, it may be desirable to utilize 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)acryloxyalkylpolyalkoxy 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.
- In certain embodiments, 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)acrylic 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 polymerizable material that comprises carboxyl such as carboxylic acid groups or an anhydride thereof. Examples of 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 maleic 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 aryl group. Specific examples of such monomers include methyl methacrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and phenyl methacrylate.
- The amount of the polymerizable carboxyl-containing ethylenically unsaturated monomers is preferably sufficient to provide a carboxyl 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. Preferably, 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 ethylenically unsaturated polymerizable monomer. Examples of such materials include hydroxyalkyl esters of (meth)acrylic acids having from 2 to 4 carbon atoms in the hydroxyalkyl group. Specific examples include hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate and 4-hydroxybutyl (meth)acrylate. The amount of the hydroxy functional ethylenically unsaturated monomer is sufficient to provide a hydroxyl content of up to 6.5 such as 0.5 to 6.5, preferably 1 to 4 percent by weight based on the weight of the total monomer combination used to prepare the (meth)acrylic polymer.
- 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. Examples of suitable N-containing ethylenically unsaturated monomers are: amino-functional ethylenically unsaturated polymerizable materials that include, without limitation, p-dimethylamino ethyl styrene, t-butylaminoethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, dimethylaminopropyl(meth)acrylate and dimethylaminopropyl(meth)acrylamide; amido-functional ethylenically unsaturated materials that include acrylamide, methacrylamide, n-methyl acrylamide and n-ethyl(meth)acrylamide; urea functional ethylenically unsaturated monomers that include methacrylamidoethylethylene urea.
- If used, 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 polymer.
- Besides the polymerizable monomers mentioned above, other polymerizable ethylenically unsaturated monomers that may be used to prepare the (meth)acrylic polymer. Examples of such monomers include poly(meth)acrylates 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 nitrites. 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 polyfunctional monomers, such as the polyacrylates, if present, are typically used in amounts up to 20 percent by weight. The monfunctional 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-ethylhexanoate; tertiary butyl peracetate; tertiary butyl perbenzoate; isopropyl percarbonate; butyl isopropyl peroxy carbonate; and similar compounds. 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 copolymerizable 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, hexyl 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.
- 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, U.S. Pat. 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, propanol, 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.
- In certain embodiments, the polymerization of the ethylenically unsaturated components is conducted at from 0° C. to 150° C., such as from 50° C. to 150° C., or, in some cases, from 80° 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.
- For the electrospinning application, 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. 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. Preferably a base such as a water-soluble organic amine is added to the water-polymer solution to catalyze the crosslinking reaction. Optionally 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. When the viscosity is sufficiently high but short of gelation, the formulation is subjected to the electrospinning process as described above.
- Typically, 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.
- When subject to the electrospinning process, 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. Typically 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 following examples are presented to demonstrate the general principles of the invention. However, the invention should not be considered as limited to the specific examples presented. All parts are by weight unless otherwise indicated.
- For each of Examples A to C in Table 1 below, a reaction flask was equipped with a stirrer, thermocouple, nitrogen inlet and a condenser. Charge A was then added and stirred with heat to reflux temperature (75° C.-80° C.) under nitrogen atmosphere. To the refluxing ethanol, charge B and charge C were simultaneously added over three hours. The reaction mixture was held at reflux condition for two hours. Charge D was then added over a period of 30 minutes. The reaction mixture was held at reflux condition for two hours and subsequently cooled to 30° C.
-
TABLE 1 Example A Example B Example C Charge A (weight in grams) Ethanol SDA 40B1 360.1 752.8 1440.2 Charge B (weight in grams) Methyl Methacrylate 12.8 41.8 137.9 Acrylic acid 8.7 18.1 34.6 Silquest A-1742 101.4 211.9 405.4 2-hydroxylethylmethacrylate 14.5 0.3 0.64 n-Butyl acrylate 0.2 0.3 0.64 Acrylamide 7.2 — — Sartomer SR 3553 — 30.3 — Ethanol SDA 40B 155.7 325.5 622.6 Charge C (weight in grams) Vazo 674 6.1 12.8 24.5 Ethanol SDA 40B 76.7 160.4 306.8 Charge D (weight in grams) Vazo 67 1.5 2.1 6.1 Ethanol SDA 40B 9.1 18.9 36.2 % Solids 17.9 19.5 19.1 Acid value 51.96 45.64 45.03 (100% resin solids) Mn — 30215 5810 1Denatured ethyl alcohol, 200 proof, available from Archer Daniel Midland Co. 2gamma-methacryloxypropyltrimethoxysilane, available from GE silicones. 3Di-trimethylolpropane tetraacrylate, available from Sartomer Company Inc. 42,2′-azo bis(2-methyl butyronitrile), available from E.I. duPont de Nemours & Co., Inc. 5Mn of soluble portion; the polymer is not completely soluble in tetrahydrofuran. - The acrylic-silane resin solution from Example C (8.5 grams) was blended with polyvinylpyrrolidone (0.2 grams) and water (1.5 grams). The formulation was stored at room temperature for 215 minutes. A portion of the resulting formulation was loaded into a 10 ml syringe and delivered via a syringe pump at a rate of 1.6 milliliters per hour to a spinneret (
stainless steel tube 1/16-inch outer diameter and 0.010-inch internal diameter). This tube was connected to a grounding aluminum collector via a high voltage source to which about 21 kV potential was applied. The delivery tube and collector were encased in a box that allowed nitrogen purging to maintain a relative humidity of less than 25%. Ribbon shaped nanofibers having a thickness of about 100-200 nanometers and a width of 500-700 nanometers were collected on the grounded aluminum panels and were characterized by optical microscopy and scanning electron microscopy. - 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.
- 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° C. for two hours. No measurable weight loss was observed. This indicates the nanofibers were completely crosslinked.
- Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims.
Claims (18)
1. A method for electrospinning a fiber from an electrically conducting solution of polymer in the presence of an electric field between a spinneret and a ground source, the polymer undergoing a crosslinking reaction prior to and during electrospinning.
2. The method of claim 1 in which the polymer contains crosslinkable groups along the polymer backbone.
3. The method of claim 2 in which the crosslinkable groups are reactive with moisture.
4. The method of claim 3 in which the crosslinkable groups are silane groups.
5. The method of claim 2 in which the polymer is a (meth)acrylic polymer.
6. The method of claim 2 in which the polymer is a (meth)acrylic polymer containing silane groups.
7. The method of claim 2 in which the polymer, besides containing crosslinkable groups, also contains groups selected from carboxyl and hydroxyl.
8. The method of claim 2 in which the polymer contains silane groups, carboxyl groups, hydroxyl groups and nitrogen-containing groups.
9. The method of claim 2 in which the silane groups are present in the polymer in amounts of 0.2 to 20 percent by weight silicon based on total polymer weight.
10. The method of claim 8 in which the polymer contains from:
(a) 0.2 to 20 percent silane group measured as silicon,
(b) 1 to 45 percent carboxyl groups,
(c) 0.5 to 6.5 percent hydroxyl groups, and
(d) 0.2 to 5.0 percent nitrogen groups;
the percentages by weight being based on total polymer weight.
11. The method of claim 1 in which the solution contains a thickener.
12. The method of claim 11 in which the thickener is polyvinyl pyrrolidone.
13. The method of claim 12 in which the polyvinyl pyrrolidone is present in amounts of no greater than 20 percent by weight based on total weight of solution.
14. An electrospun fiber comprising a polymer that has been crosslinked prior to and during the electrospinning process.
15. The electrospun fiber of claim 14 having a diameter of from 5 to 5,000 nanometers.
16. The electrospun fiber of claim 14 having —Si—O—Si— crosslinks.
17. The electrospun fiber of claim 14 being a crosslinked (meth)acrylic polymer.
18. The electrospun fiber of claim 14 being a (meth)acrylic polymer with —Si—O—Si— crosslinks.
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/610,726 US20080145655A1 (en) | 2006-12-14 | 2006-12-14 | Electrospinning Process |
BRPI0719721-7A BRPI0719721A2 (en) | 2006-12-14 | 2007-11-12 | METHOD FOR ELECTROPHIATION OF A FIBER FROM AN ELECTRICALLY CONDUCTING POLYMER AND RESULTANT ELECTRIC FIBER SOLUTION |
RU2009126755/05A RU2435876C2 (en) | 2006-12-14 | 2007-11-12 | Method of electrospinning |
AT07864252T ATE481513T1 (en) | 2006-12-14 | 2007-11-12 | ELECTROSPINNING PROCESS |
KR1020097012172A KR20090080124A (en) | 2006-12-14 | 2007-11-12 | Electrospinning process |
MX2009006204A MX2009006204A (en) | 2006-12-14 | 2007-11-12 | Electrospinning process. |
CN200780046137.9A CN101558189B (en) | 2006-12-14 | 2007-11-12 | Electrospinning process |
EP07864252A EP2102394B1 (en) | 2006-12-14 | 2007-11-12 | Electrospinning process |
JP2009541448A JP2010512472A (en) | 2006-12-14 | 2007-11-12 | Electrospinning method |
AU2007333369A AU2007333369B2 (en) | 2006-12-14 | 2007-11-12 | Electrospinning process |
CA002671499A CA2671499A1 (en) | 2006-12-14 | 2007-11-12 | Electrospinning process |
PCT/US2007/084381 WO2008073662A1 (en) | 2006-12-14 | 2007-11-12 | Electrospinning process |
DE602007009320T DE602007009320D1 (en) | 2006-12-14 | 2007-11-12 | ELECTRIC SPINNING PROCESS |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/610,726 US20080145655A1 (en) | 2006-12-14 | 2006-12-14 | Electrospinning Process |
Publications (1)
Publication Number | Publication Date |
---|---|
US20080145655A1 true US20080145655A1 (en) | 2008-06-19 |
Family
ID=39111761
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/610,726 Abandoned US20080145655A1 (en) | 2006-12-14 | 2006-12-14 | 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) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100173551A1 (en) * | 2007-01-05 | 2010-07-08 | Suman Bretas Rosario Elida | Production of nanofibers and products comprised thereof |
WO2013103332A2 (en) * | 2011-10-03 | 2013-07-11 | Ndsu Research Foundation | Liquid silane-based compositions and methods of fabrication |
RU2497983C2 (en) * | 2008-06-24 | 2013-11-10 | Стелленбош Юниверсити | Method and apparatus for producing fine fibres |
US9346966B2 (en) | 2010-04-06 | 2016-05-24 | Ndsu Research Foundation | Liquid silane-based compositions and methods for producing silicon-based materials |
US10870928B2 (en) | 2017-01-17 | 2020-12-22 | Ian McClure | Multi-phase, variable frequency electrospinner system |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010025140A2 (en) | 2008-08-29 | 2010-03-04 | Dow Corning Corporation | Metallized particles formed from a dispersion |
TW201016909A (en) * | 2008-08-29 | 2010-05-01 | Dow Corning | Article formed from electrospinning a dispersion |
WO2010108124A2 (en) * | 2009-03-19 | 2010-09-23 | Nanostatics Corporation | Fluid formulations for electric-field-driven spinning of fibers |
KR20130125287A (en) | 2010-05-29 | 2013-11-18 | 애쉴리 에스. 스코트 | 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 |
RU2019125715A (en) | 2017-01-23 | 2021-02-24 | Афикс Терапьютикс А/С | METHOD FOR PRODUCING TWO-LAYER PRODUCT BASED ON ELECTRICALLY SPOTTED FIBERS |
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 |
Citations (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6265333B1 (en) * | 1998-06-02 | 2001-07-24 | Board Of Regents, University Of Nebraska-Lincoln | Delamination resistant composites prepared by small diameter fiber reinforcement at ply interfaces |
US20030168756A1 (en) * | 2002-03-08 | 2003-09-11 | Balkus Kenneth J. | Electrospinning of polymer and mesoporous composite fibers |
US6713011B2 (en) * | 2001-05-16 | 2004-03-30 | The Research Foundation At State University Of New York | Apparatus and methods for electrospinning polymeric fibers and membranes |
US6743273B2 (en) * | 2000-09-05 | 2004-06-01 | Donaldson Company, Inc. | Polymer, polymer microfiber, polymer nanofiber and applications including filter structures |
US20050235619A1 (en) * | 2002-05-28 | 2005-10-27 | Beate Heinz | Filter medium |
US20060024483A1 (en) * | 2004-07-29 | 2006-02-02 | Koch William J | Transparent composite panel |
US7105124B2 (en) * | 2001-06-19 | 2006-09-12 | Aaf-Mcquay, Inc. | Method, apparatus and product for manufacturing nanofiber media |
US20070018361A1 (en) * | 2003-09-05 | 2007-01-25 | Xiaoming Xu | Nanofibers, and apparatus and methods for fabricating nanofibers by reactive electrospinning |
US20070144124A1 (en) * | 2005-12-23 | 2007-06-28 | Boston Scientific Scimed, Inc. | Spun nanofiber, medical devices, and methods |
US20070148471A1 (en) * | 2004-09-01 | 2007-06-28 | Rukavina Thomas G | Impact resistant polyurethane and poly(ureaurethane) articles and methods of making the same |
US20070149748A1 (en) * | 2004-09-01 | 2007-06-28 | Rukavina Thomas G | Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same |
US20070149749A1 (en) * | 2004-09-01 | 2007-06-28 | Rukavina Thomas G | Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same |
US20070149747A1 (en) * | 2004-09-01 | 2007-06-28 | Rukavina Thomas G | Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same |
US20070155936A1 (en) * | 2004-09-01 | 2007-07-05 | Rukavina Thomas G | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20070155942A1 (en) * | 2004-09-01 | 2007-07-05 | Rukavina Thomas G | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20070155895A1 (en) * | 2004-09-01 | 2007-07-05 | Rukavina Thomas G | Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same |
US20070155935A1 (en) * | 2004-09-01 | 2007-07-05 | Rukavina Thomas G | Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same |
US20070167600A1 (en) * | 2004-09-01 | 2007-07-19 | Rukavina Thomas G | Polyurethanes prepared from polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same |
US20070167601A1 (en) * | 2004-09-01 | 2007-07-19 | Rukavina Thomas G | Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same |
US20070173601A1 (en) * | 2004-09-01 | 2007-07-26 | Rukavina Thomas G | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20070173627A1 (en) * | 2004-09-01 | 2007-07-26 | Rukavina Thomas G | Poly(ureaurethanes)s, articles and coatings prepared therefrom and methods of making the same |
US20070173582A1 (en) * | 2004-09-01 | 2007-07-26 | Rukavina Thomas G | Reinforced polyurethanes and poly(ureaurethane)s, methods of making the same and articles prepared therefrom |
US20070225468A1 (en) * | 2004-09-01 | 2007-09-27 | Rukavina Thomas G | Polyurethanes prepared from polyester polyols and/or polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same |
US20070248827A1 (en) * | 2004-09-01 | 2007-10-25 | Rukavina Thomas G | Multilayer laminated articles including polyurethane and/or poly(ureaurethane) layers and methods of making the same |
US20070251421A1 (en) * | 2004-09-01 | 2007-11-01 | Rukavina Thomas G | Powder coatings prepared from polyurethanes and poly(ureaurethane)s, coated articles and methods of making the same |
US20070256597A1 (en) * | 2004-09-01 | 2007-11-08 | Rukavina Thomas G | Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same |
US20080187996A1 (en) * | 2006-09-06 | 2008-08-07 | Baca Adra S | Nanofibers, nanofilms and methods of making/using thereof |
US20090155342A1 (en) * | 2005-02-15 | 2009-06-18 | Virginia Commonwealth University | Mineral technologies (MT) for acute hemostasis and for the treatment of acute wounds and chronic ulcers |
US20090280329A1 (en) * | 2004-09-01 | 2009-11-12 | Ppg Industries Ohio, Inc. | Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same |
US20090280709A1 (en) * | 2004-09-01 | 2009-11-12 | Ppg Industries Ohio, Inc. | Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same |
US20090281268A1 (en) * | 2004-09-01 | 2009-11-12 | Ppg Industries Ohio, Inc. | Methods for preparing polyurethanes |
US7632563B2 (en) * | 2006-12-14 | 2009-12-15 | Ppg Industries Ohio, Inc. | Transparent composite articles |
US20100124649A1 (en) * | 2004-09-01 | 2010-05-20 | Rukavina Thomas G | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03220305A (en) * | 1989-11-21 | 1991-09-27 | I C I Japan Kk | Production of antistatic spun yarn |
JPH09324319A (en) * | 1996-06-04 | 1997-12-16 | Nippon Shokubai Co Ltd | Transparent fiber and its production |
JP3056485B1 (en) * | 1999-05-27 | 2000-06-26 | オーケー化成株式会社 | Pattern material for synthetic resin |
DE102005008926A1 (en) * | 2005-02-24 | 2006-11-16 | Philipps-Universität Marburg | Process for the preparation of nano- and mesofibres by electrospinning of colloidal dispersions |
JP2006283240A (en) * | 2005-04-01 | 2006-10-19 | Oji Paper Co Ltd | Web-producing apparatus |
-
2006
- 2006-12-14 US US11/610,726 patent/US20080145655A1/en not_active Abandoned
-
2007
- 2007-11-12 CN CN200780046137.9A patent/CN101558189B/en not_active Expired - Fee Related
- 2007-11-12 WO PCT/US2007/084381 patent/WO2008073662A1/en active Application Filing
- 2007-11-12 DE DE602007009320T patent/DE602007009320D1/en active Active
- 2007-11-12 AU AU2007333369A patent/AU2007333369B2/en not_active Ceased
- 2007-11-12 JP JP2009541448A patent/JP2010512472A/en active Pending
- 2007-11-12 BR BRPI0719721-7A patent/BRPI0719721A2/en not_active IP Right Cessation
- 2007-11-12 RU RU2009126755/05A patent/RU2435876C2/en not_active IP Right Cessation
- 2007-11-12 EP EP07864252A patent/EP2102394B1/en not_active Not-in-force
- 2007-11-12 MX MX2009006204A patent/MX2009006204A/en active IP Right Grant
- 2007-11-12 KR KR1020097012172A patent/KR20090080124A/en not_active Application Discontinuation
- 2007-11-12 CA CA002671499A patent/CA2671499A1/en not_active Abandoned
- 2007-11-12 AT AT07864252T patent/ATE481513T1/en not_active IP Right Cessation
Patent Citations (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6265333B1 (en) * | 1998-06-02 | 2001-07-24 | Board Of Regents, University Of Nebraska-Lincoln | Delamination resistant composites prepared by small diameter fiber reinforcement at ply interfaces |
US6743273B2 (en) * | 2000-09-05 | 2004-06-01 | Donaldson Company, Inc. | Polymer, polymer microfiber, polymer nanofiber and applications including filter structures |
US6924028B2 (en) * | 2000-09-05 | 2005-08-02 | Donaldson Company, Inc. | Polymer, polymer microfiber, polymer nanofiber and applications including filter structures |
US6713011B2 (en) * | 2001-05-16 | 2004-03-30 | The Research Foundation At State University Of New York | Apparatus and methods for electrospinning polymeric fibers and membranes |
US7105124B2 (en) * | 2001-06-19 | 2006-09-12 | Aaf-Mcquay, Inc. | Method, apparatus and product for manufacturing nanofiber media |
US20030168756A1 (en) * | 2002-03-08 | 2003-09-11 | Balkus Kenneth J. | Electrospinning of polymer and mesoporous composite fibers |
US7390452B2 (en) * | 2002-03-08 | 2008-06-24 | Board Of Regents, The University Of Texas System | Electrospinning of polymer and mesoporous composite fibers |
US20050235619A1 (en) * | 2002-05-28 | 2005-10-27 | Beate Heinz | Filter medium |
US20070018361A1 (en) * | 2003-09-05 | 2007-01-25 | Xiaoming Xu | Nanofibers, and apparatus and methods for fabricating nanofibers by reactive electrospinning |
US20060024483A1 (en) * | 2004-07-29 | 2006-02-02 | Koch William J | Transparent composite panel |
US20070155895A1 (en) * | 2004-09-01 | 2007-07-05 | Rukavina Thomas G | Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same |
US20070225468A1 (en) * | 2004-09-01 | 2007-09-27 | Rukavina Thomas G | Polyurethanes prepared from polyester polyols and/or polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same |
US20070149749A1 (en) * | 2004-09-01 | 2007-06-28 | Rukavina Thomas G | Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same |
US20070149747A1 (en) * | 2004-09-01 | 2007-06-28 | Rukavina Thomas G | Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same |
US20070155936A1 (en) * | 2004-09-01 | 2007-07-05 | Rukavina Thomas G | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20070155942A1 (en) * | 2004-09-01 | 2007-07-05 | Rukavina Thomas G | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20070148471A1 (en) * | 2004-09-01 | 2007-06-28 | Rukavina Thomas G | Impact resistant polyurethane and poly(ureaurethane) articles and methods of making the same |
US20070155935A1 (en) * | 2004-09-01 | 2007-07-05 | Rukavina Thomas G | Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same |
US20070167600A1 (en) * | 2004-09-01 | 2007-07-19 | Rukavina Thomas G | Polyurethanes prepared from polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same |
US20070167601A1 (en) * | 2004-09-01 | 2007-07-19 | Rukavina Thomas G | Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same |
US20070173601A1 (en) * | 2004-09-01 | 2007-07-26 | Rukavina Thomas G | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20070173627A1 (en) * | 2004-09-01 | 2007-07-26 | Rukavina Thomas G | Poly(ureaurethanes)s, articles and coatings prepared therefrom and methods of making the same |
US20070173582A1 (en) * | 2004-09-01 | 2007-07-26 | Rukavina Thomas G | Reinforced polyurethanes and poly(ureaurethane)s, methods of making the same and articles prepared therefrom |
US20070149748A1 (en) * | 2004-09-01 | 2007-06-28 | Rukavina Thomas G | Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same |
US20070248827A1 (en) * | 2004-09-01 | 2007-10-25 | Rukavina Thomas G | Multilayer laminated articles including polyurethane and/or poly(ureaurethane) layers and methods of making the same |
US20070251421A1 (en) * | 2004-09-01 | 2007-11-01 | Rukavina Thomas G | Powder coatings prepared from polyurethanes and poly(ureaurethane)s, coated articles and methods of making the same |
US20070256597A1 (en) * | 2004-09-01 | 2007-11-08 | Rukavina Thomas G | Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same |
US20100124649A1 (en) * | 2004-09-01 | 2010-05-20 | Rukavina Thomas G | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20090281268A1 (en) * | 2004-09-01 | 2009-11-12 | Ppg Industries Ohio, Inc. | Methods for preparing polyurethanes |
US20090280709A1 (en) * | 2004-09-01 | 2009-11-12 | Ppg Industries Ohio, Inc. | Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same |
US20090280329A1 (en) * | 2004-09-01 | 2009-11-12 | Ppg Industries Ohio, Inc. | Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same |
US20090155342A1 (en) * | 2005-02-15 | 2009-06-18 | Virginia Commonwealth University | Mineral technologies (MT) for acute hemostasis and for the treatment of acute wounds and chronic ulcers |
US20070144124A1 (en) * | 2005-12-23 | 2007-06-28 | Boston Scientific Scimed, Inc. | Spun nanofiber, medical devices, and methods |
US20080187996A1 (en) * | 2006-09-06 | 2008-08-07 | Baca Adra S | Nanofibers, nanofilms and methods of making/using thereof |
US7632563B2 (en) * | 2006-12-14 | 2009-12-15 | Ppg Industries Ohio, Inc. | Transparent composite articles |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100173551A1 (en) * | 2007-01-05 | 2010-07-08 | Suman Bretas Rosario Elida | Production of nanofibers and products comprised thereof |
RU2497983C2 (en) * | 2008-06-24 | 2013-11-10 | Стелленбош Юниверсити | Method and apparatus for producing fine fibres |
US9346966B2 (en) | 2010-04-06 | 2016-05-24 | Ndsu Research Foundation | 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 |
WO2013103332A3 (en) * | 2011-10-03 | 2013-10-10 | Ndsu Research Foundation | Liquid silane-based compositions and methods of fabrication |
US10870928B2 (en) | 2017-01-17 | 2020-12-22 | Ian McClure | Multi-phase, variable frequency electrospinner system |
Also Published As
Publication number | Publication date |
---|---|
MX2009006204A (en) | 2009-06-22 |
RU2435876C2 (en) | 2011-12-10 |
CN101558189A (en) | 2009-10-14 |
WO2008073662A1 (en) | 2008-06-19 |
EP2102394A1 (en) | 2009-09-23 |
CA2671499A1 (en) | 2008-06-19 |
AU2007333369B2 (en) | 2010-11-25 |
DE602007009320D1 (en) | 2010-10-28 |
JP2010512472A (en) | 2010-04-22 |
BRPI0719721A2 (en) | 2013-12-10 |
RU2009126755A (en) | 2011-01-20 |
KR20090080124A (en) | 2009-07-23 |
ATE481513T1 (en) | 2010-10-15 |
AU2007333369A1 (en) | 2008-06-19 |
CN101558189B (en) | 2011-10-26 |
EP2102394B1 (en) | 2010-09-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2102394B1 (en) | Electrospinning process | |
US8088323B2 (en) | Process of electrospinning organic-inorganic fibers | |
US7632563B2 (en) | Transparent composite articles | |
JP5322116B2 (en) | Method for producing nanofibers and mesofibers by electrospinning a colloidal dispersion having at least one substantially water-insoluble polymer | |
CA1208847A (en) | Polymerization process for carboxyl containing polymers | |
US8298471B2 (en) | Process for producing nano- and mesofibers by electrospinning colloidal dispersions comprising at least one essentially water-insoluble polymer | |
US9879362B2 (en) | Method for producing nanofibers capable of storing and transferring nitric oxide and nanofibers capable of storing and transferring nitric oxide produced thereby | |
US20060148978A1 (en) | Polymer structures formed on fibers and/or nanofiber | |
JP4220620B2 (en) | High light-resistant polyurethane fiber and method for producing the fiber | |
CA1171996A (en) | Composition including a multiphase core/shell polymer and a polyamide matrix | |
CN111886266B (en) | Thermoplastic acrylic resin, process for producing the same, and resin composition | |
Jafarpour et al. | Electrospinning of ternary composite of PMMA-PEG-SiO2 nanoparticles: Comprehensive process optimization and electrospun properties | |
CN103201417B (en) | Porous electrospun fiber and preparation method thereof | |
CN113136628A (en) | Biological fiber, preparation method thereof and wet spinning device | |
CN104947247B (en) | A kind of preparation method of lignin-base carbon nano-fiber | |
CN110158177B (en) | Polymerization method based on electrostatic spinning technology | |
JP4056361B2 (en) | Polyglycolic acid fiber structure and method for producing the same | |
KR20060008944A (en) | Elongation-increasing agent for the production of synthetic threads from melt-spinnable fiber-forming matrix polymers | |
CN114716627A (en) | High-molecular UV absorbent for outdoor non-woven fabric and preparation method thereof | |
US20080157440A1 (en) | Process for electroblowing a multiple layered sheet | |
EP3040455B1 (en) | Fiber-forming composition and bio-compatible material using said fiber | |
JPH1060416A (en) | Antistatic material | |
JP2004091943A (en) | Method for producing acrylic fiber | |
CN105492478A (en) | Viscosifier comprising filamentous polymer particles | |
WO2023190608A1 (en) | Thermoplastic modacrylic resin, and thermoplastic modacrylic resin composition containing same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: PPG INDUSTRIES OHIO, INC., PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HELLRING, STUART D.;RAGUNATHAN, KALIAPPA G.;BALOG, KENNETH J.;REEL/FRAME:019051/0041;SIGNING DATES FROM 20061208 TO 20061214 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |