CN102187022B - Article formed from electrospinning dispersion - Google Patents

Article formed from electrospinning dispersion Download PDF

Info

Publication number
CN102187022B
CN102187022B CN2009801405233A CN200980140523A CN102187022B CN 102187022 B CN102187022 B CN 102187022B CN 2009801405233 A CN2009801405233 A CN 2009801405233A CN 200980140523 A CN200980140523 A CN 200980140523A CN 102187022 B CN102187022 B CN 102187022B
Authority
CN
China
Prior art keywords
dispersion
liquid
goods
silicon rubber
thickener
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.)
Expired - Fee Related
Application number
CN2009801405233A
Other languages
Chinese (zh)
Other versions
CN102187022A (en
Inventor
R·M·希尔
E·J·乔夫里
D·T·莱尔斯
B·J·路德维格
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones Corp
Original Assignee
Dow Corning Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Publication of CN102187022A publication Critical patent/CN102187022A/en
Application granted granted Critical
Publication of CN102187022B publication Critical patent/CN102187022B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/681—Spun-bonded nonwoven fabric

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nonwoven Fabrics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

An article of fibers includes a cured compound. The fibers are formed from electrospinning a dispersion. The dispersion includes a liquid and a condensation curable compound. A content of the liquid in the dispersion is reduced such that the condensation curable compound cures. The article is formed from a method of manufacturing which includes the step of forming the dispersion. The method also includes the step of electro spinning the dispersion to reduce the content of the liquid such that the condensation curable compound cures.

Description

The goods that formed by the electrostatic spinning dispersion
Invention field
The method of relate generally to goods of the present invention and these goods of manufacturing.More specifically, the method comprises the dispersion that forms the compound that contains liquid and condensation curable, and this dispersion of electrostatic spinning, makes goods.
The explanation of related art
The fiber that exploitation has micron and nanometer diameter is the focus of a large amount of research and development of industry, academia and government at present.Can be by organic and inorganic material, polyaniline for example, polypyrrole, Polyvinylidene, polyacrylonitrile, polyvinyl chloride, polymethyl methacrylate, the polyacetylene that polythiophene and iodine mix forms the fiber of these types.Except polyethylene and synthesis hydrophilic polymer, for example beyond the poly(ethylene oxide), also by hydrophilic biopolymer, protein for example, polysaccharide, collagen, fibrinogen, silk and hyaluronic acid form this fibrid.
Can form by the method that this area is called electrostatic spinning the fiber of many these types.Electrostatic spinning is to comprise the universal method of using electrostatic charge to form fiber mat.Typically, electrostatic spinning comprises solution loaded in the syringe, and drives this solution to the tip of syringe with syringe pump, forms drop at the tip.Electrostatic spinning also generally includes and applies voltage to pin, forms the charged jet of solution.Then extend jet, and twist thread continuously by Coulomb repulsion, until it is deposited on the ground connection collector, thereby form fiber mat.
Can be in wide in range various industry, comprising in medical science and science application, using the fiber that forms by electrostatic spinning.More specifically, used this fibrid to strengthen some composites.The nanotube that has also used these procedure of fibre productions in medical science dialysis, gas separation, infiltration and water treatment, to use.
In some applications, by all kinds of two-phases of electrostatic spinning and three-phase system emulsion for example, form fiber.The electrostatic spinning technique that uses with these systems typically produces the fiber that demonstrates the non-required mechanical features of giving fiber weakness and brittleness.Therefore, still need to form and demonstrate by dispersion the fibre of improved stress and strain performance.Still need to develop the method that forms this goods.
Summary of the invention and advantage
The invention provides the method for goods and these goods of manufacturing of fiber.Fiber comprises the compound of curing and is formed by the electrostatic spinning dispersion.This dispersion comprises liquid and curable compound.The method comprises the step that forms dispersion and this dispersion of electrostatic spinning.In one embodiment, the method comprises the step of the compound of cure curable.
The electrostatic spinning dispersion allows to form the fiber that demonstrates the compound characteristic feature of curing and demonstrate improved stress and strain performance.Form this fiber and allow more effectively and accurately to produce the various materials that in medical science, science and process industry, use.Using this dispersion also to allow to use the compound of all kinds of condensation curables to form can be based on the treatable product of required physics and chemistry.
The accompanying drawing summary
To easily understand other advantages of the present invention, because when taking into consideration with accompanying drawing, by the reference following detailed description, will understand better these advantages, wherein Fig. 1 is the scanning electron microscope image that contains the goods of fiber of the present invention, and described fiber comprises fiber-fiber contact and ball defects.
Detailed Description Of The Invention
The invention provides article comprising fibers (being fibre), as shown in Figure 1.The present invention also provides the method for making goods.The method comprises the step of electrostatic spinning, as described in more detail below.
Goods can comprise single layer fibre or multi-layer fiber.Just because of this, the thickness of goods can be at least 0.01 micron.More typically, the thickness of goods is approximately 1 micron-Yue 100 microns, and the most typically thickness is approximately 25 microns-Yue 100 microns.Goods are not limited to the fiber number of plies of any given number.Goods can be weaved or be non-woven, and can demonstrate microphase-separated.In one embodiment, fiber and goods right and wrong are woven, and goods are further defined as mat.In another embodiment, fiber and goods right and wrong are woven, and goods are further defined as net.Perhaps, goods can be films.Fiber also can be even or inhomogeneous and can have any surface roughness.Goods can waterproof, and are water-fast, fire-retardant, conduction, and automatically cleaning, draining, sagging reduces, and combination.In one embodiment, goods are coatings.Also think, goods can be fabrics, breathable fabric, filter, or its combination.In addition, can be in various industry, for example at catalyst, filter, solar cell, electronic building brick, these goods of use in skin patch, bandage, drug delivery system and in antimicrobial application.The potential application of another of goods can be as super hydrophobic perforated membrane in order to oil-moisture from or at biomedical devices, for example use in the blood vessel substitute, and in burn bandage, use, but so that NA respiratory to be provided.
Goods can be super hydrophobic fibers, and can demonstrate greater than approximately 150 the degree water contact angles.In various embodiments, goods demonstrate 150-180,155-175,160-170, and the water contact angle of 160-165 degree.Goods also can demonstrate the water contact angle that is lower than 15 degree and lag behind.In various embodiments, goods demonstrate 0-15,5-10, and the water contact angle of 8-13 and 6-12 lags behind.Goods also can demonstrate isotropism or the non-isotropic character that water contact angle and/or water contact angle lag behind.Perhaps, goods can comprise the zone that demonstrates isotropic nature and the zone that demonstrates non-isotropy character.
Fiber can have any size and dimension, and typically is cylindrical.Typically, the diameter of fiber is 0.01-100,0.05-10 more typically, and 0.1-1 micron the most typically.In various embodiments, the diameter of fiber is 1 nanometer-30 micron, the 1-500 nanometer, the 1-100 nanometer, 100-300 nanometer, 100-500 nanometer, the 50-400 nanometer, 300-600 nanometer, 400-700 nanometer, the 500-800 nanometer, the 500-1000 nanometer, 1500-3000 nanometer, 1000-5000 nanometer, 2000-5000 nanometer, or 3000-4000 nanometer.Fiber also typically has the size of 5-20 micron, and more typically has the size of 10-15 micron.Yet fiber is not limited to any specific size.Fiber usually is called " fine fibre ", and it comprises the fiber (being the fiber of at least 1 micron of diameter) with micron order diameter and the fiber with nanometer grade diameter (be diameter less than 1 micron fiber).Glass transition temperature (the T of this fiber g) also can be 25 ℃-500 ℃.
Also can be by any mode known in the art, fiber is connected to each other goes up.For example, fiber therein their places overlapping or that can physically separate fuses together, so that fiber only is laid on each other and goes up in goods.Think that fiber when connecting, can form net or pad that cell size is the 0.01-100 micron.In various embodiments, the cell size range size is 0.1-100,0.1-50,0.1-10,0.1-5,0.1-2 or 0.1-1.5 micron.Be appreciated that cell size can be even or inhomogeneous.That is to say, goods can be included in a certain zone or have the zones of different of different cell sizes between each zone.In addition, fiber can have any section feature, comprising but be not limited to the belt section feature, the elliptic cross-section feature, the circular cross-section feature, and the combination.In some embodiments, can be observed " becoming bead (beading) " of fiber, this uses for great majority is acceptable.The existence of bead, the cross section curve of fiber (changing to band shape from circle), and the diameter of fiber is the function of condition that forms the method for fiber, as described further below.
In some embodiments, fiber is fireproof also, as mentioned above.The UL-94V-0 testing vertical flammability of use on the small pieces of the non-woven mat that aluminum foil substrate deposits, the fire line of test fiber, especially fibrous non-woven mat.In this test, with rectangular flame top approximately 10 seconds that remain on of non-woven mat.Then remove flame 10 seconds, and applied again other 10 seconds.In this technical process, observe the red-hot dropping of sample propagating flame, residual flame and residual vehement existence, and along the ignition distance of the height of sample.For the non-woven mat that contains fiber of the present invention, below those fibers of burning, typically observe complete fiber.The non-woven mat imperfect combustion is the evidence from fire extinguishing, a kind of typical behavior of fire proofing and be regarded as good fire resistance.In many cases, non-woven mat can even be realized UL 94 V-0 grades.In the situation that do not wish to be bound by any particular theory, think that fire resistance typically is attributable to the interior organic group of fiber low with the ratio of silicon atom.The ratio of organic group and silicon atom is low to be attributable to not have organic polymer and organic copolymer in fiber.Yet, think that also fire resistance may be due to the ratio of organic group and silicon atom in the fiber factor low.
Can form fiber by dispersion.As known in the art, dispersion comprises with another phase unmixing of material and a phase of a kind of material that disperses, i.e. decentralized photo in continuous phase within it.In the present invention, dispersion comprises liquid and curable compound, as described in more detail below.In one embodiment, liquid is nonpolar liquid.In another embodiment, liquid is polar liquid, and is for example pure, ionic liquid, or water.Typically, liquid is water.Water can be running water, well water, and purified water, deionized water, and combination, and can be present in the dispersion by various consumptions, this depends on the type of dispersion.Liquid can be decentralized photo or continuous phase.In one embodiment, dispersion comprises the solid particle of decentralized photo form and the liquid of continuous phase form.In another embodiment, dispersion comprise nonpolar liquid as decentralized photo and polar liquid as continuous phase.In various embodiments, the amount of liquid can be 20-80, and 30-70,40-60 or consumption are about 50 weight portions, with respect to 100 weight portion dispersion meters, as long as the total amount of dispersion is no more than 100 weight portions.
Dispersion can be further defined as " colloid " or " aqueous colloidal dispersion ", and these two terms are used interchangeably.Typically, colloid is included in the size of dispersion in the continuous phase less than the particle of 100 nanometers.Colloid can be classified according to variety of way.For purpose of the present invention, colloid also can be categorized as gel (liquid dispersion phase and solid continuous phase), emulsion (liquid dispersion phase and liquid continuous phase), and/or foam (gas dispersion phase and liquid continuous phase).Colloid can turning (namely to exist greater than a kind of state) or is not turning.In addition, colloid can be elasticity or viscoelastic.
In one embodiment, dispersion is further defined as emulsion, at first introduces as above.According to disperseing and the chemical property of continuous phase, emulsion typically is categorized as a kind of in four classes.The first kind is oil-in-water (O/W) emulsion.The O/W emulsion typically is included in the nonpolar decentralized photo (for example, oil) in the water continuous phase (for example water) of containing that forms drop (described drop is typically called emulsion particle).For purpose of the present invention, term " oil " comprises nonpolar molecule and can comprise curable compound.The second emulsion is Water-In-Oil (W/O) emulsion.The W/O emulsion typically is included in the polarity decentralized photo in the nonpolar continuous phase, thereby forms the upset emulsion.The 3rd class is W/O/W (W/O/W) emulsion.The emulsion of these types is included in the polarity decentralized photo in the nonpolar continuous phase, and described nonpolar continuous phase is dispersed in again in the polarity continuous phase itself.For example, the W/O/W emulsion can comprise the water droplet that is captured in than in the larger oil droplet, describedly is dispersed in again in the continuous water than larger oil droplet itself.The 4th class is water Bao Shui (W/W) emulsion.The emulsion of these types is included in the aqueous solvent chemoattractant molecule in the continuous aqueous solution, and wherein the aqueous solvent chemoattractant molecule comprises water-soluble different molecule with the continuous aqueous solution.In the situation that do not plan to be bound by any particular theory, thinking that the emulsion of aforementioned type depends on disperses and the two hydrogen bonding of continuous phase pi accumulation, and/or salt bridging.In the present invention, dispersion can be further defined as any in this four classes emulsion.
This area is also known, and to a certain extent, dispersion is unstable.Typically, there are three class dispersion unstability, flocculate comprising (i), wherein the particle of decentralized photo forms agglomerate in continuous phase, (ii) creaming, wherein the particle of decentralized photo towards the surface of continuous phase or the bottom concentrate and (iii) breakdown of emulsion and coalescent, the wherein particles coalesce of decentralized photo and in continuous phase, form liquid level.Dispersion of the present invention can demonstrate the unstability of one or more these types.
Dispersion of the present invention can comprise the particle of change in size.In one embodiment, dispersion comprises the particle of 1 nanometer-10 micron, 1 nanometer-1 micron more typically, and 1-100 nanometer the most typically.In another embodiment, dispersion can be categorized as nanoemulsions.Dispersion can comprise the particle little or larger than above-described size, and this depends on those skilled in the art's demand.
As mentioned above, dispersion also comprises curable compound.Curable compound can be curable any organic or inorganic compound known in the art.The non-limiting example of suitable curable compound comprises the compound by free radical mechanism, hydrosilylation, condensation, addition reaction, ultraviolet light, microwave and heat cure.The example of this curable compound includes but not limited to peroxide, acid amides, and acrylate, ester, ether, acid imide, oxirane, sulfone, urea, carbamate has the compound of ethylenic unsaturated bond and combination thereof.In one embodiment, curable compound is selected from silane, siloxanes, silazane, silicone, silica, silene (silenes), silsesquioxane, and combination.In this embodiment, curable compound typically solidifies by free radical, condensation and/or hydrosilylation mechanism.In various embodiments, the amount of curable compound can be 20-80,30-70, and 40-60, or consumption is about 50 weight portions, with respect to 100 weight portion dispersion meters, as long as the total amount of dispersion is no more than 100 weight portions.
Perhaps, curable compound can be further defined as the compound of condensation curable.As known in the art, the compound of condensation curable solidifies by condensation reaction.Condensation reaction be wherein two molecules in conjunction with forming new single molecule and losing for example chemical reaction of water of little molecule.When losing water, condensation reaction also can be described as dehydration.Just to the purpose of describing, below listed general condensation (dehydration) reacting flow chart:
Figure BDA0000055051390000061
Wherein R is the organic or inorganic part.Condensation reaction is not limited to lose water, also can comprise losing organic or inorganic compound or hydrogen molecule.In the situation that one or more silicon atoms in the reacting flow chart are substituted by carbon (C) atom therein, also condensation reaction can occur.
The compound of condensation curable can comprise monomer, dimer, oligomer, polymer, prepolymer, copolymer, block polymer, star polymer, graft polymers, random copolymer, macromonomer, telechelic oligoner, nano particle, and combination.Term as used herein " oligomer " comprises the reactive appraisable chemical group that partly links together by the energy condensation, comprising dimer, and tripolymer, the tetramer and/or pentamer.The example that can be included in the preferred organic reaction part that can condensation in the compound of condensation curable includes but not limited to hydrolyzable part, hydroxylic moiety, hydride, isocyanate moiety, amine moiety, amide moieties, acid moieties, alcohol moiety, amine moiety, acrylate part, carbonate moiety, epoxide moiety, ester moiety, and combination.The compound of condensation curable also can comprise inorganic part, comprising but be not limited to silicone, siloxanes, silane, transistion metal compound, and the combination.Except condensation reaction, goods of the present invention also can be by various addition reactions, free radical addition for example, and the Miachael addition, hydrosilylation reactions, and/or Diels Alder reaction forms.Also can adopt ring-opening polymerization.
In one embodiment, the compound of condensation curable can be any compound in 11/20/07 U.S. Provisional Application of submitting to number 61/003726, at this specially by with reference to introducing.In another embodiment, the compound of condensation curable can comprise organic and inorganic polymer, polyester for example, polyamide, polyimides, polyureas, polyethers, polyamine, polyurethane, aramid, Merlon, carbonic acid ester, and combination.Perhaps, the curable formation of the compound of condensation curable is selected from the compound of polyester, nylon, polyurethane, aromatic polyamides, carbonic acid ester and combination thereof.
(condensation) curable compound can be substantially free of silicon (being the compound of silicon atom and/or silicon atoms).Be appreciated that term " be substantially free of " refer to silicon concentration less than 5000, more typically less than 900, with the most typically less than the compound of 100 parts of silicon atoms, with respect to the compound meter of 1,000,000 parts of condensation curables.Think that also (condensation) curable compound can be fully not siliceous.
Perhaps, (condensation) curable compound can comprise the polymerizate of at least a silicon monomer and organic monomer.Think that organic monomer and/or silicon monomer can be present in (condensation) curable compound with any volume fraction.In various embodiments, organic monomer and/or silicon monomer be with 0.05-0.9,0.1-0.6, and 0.3-0.5,0.4-0.9,0.1-0.9, the volume fraction of 0.3-0.6 or 0.05-0.9 exists.
Organic monomer can comprise above-described any organic moiety.Term " silicon monomer " comprises any monomer that contains at least one silicon (Si) atom, silane for example, siloxanes, silazane, silicone, silica, silene, silsesquioxane, and combination.Be appreciated that silicon monomer can comprise the group of polymerization and keep silicon monomer, as long as it keeps the ability of polymerization.In one embodiment, silicon monomer is selected from silane, silsesquioxane, siloxanes, and combination.
In can supplying the embodiment that substitutes, (condensation) curable compound is selected from organosilanes, organopolysiloxane, and combination.In this embodiment, organopolysiloxane can be selected from silanol stopped siloxanes, the siloxanes of alkoxysilyl end-blocking, and combination.
(condensation) curable compound can be straight chain or non-straight chain, and can comprise that hydroxyl and/or organic group siloxy are (SiOR), and can comprise hydroxy-end capped dimethyl silicone polymer.(condensation) curable compound can comprise following formula:
Figure BDA0000055051390000081
Each R wherein 1And R 2Comprise independently hydrogen, hydroxyl, alkyl, the alkyl that halogen replaces, alkenyl, aryl, the aryl that halogen replaces, alkaryl, alkoxyl, acyloxy, ketoxime base (ketoximate), amino, amide groups, sour amide groups, aminooxy group, sulfydryl, and in the alkenyl oxy one, and n can be any integer.
Perhaps, (condensation) curable compound can comprise alkylene and/or fluoro alkylene.Alkylene comprises the divalent moiety of carbon containing and hydrogen.The fluoro alkylene comprises the alkylene part that at least one hydrogen is replaced by at least one fluorine atom.Typical fluoro alkylene comprises the partially or completely alkylidene of fluorine replacement.(condensation) curable compound also can comprise hydrocarbon fraction, comprising the acrylate part, and methacrylic acid ester moiety, vinyl segment, acetenyl part, and combination.
If (condensation) curable compound comprises hydroxyl, then (condensation) curable organopolysiloxane can comprise having at least one terminal silanol or be bonded to hydrogen atom on the silicon or the type siloxane of hydrolyzable groups, and described hydrolyzable groups forms silanol group when being exposed to moisture lower time.The silanol group that end or side are hung or its precursor allow condensation.
Perhaps, (condensation) curable compound can be further defined as elastomer or curable elastomer.Just as known in the art, " elastomer " is to demonstrate elasticity, can be out of shape and return to the roughly compound of original shape under stress.In the present invention, term " elastomer " is not limited to polymer or monomer, and can comprise a kind of or these two.In addition, elastomer can comprise any aforementioned (condensation) curable compound.In one embodiment, curable elastomer is available commercially from Dow CorningCorporation of Midland, MI with trade name Dow Corning 84 Additive.
In one embodiment, the number-average molecular weight (M of curable compound n) greater than 5000g/mol, and more typically greater than 10,000g/mol.Yet curable compound is not limited to this number-average molecular weight.In another embodiment, the number-average molecular weight of curable compound is greater than approximately 100,000g/mol.In various other embodiments, the number-average molecular weight of curable compound is 100,000-5,000,000g/mol, 100,000-1,000,000g/mol, 100,000-500,000g/mol, 200,000-300,000g/mol is higher than approximately 250,000g/mol, or approximately 150,000g/mol.In an embodiment again, the number-average molecular weight of curable compound is greater than 50,000g/mol, and more typically greater than 100,000g/mol.In can be for the embodiment that substitutes, the number-average molecular weight of curable compound can be at least about 300g/mol, approximately 1, and 000-approximately 2, and 000g/mol, or approximately 2,000g/mol-approximately 2,000,000g/mol.In other embodiments, the number-average molecular weight of curable compound is greater than 350g/mol, and approximately 5,000-approximately 4,000, and 000g/mol, or approximately 500,000-approximately 2,000,000g/mol.
Except curable compound, dispersion also can comprise one or more surfactants.In various embodiments, dispersion comprises (first) surfactant and second surface activating agent or kinds of surface activating agent.Before forming dispersion, surfactant can with liquid, with curable compound, or with liquid and curable the two combination of compound.Typically, before forming dispersion, surfactant is combined with liquid.Surfactant is also referred to as surface-active agents, surface-activity solute, emulsifying agent, emulgent, and interfacial agent.With respect to the present invention, term " surface-active agents ", " surface-activity solute ", " surfactant ", " emulsifying agent ", " emulgent " and " interfacial agent " is used interchangeably.Surfactant reduces the surface tension of liquid by in liquid-gas interface place absorption.Surfactant also by in the absorption of liquid-liquid interface place, reduces the interfacial tension between polarity and the nonpolar molecule.In the situation that do not plan to be bound by any particular theory, think that surfactant works at the interface at these, and depend on various factors, comprising the excluded volume repulsive force, electrostatic interaction power, Van der Waals force, entropic force and steric hindrance power.In the present invention, can based on one or more these factors, select or the control surface activating agent.
Surfactant, the first and second surfactants, or the first/the second/can be independently selected from non-ionic surface active agent with the kinds of surface activating agent, cationic surfactant, anion surfactant, amphoteric surfactant, and combination.Suitable ionic surfactant pack is drawn together but is not limited to the alkylphenol alkoxide, and pure b-oxide is comprising aliphatic alcohol ethyl oxide, glyceride, Isosorbide Dinitrate, sucrose and glucose ester, comprising alkyl poly glucoside and hydroxyalkyl glycan glycosides, alkanolamide, N-alkyl glucose amide, the alkylene oxide block copolymer, for example oxirane, expoxy propane and/or epoxy butane block copolymer, polyhydroxy and many alkoxyls derivative of fatty acid, amine oxide, siloxy group polyethers, and combination.
Suitable cationic surfactant includes but not limited to the interfacial activity compound, and comprising ammonium, for example alkyl dimethyl ammonium halide, and chemical formula is RR`R``R```N +X -Compound, wherein R, R`, R`` and R``` are independently selected from alkyl, aryl, alkyl alkoxy, alkoxy aryl, hydroxyalkyl (alkoxyl) and hydroxyaryl (alkoxyl), and wherein X is anion.Suitable anion surfactant includes but not limited to aliphatic alcohol sulfate.The further non-limiting example of suitable anion surfactant comprises alkyl sulfonate, linear alkylbenzene sulfonate (LAS) and straight chained alkyl toluene fulfonate.Again further; anion surfactant can comprise alkene sulfonate and disulfonate, the mixture of olefine and hydroxyl alkane-sulfonate or disulfonate, alkyl ester sulfonate; the sulfonation polycarboxylic acids; alkyl glycerol sulfonate, fatty acid glyceride sulfonate, alkyl phenol polyglycol ether sulfate; alkene sulfonate; alkane sulfonate, alkylphosphonic, the different thiosulfate of acyl group; acyl taurine salt; acyl methyl taurine salt, alkyl succinic acid, sulfosuccinate; alkenyl succinic and corresponding ester and acid amides; alkyl sulfosuccinic acid and corresponding acid amides, the monoesters of sulfosuccinic acid and diester, acyl sarcosinates; the sulphation alkyl poly glucoside; alkyl polyglycols carboxylic acid ester, hydroxyalkyl sarcosinate, and combination.Suitable amphoteric surfactant includes but not limited to contain the second month in a season of anionic group and/or the aliphatic derivatives of tertiary amine, betaine, and combination.
In addition, surfactant and/or the first and second surfactants can comprise aliphatic series and/or aromatics alkoxylated alcohols independently, LAS (linear alkylbenzene sulfonate (LAS)), alkane sulfonate, FAS (aliphatic alcohol sulfate), FAES (fatty alcohol ether sulphate), aklylene glycol, the trimethylolpropane b-oxide, the glycerine b-oxide, pentaerythrite b-oxide, the alkoxide of bisphenol-A, with the alkoxide of 4-methyl cyclohexanol and 5-methyl-2-propyl enanthol, and combination.Typically, the amount of surfactant is with respect to 100 weight portion dispersion meter 0.1-100 weight portions, 0.01-5 weight portion more typically, even 0.5-5 weight portion more typically, and 1.5-5 weight portion the most typically.
Dispersion also can comprise thickener.As known in the art, thickener increases the viscosity of dispersion under low shearing speed, keeps the mobile performance of dispersion simultaneously under higher shear rate.The suitable thickener that uses in the present invention includes but not limited to polyalkylene oxide, poly(ethylene oxide) for example, poly(propylene oxide), polybutylene oxide, and combination.In one embodiment, thickener is selected from alginic acid and derivative thereof, poly(ethylene oxide), polyvinyl alcohol, methylcellulose, hydroxypropyl methylcellulose, alkyl and hydroxy alkyl cellulose, carboxymethyl cellulose, hydroxyethylcellulose, guar gum, Arabic gum, ghatti gum, polyvinylpyrrolidone, starch, modified starch, tamarind gum, xanthans, polyacrylamide, polyacrylic acid, and combination.Thickener also can comprise nano particle, for example titanium dioxide and/or nanoclay, for example bentonite.Thickener also can be conduct electricity, partly lead, insulation, magnetic or luminous.Perhaps, thickener can comprise conducting polymer, polypyrrole for example, polyaniline, and/or polyacetylene.Thickener also can comprise biological components, for example protein or DNA.
Before forming dispersion, can be in conjunction with thickener and liquid, with curable compound, or with liquid and curable compound these two.Typically, before forming dispersion, in conjunction with thickener and liquid.The amount of thickener typically is 0.001-25, and 0.05-5 more typically, and 0.1-5 weight portion the most typically are with respect to 100 weight portion dispersion meters.
This area is also known, and dispersion typically has two kinds of dissimilar viscosity, the viscosity of total viscosity and decentralized photo.The total viscosity of dispersion of the present invention under 25 ℃ temperature typically is at least 20 centistokes.In various embodiments, use is furnished with hot pond and the Brookfield rotating disc viscosimeter of the SC4-31 spindle that operates under the rotary speed of 25 ℃ constant temperature and 5rpm, under 25 ℃ temperature, the viscosity of dispersion is at least 20 centistokes, about about 100 centistokes of 30-more typically, about about 75 centistokes of 40-.Do not limit the viscosity of decentralized photo, and think that it does not affect total viscosity.In one embodiment, decentralized photo is solid and has unlimited viscosity.
The zero shear rate viscosity of this dispersion also can be 0.1-10,0.5-10,1-10,5-8, or about 6PaS.In addition, the conductivity of dispersion can be 0.01-25mS/m.In various embodiments, the conductivity scope of dispersion is 0.1-10mS/m, 0.1-5mS/m, 0.1-1mS/m, 0.1-0.5mS/m, or about 0.3mS/m.The surface tension of this dispersion also can be 10-100mN/m.In different embodiments, the surface tension scope is 20-80mN/m, or 20-50mN/m.In one embodiment, the surface tension of dispersion is about 30mN/m.The dielectric constant of this dispersion also can be 1-100.In various embodiments, dielectric constant is 5-50,10-70, or 1-20.In one embodiment, the dielectric constant of dispersion is approximately 10.
Dispersion also can comprise additive.Additive can include but not limited to that conductivity improves additive, salt, dyestuff, colouring agent, labelled reagent, and combination.Conductivity improves additive and can help good fiber to form, and can be further can so that fibre diameter minimize, particularly when by electrostatic spinning formation fiber.In one embodiment, conductivity raising additive comprises ionic compound.In another embodiment, conductivity improves additive and usually is selected from amine, organic salt and inorganic salts, and composition thereof.Typical conductivity improves additive and comprises amine, quaternary ammonium salt, quaternary alkylphosphonium salt, uncle's sulfonium salt, and the mixture of inorganic salts and organic ligand.More typical conductivity improves additive and comprises quaternary ammonium group organic salt, comprising but be not limited to tetrabutylammonium chloride, TBAB, tetrabutylammonium iodide, the phenyl trimethyl ammonium chloride, phenyl triethyl ammonium chloride, phenyl trimethylammonium bromide, phenyl trimethyl ammonium iodide, Dodecyl trimethyl ammonium chloride, DTAB, dodecyl trimethyl ammonium iodide, tetradecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, myristyl trimethyl ammonium iodide, hexadecyltrimethylammonium chloride, softex kw, and cetyl trimethyl ammonium iodide.Additive can be present in the continuous phase or decentralized photo of dispersion with any consumption that those skilled in the art select, as long as the consumption of additive allows curable compound to occur to solidify.In various embodiments, the consumption of additive typically is approximately 0.0001-approximately 25%, and about 0.001-approximately 10% more typically, and about 0.01-approximately 1% more typically are based on the gross weight of fiber.In one embodiment, additive comprises the methyl aminomethyl propanol.
The method of making goods now is discussed, and the method comprises the step that forms as mentioned above dispersion.Can by adding together curable compound and liquid and mixing, form dispersion.In one embodiment, the method comprises the compound that adds together condensation curable and liquid and the step of mixing.Blend step can comprise the use ribbon blender, plough formula mixer, and the fluidisation blade-paddle mixer, ∑ (sigma) blade mixer, the rotary drum mixing machine, the eddy current mixer, the raw material mixer, vertical mixer, horizontal mixer, the rotor-stator mixer, ultrasonic device, And the combination mechanical mixture of carrying out.
The invention is not restricted to any specific interpolation order.In one embodiment, by forming mixture in conjunction with thickener and water, and add this mixture in curable compound, form dispersion.Perhaps, can by any method known in the art, form dispersion.
The method also comprises the step of electrostatic spinning dispersion.In one embodiment, this step reduces the content of liquid (for example water), so that the compound of condensation curable solidifies.In the situation that do not plan to be bound by any particular theory, think that electrostatic spinning causes for example at least part of evaporation of water of liquid, the compound of condensation curable solidifies as a result.The loss of solvent can allow curable compound blend, i.e. close contact, thus allow to solidify.In the situation that do not plan to be subject to any particular theory, think the electric field force adjustable functional group that in electrostatic spinning, uses, so that they contact more easily.Can carry out the electrostatic spinning step by any method known in the art.Typical electrospinning process comprises that the use electric charge forms fiber.Typically, will form the employed dispersion of fiber and load in the syringe, adopt syringe pump, drive dispersion to syringe tip, and form drop at the place, tip of syringe.Pump can be controlled and form the flow that the employed dispersion of fiber arrives spinneret.The employed dispersion of formation fiber can have impact to the formation of fiber by the flow of syringe tip.The flow of dispersion by the tip of syringe can be the about about 0.5ml/min ml/min of 0.005ml/min-, about 0.005ml/min-approximately 0.1 typically, the about about 0.1ml/min of 0.01ml/min-more typically, and the about about 0.1ml/min of 0.02ml/min-.In a specific embodiment, the flow of dispersion by syringe tip can be about 0.05ml/min.
Then, typically drop is exposed under the high-tension electric field.In the situation that there is not high voltage electric field, drop leaves the tip of syringe with 1/4 spherical form, and this is the result of drop inner surface tension force.Applying electric field causes sphere to be deformed into taper.The explanation that this distortion of droplet profile is accepted usually is that the surface tension in drop is neutralized by electric field force.The narrow diameter jet of dispersion flows out from cone is most advanced and sophisticated.Under some process conditions, the jet of dispersion experience " (whipping) twists thread " unstability phenomenon.This unstability that twists thread causes repeatedly bifurcated of jet, thereby obtains network of fibers.Finally collect fiber in collector plate.Think in the electrostatic spinning process process, liquid is water rapid evaporation from dispersion for example, stays the solid portion in the dispersion, forms fiber and solidifies this curable compound.Typically by solid conductive material, such as but not limited to aluminium, steel, nickel alloy, silicon chip,
Figure BDA0000055051390000141
Fabric, and cellulose (for example paper) forms collector plate.In the process of electrostatic spinning dispersion, collector plate plays electric current by the effect in the ground connection source of fiber.Along with time lapse, the fiber number of collecting in collector plate increases, and forms non-woven fibre mat in collector plate.Perhaps, replace using collecting board, can collect fiber at liquid surface, described liquid is not the part of dispersion, thereby realizes the self-supporting non-woven mat.An example collecting the spendable liquid of fiber is water.
In various embodiments, the electrostatic spinning step comprises from having approximately supply electricity the DC electric organ of 100 kilovolts of (KV) generating capacities of about 10-.Especially, syringe is electrically connected on the electric organ.Drop is exposed to step under the high voltage electric field typically to be comprised and applies voltage and current to syringe.The voltage that applies can be the about about 100KV of 5KV-, the about about 40KV of 10KV-typically, the about about 35KV of 15KV-more typically, the about about 30KV of 20KV-.In a concrete example, the voltage that applies can be about 30KV.The electric current that applies can be about 0.01nA-approximately 100,000nA, the about about 1000nA of 10nA-typically, the about about 500nA of 50nA-more typically, the about about 100nA of 75nA-.In a specific embodiment, electric current is about 85nA.Typically, when electrostatic spinning, dispersion 60 ℃ of environment temperature with interior temperature under.More typically, when electrostatic spinning, dispersion 60 ℃ of processing temperature with interior temperature under.
Think the compound of at least part of curing condensation curable of step of electrostatic spinning.In one embodiment, the step of electrostatic spinning is solidified the compound of condensation curable fully.In other embodiments, the step of electrostatic spinning do not solidify fully or even partly solidified curable compound, the result needs extra curing schedule.The method can comprise drying steps, with the compound of cure curable more fully.When curable compound is further defined as the compound of condensation curable, think that drying steps removes liquid (for example water) and drive condensation reaction to the right, namely towards finishing.
The method also can comprise the step of the compound of aforesaid cure curable.Can be independent of electrostatic spinning step or with it combination, implement curing schedule.This step can comprise any curing schedule known in the art, comprising but be not limited to relate to radically curing, hydrosilylation cure, condensation cured, the UV photocuring, microwave curing, heat cure, and the combination those.
The method also can comprise the step that makes fiber annealing.Can finish this step by any method known in the art.In one embodiment, can use annealing steps to improve the hydrophobicity of fiber.In another embodiment, annealing steps can improve the rule degree of fiber microfacies.Annealing steps can comprise heating product.Typically, in order to carry out annealing steps, heating product is to than about 20 ℃ the high temperature of environment temperature.More typically, heating product is to approximately 40 ℃-400 ℃ temperature Yue, more typically approximately 40 ℃-Yue 200 ℃.Heating product can cause the fusion of the increase of fiber contact in goods, produces chemistry or physical bond (being commonly referred to " crosslinked ") in fiber, makes one or more component volatilizations in the fiber, and/or the variation of fiber surface pattern.
Embodiment
The method according to this invention forms a series of fiber and non-woven mat (being goods of the present invention).Non-woven mat comprises the fiber that is formed as the dispersion of the compound of condensation curable by the silicone-containing elastomer.
More specifically, the aqueous solution of 2g 2.5% poly(ethylene oxide) (2,000,000 number-average molecular weight) being joined 10g contains in the dispersion of 63wt%Dow Corning 84 Additive in water.Dow Corning Additive 84 comprises silica and contains the mixture of the crosslinked silicon rubber that can experience condensation cured functional group.Stir poly(ethylene oxide) and dispersion, form translucent white dispersion.Then in the preparation of electrostatic spinning, send dispersion in the stainless steel tube of 0.040 inch of internal diameter by syringe/syringe pump.Between the aluminium foil of stainless steel tube and a slice ground connection, apply electric field.When applying electric field, the drop of locating at the tip of stainless steel tube is become thin white fiber by electrostatic spinning, and described white fiber is deposited on the aluminium foil of ground connection.In the sheet separation of 30cm, stretch out at the tip of 3cm, under the flow that applies voltage and 1ml/h of 22kV, carries out the electrostatic spinning step, carried out electrostatic spinning 1 hour.The gained fibre diameter is the 1-5 micron and tends to have fiber-fiber contact.As shown in Figure 1, in fiber, there is ball defects.
After electrostatic spinning 1 hour, fiber forms approximately 200 microns opaque white color film of thickness.After 24 hours, from aluminium foil, peel off film and use the AllianceRT/5 Tensile Tester test that is available commercially from RTS, with the tensile property (stress/strain) that is determined at the breakaway poing place.More specifically, under the draw rate of 100mm/min, be the sample of " dog bone " shape of 0.1 inch film at the maximum load pond of 10N build-in test width.Also generate load-deformation curve.The peak stress measured value of fiber is about 19psi, and the strain measurement value is approximately 120%.In addition, load-deformation curve is roughly straight line, thereby shows that at breakaway poing place fiber be flexible.
The fiber of formation shows in the aforementioned embodiment, and the electrostatic spinning dispersion allows to form opposite with continuous phase, demonstrates the fiber of decentralized photo (being the compound of condensation curable) feature.The fiber that forms in this embodiment demonstrates elastic stress and strain property, and elastic stress-strain curve.Form this fibrid and allow more effectively and accurately to produce the various materials that in medical science, science and process industry, use.Use dispersion also to allow to use all kinds of curable compounds, thereby form new product.Example is that the dispersion of water allows to carry out electrostatic spinning process by evaporating harmless volatile liquid such as continuous phase wherein.In continuous phase, use active material for example bacterium can allow to be created on biological functionalized fiber curable in the one-step technology.
Describe the present invention in illustrative mode, and be appreciated that it is wording character rather than the restriction of explanation that employed term is planned.Obviously, in view of above-mentioned instruction, many modifications of the present invention and variation are possible, and can put into practice the present invention beyond describing particularly.

Claims (39)

1. method of making fibre, described goods comprise the fiber that is formed by dispersion, described method comprises the steps:
A. form and contain following compositions (i) and dispersion (ii):
(i) liquid, and
(ii) silicon rubber of condensation curable, and
B. this dispersion of electrostatic spinning reduces the content of liquid, so that the silicon rubber of condensation curable is by condensation cured.
2. the process of claim 1 wherein that dispersion further comprises surfactant.
3. the method for claim 2 wherein before forming dispersion, is combined surfactant with liquid.
4. the method for claim 2, wherein based on the weight of the silicon rubber of condensation curable, the amount of surfactant in dispersion is 0.5-5wt%.
5. the process of claim 1 wherein that dispersion further comprises thickener.
6. the method for claim 5, wherein thickener is further defined as poly(ethylene oxide).
7. the method for claim 5 wherein before forming dispersion, is combined thickener with liquid.
8. the method for claim 5, wherein based on the weight of dispersion, the amount of thickener in dispersion is 0.05-5wt%.
9. any one method of claim 1-8, wherein dispersion further comprises the organic compound of condensation curable.
10. any one method of claim 1-8, wherein dispersion comprises the silicon rubber of 20-80 weight portion condensation curable, with respect to 100 weight portion dispersion meters, as long as the total amount of dispersion is no more than 100 weight portions.
11. the method for claim 10, wherein dispersion comprises 20-80 weight portion liquid, with respect to 100 weight portion dispersion meters, as long as the total amount of dispersion is no more than 100 weight portions.
12. any one method of claim 1-8, wherein liquid is further defined as water.
13. the method for claim 12, wherein the silicon rubber of condensation curable is dispersed in water.
14. any one method of claim 1-8, further comprise dried fibres with the content of further reduction liquid so that the step that the silicon rubber of condensation curable solidifies.
15. the process of claim 1 wherein that dispersion comprises the decentralized photo of the silicon rubber that contains condensation curable, and contain the continuous phase of liquid, surfactant and thickener.
16. any one method of claim 1-8, wherein the fracture strength of fiber is for 15psi and breaking strain are at least 100% at least.
17. a fibre, it comprises the compound of curing and is formed by the dispersion that electrostatic spinning contains following component A and B:
A. liquid; With
B. the silicon rubber of condensation curable;
Wherein reduce the content of described liquid, so that the silicon rubber of described condensation curable solidifies.
18. the goods of claim 17, wherein said dispersion further comprises surfactant.
19. the goods of claim 18 are wherein before forming described dispersion, in conjunction with described surfactant and described liquid.
20. the goods of claim 18, wherein based on the weight of the silicon rubber of described condensation curable, the amount of described surfactant in described dispersion is 0.5-5wt%.
21. the goods of claim 17, wherein said dispersion further comprises thickener.
22. the goods of claim 21, wherein said thickener is further defined as poly(ethylene oxide).
23. the goods of claim 21 are wherein before forming described dispersion, in conjunction with described thickener and described liquid.
24. the goods of claim 21, wherein based on the weight of described dispersion, the amount of described thickener in described dispersion is 0.05-5wt%.
25. any one goods of claim 17-24, wherein said dispersion further comprises the organic compound of condensation curable.
26. any one goods of claim 17-24, wherein said dispersion comprises the silicon rubber of the described condensation curable of 20-80 weight portion, with respect to the described dispersion of 100 weight portions, as long as the total amount of described dispersion is no more than 100 weight portions.
27. the goods of claim 26, wherein said dispersion comprise the described liquid of 20-80 weight portion, with respect to the described dispersion of 100 weight portions, as long as the total amount of described dispersion is no more than 100 weight portions.
28. any one goods of claim 17-24, wherein said liquid is further defined as water.
29. the goods of claim 17, wherein said dispersion comprises the decentralized photo of the silicon rubber that contains described condensation curable, and contains the continuous phase of described liquid, surfactant and thickener.
30. the goods of claim 29, the silicon rubber of wherein said condensation curable comprises that with respect to the described dispersion meter of 100 weight portions amount be the silicone elastomer of 20-80 weight portion, described liquid is further defined as water and is the 20-80 weight portion with respect to 100 weight portion dispersion meter amounts, described surfactant comprises that with respect to the described dispersion meter of 100 weight portions amount be the methyl aminomethyl propanol of 0.5-5 weight portion, and described thickener is further defined as poly(ethylene oxide) and is the 0.05-5 weight portion with respect to the described dispersion meter of 100 weight portions amount.
31. any one goods of claim 17-24, it is further defined as non-woven mat.
32. a method of making fibre, described goods comprise the fiber that is formed by dispersion, and described method comprises the steps:
A. form and contain following compositions (i) and dispersion (ii):
(i) liquid, and
(ii) curable silicon rubber,
B. the electrostatic spinning dispersion forms fiber; With
C. solidify this curable silicon rubber.
33. the method for claim 32, wherein dispersion further comprises surfactant and thickener.
34. the method for claim 33, wherein based on the weight of curable silicon rubber, the amount of surfactant in dispersion is 0.5-5wt%.
35. the method for claim 33, wherein thickener is further defined as poly(ethylene oxide).
36. the method for claim 33, wherein the amount of thickener in dispersion is the 0.05-5% of dispersion weight.
37. any one method of claim 32-36, wherein dispersion comprises 20-80 weight portion liquid, with respect to 100 weight portion dispersion meters, as long as the total amount of dispersion is no more than 100 weight portions.
38. any one method of claim 32-36, wherein liquid is further defined as water.
39. the method for claim 38, wherein curable silicon rubber is dispersed in water.
CN2009801405233A 2008-08-29 2009-08-28 Article formed from electrospinning dispersion Expired - Fee Related CN102187022B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US9297908P 2008-08-29 2008-08-29
US61/092,979 2008-08-29
PCT/US2009/055386 WO2010025381A2 (en) 2008-08-29 2009-08-28 Article formed from electrospinning a dispersion

Publications (2)

Publication Number Publication Date
CN102187022A CN102187022A (en) 2011-09-14
CN102187022B true CN102187022B (en) 2013-10-23

Family

ID=41631762

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009801405233A Expired - Fee Related CN102187022B (en) 2008-08-29 2009-08-28 Article formed from electrospinning dispersion

Country Status (10)

Country Link
US (1) US20110165811A1 (en)
EP (1) EP2318575A2 (en)
JP (1) JP2012501390A (en)
KR (1) KR20110058827A (en)
CN (1) CN102187022B (en)
CA (1) CA2735440A1 (en)
IL (1) IL211432A0 (en)
MX (1) MX2011002221A (en)
TW (1) TW201016909A (en)
WO (1) WO2010025381A2 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2321123B1 (en) 2008-08-29 2018-08-08 Dow Silicones Corporation Metallized particles formed from a dispersion
KR20110061751A (en) * 2009-12-02 2011-06-10 한국전자통신연구원 Organic-inorganic hybrid nanofibers for thermoelectric devices and method for forming the same
JP5747376B2 (en) * 2010-06-04 2015-07-15 Jnc株式会社 Fibers obtained from a polymer containing a silsesquioxane skeleton, fiber assemblies, and methods for producing them
AU2012220738A1 (en) 2011-02-22 2013-10-10 Regents Of The University Of Minnesota Silica encapsulated biomaterials
KR101272248B1 (en) 2011-05-04 2013-06-13 한국과학기술연구원 Organic/inorganic hybrid polysilsesquioxane microfiber using electrospinning, and the method for preparing the same
TWI455334B (en) 2011-06-01 2014-10-01 Taiwan Textile Res Inst Method of fabricating photoanode for dye-sensitized solar cell
KR101310523B1 (en) * 2011-07-15 2013-09-23 삼성전기주식회사 Porous sheet and method for manufacturing the same
DE102011109767A1 (en) * 2011-08-09 2013-02-14 Mann + Hummel Gmbh Process for the production of polyamide nanofibers by electrospinning, polyamide nanofibers, a filter medium with polyamide nanofibers and a filter element with such a filter medium
EP2804890A1 (en) 2012-01-18 2014-11-26 Dow Corning Corporation Methods of making saccharide siloxane copolymers
DE102013201124A1 (en) 2013-01-24 2014-07-24 Wacker Chemie Ag Nonwovens made of thermoplastic silicone elastomers, producible by electrospinning
US9534236B2 (en) 2013-03-08 2017-01-03 Regents Of The University Of Minnesota Membranes for wastewater-generated energy and gas
US10035719B2 (en) 2014-10-15 2018-07-31 Regents Of The University Of Minnesota System and membrane for wastewater-generated energy and gas
JP6701896B2 (en) * 2016-04-04 2020-05-27 信越化学工業株式会社 Silicone-modified polyurethane fiber and method for producing the same
US20220111113A1 (en) * 2019-01-31 2022-04-14 Rensselaer Polytechnic Institute Nanocomposite fibers with a dramatic reduction in human plasma coagulation time
TWI792633B (en) 2020-11-03 2023-02-11 中央研究院 Method for manufacturing a polymer-based fibrous scaffold
CN112899890B (en) * 2021-01-25 2022-02-18 浙江祥隆科技有限公司 Nano SiO2 grafted polyacrylonitrile waterproof breathable fiber membrane and preparation method thereof
CN115212730A (en) * 2021-04-18 2022-10-21 中国科学院化学研究所 Separation membrane material based on biomass and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005026398A2 (en) * 2003-09-05 2005-03-24 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Nanofibers, and apparatus and methods for fabricating nanofibers by reactive electrospinning
WO2008010199A2 (en) * 2006-07-18 2008-01-24 Nanopeutics S.R.O. A nanofibre product
WO2008022993A2 (en) * 2006-08-21 2008-02-28 Basf Se Process for producing nano- and mesofibres by electrospinning colloidal dispersions
DE102006049666A1 (en) * 2006-10-18 2008-04-30 Carl Freudenberg Kg Producing polymer fibers for the manufacture of cleaning, hygiene or medical products comprises electrospinning a colloidal dispersion of a water-insoluble polymer

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH106968D (en) * 1965-01-21 1900-01-01
JPS51126300A (en) * 1975-04-26 1976-11-04 Res Inst Iron Steel Tohoku Univ Method for manufacturing an organoo silicon polymer having silicon and carbon atoms as main skeleton component
US4938556A (en) * 1983-11-25 1990-07-03 The Board Of Trustees Of The Leland Stanford Junior University Superfluorescent broadband fiber laser source
US4704444A (en) * 1984-02-10 1987-11-03 Minnesota Mining And Manufacturing Company Polyhydridosilanes and their conversion to pyropolymers
FR2581391B1 (en) * 1985-05-06 1987-06-05 Rhone Poulenc Rech ORGANO-POLYSILAZANE COMPOSITION COMPRISING FREE RADICAL GENERATORS AND CROSSLINKABLE BY ENERGY SUPPLY
JPH0816193B2 (en) * 1985-06-03 1996-02-21 ゼロツクス コ−ポレ−シヨン Thermally stabilized silicone elastomer
DE3717073A1 (en) * 1987-05-21 1988-12-08 Wacker Chemie Gmbh SILICONE RESIN POWDER AND METHOD FOR THE PRODUCTION THEREOF
DE3717075A1 (en) * 1987-05-21 1988-12-08 Wacker Chemie Gmbh METHOD FOR PRODUCING COLLOIDAL SUSPENSIONS OF ORGANOPOLYSILOXANS
DE3811155A1 (en) * 1988-03-31 1989-10-19 Wacker Chemie Gmbh ORGANOSOLS OF ORGANOPOLYSILOXANES AND METHOD FOR THE PRODUCTION THEREOF
JPH03161502A (en) * 1989-11-20 1991-07-11 I C I Japan Kk Production of electrostatic spun yarn
US5945158A (en) * 1996-01-16 1999-08-31 N.V. Union Miniere S.A. Process for the production of silver coated particles
US6344272B1 (en) * 1997-03-12 2002-02-05 Wm. Marsh Rice University Metal nanoshells
JP3603945B2 (en) * 1999-10-06 2004-12-22 信越化学工業株式会社 Conductive silicone rubber composition
US7507687B2 (en) * 2000-03-22 2009-03-24 Cabot Corporation Electrocatalyst powders, methods for producing powder and devices fabricated from same
EP1195417B1 (en) * 2000-10-05 2009-10-14 Evonik Degussa GmbH Silicone-organic nanocapsules
JP3963439B2 (en) * 2001-06-08 2007-08-22 日本バイリーン株式会社 Inorganic structure manufacturing method and inorganic structure
TW557237B (en) * 2001-09-14 2003-10-11 Sekisui Chemical Co Ltd Coated conductive particle, coated conductive particle manufacturing method, anisotropic conductive material, and conductive connection structure
US7008982B2 (en) * 2003-09-29 2006-03-07 J.M. Huber Corporation Surface treated silicas
US7141518B2 (en) * 2003-10-16 2006-11-28 Kimberly-Clark Worldwide, Inc. Durable charged particle coatings and materials
US20050164584A1 (en) * 2003-12-31 2005-07-28 Baratian Stephen A. Retractable nonwoven layers having minimal application of coalesced elastomers
US7709088B2 (en) * 2004-06-23 2010-05-04 Teijin Limited Inorganic fibers, fiber structure and process for their production
US20060085063A1 (en) * 2004-10-15 2006-04-20 Shastri V P Nano- and micro-scale engineering of polymeric scaffolds for vascular tissue engineering
DE102005008926A1 (en) * 2005-02-24 2006-11-16 Philipps-Universität Marburg Process for the preparation of nano- and mesofibres by electrospinning of colloidal dispersions
CN101137779B (en) * 2005-03-10 2013-07-03 麻省理工学院 Superhydrophobic fibers and methods of preparation and use thereof
JP2006283240A (en) * 2005-04-01 2006-10-19 Oji Paper Co Ltd Web-producing apparatus
KR100812357B1 (en) * 2005-12-23 2008-03-11 한국과학기술연구원 Ultra-sensitive metal oxide gas sensor and fbrication method thereof
DK1993501T3 (en) * 2006-02-03 2013-06-03 Univ Akron Absorbent nonwoven fiber mats and method of making them
JP5309505B2 (en) * 2006-09-01 2013-10-09 信越化学工業株式会社 Amorphous inorganic ceramic material and method for producing the same
JP2008081920A (en) * 2006-09-01 2008-04-10 Shin Etsu Chem Co Ltd Silicone-based fiber, nonwoven fabric formed therefrom, and method of producing the same
WO2008030457A2 (en) * 2006-09-06 2008-03-13 Corning Incorporated Nanofibers, nanofilms and methods of making/using thereof
US20080145655A1 (en) * 2006-12-14 2008-06-19 Ppg Industries Ohio, Inc. Electrospinning Process
US8585795B2 (en) * 2007-03-12 2013-11-19 Univesity of Florida Research Foundation, Inc. Ceramic nanofibers for liquid or gas filtration and other high temperature (> 1000° C.) applications
EP2212457B1 (en) * 2007-11-20 2013-07-24 Dow Corning Corporation Article and method of manufacturing same
US8298471B2 (en) * 2007-12-11 2012-10-30 Basf Se Process for producing nano- and mesofibers by electrospinning colloidal dispersions comprising at least one essentially water-insoluble polymer
US20110192789A1 (en) * 2008-09-02 2011-08-11 Drexel University Metal or metal oxide deposited fibrous materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005026398A2 (en) * 2003-09-05 2005-03-24 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Nanofibers, and apparatus and methods for fabricating nanofibers by reactive electrospinning
WO2008010199A2 (en) * 2006-07-18 2008-01-24 Nanopeutics S.R.O. A nanofibre product
WO2008022993A2 (en) * 2006-08-21 2008-02-28 Basf Se Process for producing nano- and mesofibres by electrospinning colloidal dispersions
DE102006049666A1 (en) * 2006-10-18 2008-04-30 Carl Freudenberg Kg Producing polymer fibers for the manufacture of cleaning, hygiene or medical products comprises electrospinning a colloidal dispersion of a water-insoluble polymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开2003-73964A 2003.03.12

Also Published As

Publication number Publication date
MX2011002221A (en) 2011-08-03
IL211432A0 (en) 2011-05-31
JP2012501390A (en) 2012-01-19
WO2010025381A4 (en) 2010-09-23
EP2318575A2 (en) 2011-05-11
US20110165811A1 (en) 2011-07-07
TW201016909A (en) 2010-05-01
KR20110058827A (en) 2011-06-01
WO2010025381A2 (en) 2010-03-04
WO2010025381A3 (en) 2010-07-22
CA2735440A1 (en) 2010-03-04
CN102187022A (en) 2011-09-14

Similar Documents

Publication Publication Date Title
CN102187022B (en) Article formed from electrospinning dispersion
CN101910492B (en) Article and method of manufacturing same
Mable et al. ABC triblock copolymer worms: Synthesis, characterization, and evaluation as pickering emulsifiers for millimeter-sized droplets
Chae et al. Micro/nanometer‐scale fiber with highly ordered structures by mimicking the spinning process of silkworm
Zhang et al. Inverse Pickering emulsions stabilized by cinnamate modified cellulose nanocrystals as templates to prepare silica colloidosomes
ES2657756T3 (en) Fiber and fiber formation process produced through the process
CN102282301B (en) Electrospinning of ptfe with high viscosity materials
US20060063882A1 (en) Process for preparing microrods using liquid-liquid dispersion
Li et al. A highly stretchable and biodegradable superamphiphobic fluorinated polycaprolactone nanofibrous membrane for antifouling
Wang et al. Formation of interfacial janus nanomicelles by reactive blending and their compatibilization effects on immiscible polymer blends
Wei et al. Design of nanocellulose fibrils containing lignin segment (L-NCF) for producing stable liquid foams as “green” flooding agents for oil recovery
EP2212384B1 (en) Article comprising fibers and a method of forming the same
Virgilio et al. Novel self-assembling close-packed droplet array at the interface in ternary polymer blends
Teng et al. Modified hyperbranched polyethylenimine as a novel demulsifier for oil-in-water emulsions
Qian et al. Water-in-water Pickering emulsions stabilized by the starch nanocrystals with various surface modifications
Carvalho et al. Polystyrene/cellulose nanofibril composites: fiber dispersion driven by nanoemulsion flocculation
CN110585476B (en) Preparation method of non-spherical hydrogel microparticle embolic agent
Duan et al. Synthesis of highly branched water-soluble polyester and its surface sizing agent strengthening mechanism
KR20100137490A (en) Silicone polymer dispersion and method of forming same
Chen et al. Immiscible polymer blends compatibilized through noncovalent forces: construction of a “quasi-block/graft copolymer” by interfacial stereocomplex crystallites
Xu et al. Synthesis, characterization and its compatibilization on polymer blends of arched Janus nanosheets
TW201734137A (en) Organopolysiloxane emulsion composition and resin composition
CN102197093B (en) Metallized particles formed from a dispersion
JPH10140480A (en) Textile treating agent
WO2014121037A1 (en) Hydroxylamine-terminated polysiloxane and methods of making and using the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20131023

Termination date: 20140828

EXPY Termination of patent right or utility model