EP2318575A2 - Article formed from electrospinning a dispersion - Google Patents

Article formed from electrospinning a dispersion

Info

Publication number
EP2318575A2
EP2318575A2 EP20090792065 EP09792065A EP2318575A2 EP 2318575 A2 EP2318575 A2 EP 2318575A2 EP 20090792065 EP20090792065 EP 20090792065 EP 09792065 A EP09792065 A EP 09792065A EP 2318575 A2 EP2318575 A2 EP 2318575A2
Authority
EP
European Patent Office
Prior art keywords
dispersion
set forth
weight
curable compound
article
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.)
Withdrawn
Application number
EP20090792065
Other languages
German (de)
English (en)
French (fr)
Inventor
Randal M. Hill
Eric J. Joffre
Donald T. Liles
Bonnie J. Ludwig
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 EP2318575A2 publication Critical patent/EP2318575A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • 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

Definitions

  • the present invention generally relates to an article and a method of manufacturing the article. More specifically, the method includes forming a dispersion including a liquid and a condensation curable compound and electro spinning the dispersion to manufacture the article.
  • Fibers having micro- and nano-diameters are currently the focus of much research and development in industry, academia, and government.
  • These types of fibers can be formed from organic and inorganic materials such as polyaniline, polypyrrole, polyvinylidene, polyacrylonitrile, polyvinyl chloride, polymethylmethacrylate, polythiophene, and iodine-doped polyacetylene.
  • Fibers of this type have also been formed from hydrophilic biopolymers such as proteins, polysaccharides, collages, fibrinogens, silks, and hyaluronic acid, in addition to polyethylene and synthetic hydrophilic polymers such as polyethylene oxide.
  • Electrospinning is a versatile method that includes use of an electrical charge to form a mat of fibers.
  • electrospinning includes loading a solution into a syringe and driving the solution to a tip of the syringe with a syringe pump to form a droplet at the tip.
  • Electrospinning also usually includes applying a voltage to the needle to form an electrified jet of the solution. The jet is then elongated and whipped continuously by electrostatic repulsion until it is deposited on a grounded collector, thereby forming the mat of fibers.
  • Fibers that are formed via electrospinning may be used in a wide variety of industries including in medical and scientific applications. More specifically, these types of fibers have been used to reinforce certain composites. These fibers have also been used to produce nanometer tubes used in medical dialysis, gas separation, osmosis, and water treatment.
  • fibers are formed from electro spinning various types of two- and three- phased systems such as emulsions.
  • the electrospinning techniques that are used with these systems typically produce fibers that exhibit undesirable mechanical characteristics rendering the fibers brittle and fragile. Accordingly, there remains an opportunity to form articles of fibers that are formed from dispersions and that exhibit improved stress and strain properties. There also remains an opportunity to develop a method of forming such articles.
  • the present invention provides an article of fibers and a method of manufacturing the article.
  • the fibers include a cured compound and are formed from electrospinning a dispersion.
  • the dispersion includes a liquid and a curable compound.
  • the method includes the steps of forming the dispersion and electrospinning the dispersion. In one embodiment, the method includes the step of curing the curable compound.
  • Electrospinning the dispersion allows the fibers that are formed to exhibit characteristics typical of the cured compound and exhibit improved stress and strain properties. This formation of fibers allows for more efficient and accurate production of a variety of materials to be used in medical, scientific, and manufacturing industries.
  • the use of the dispersion also allows for a variety of types of condensation curable compounds to be utilized to form products that can be manipulated based on desired physical and chemical properties.
  • Figure 1 is a scanning electron microscope image of an article including fibers of the instant invention including fiber-fiber junctions and spherical defects.
  • the present invention provides an article including fibers (i.e., an article of fibers), as shown in Figure 1.
  • the present invention also provides a method of manufacturing the article. The method, which includes a step of electrospinning, is described in greater detail below.
  • the article may include a single layer of fibers or multiple layers of fibers. As such, the article may have a thickness of at least 0.01 ⁇ m. More typically, the article has a thickness of from about 1 ⁇ m to about 100 ⁇ m and most typically has a thickness of from about 25 ⁇ m to about 100 ⁇ m.
  • the article is not limited to any particular number of layers of fibers.
  • the article may be woven or non- woven, and may exhibit a microphase separation. In one embodiment, the fibers and the article are non-woven and the article is further defined as a mat. In another embodiment, the fibers and the article are non- woven and the article is further defined as a web. Alternatively, the article may be a membrane.
  • the fibers may also be uniform or nonuniform and may have any surface roughness.
  • the article may be waterproof, water resistant, fire resistant, electrically conductive, self-cleaning, water draining, drag reducing, and combinations thereof.
  • the article is a coating. It is also contemplated that the article may be a fabric, a breathable fabric, a filter, or combinations thereof. Further, the article may be used in a variety of industries such as in catalysts, filters, solar cells, electrical components, transdermal patches, bandages, drug delivery systems, and in antimicrobial applications.
  • the article may be a superhydrophobic fiber mat and may exhibit a water contact angle of greater than about 150 degrees. In various embodiments, the article exhibits water contact angles of from 150 to 180, 155 to 175, 160 to 170, and 160 to 165, degrees. The article may also exhibit a water contact angle hysteresis of below 15 degrees. In various embodiments, the article exhibits water contact angle hystereses of from 0 to 15, 5 to 10, 8 to 13, and 6 to 12.
  • the article may also exhibit an isotropic or non-isotropic nature of the water contact angle and/or the water contact angle hysteresis.
  • the article may include domains that exhibit an isotropic nature and domains that exhibit a non-isotropic nature.
  • the fibers may also be of any size and shape and are typically cylindrical. Typically, the fibers have a diameter of from 0.01 to 100, more typically of from 0.05 to 10, and most typically of from 0.1 to 1, micrometers ( ⁇ m).
  • the fibers have a diameter of from 1 nm to 30 microns, from 1-500 nm, from 1-100 nm, from 100-300 nm, from 100-500 nm, from 50-400 nm, from 300-600 nm, from 400-700 nm, from 500-800 nm, from 500-1000 nm, from 1500-3000 nm, from 1000-5000 nm, from 2000-5000 nm, or from 3000-4000 nm.
  • the fibers also typically have a size of from of from 5 to 20 microns and more typically have a size of from 10-15 microns. However, the fibers are not limited to any particular size.
  • the fibers are often referred to as "fine fibers", which encompasses fibers having both micron-scale diameters (i.e., fibers having a diameter of at least 1 micron) and fibers having nanometer-scale diameters (i.e., fibers having a diameter of less than 1 micron).
  • the fibers may also have a glass transition temperature (T g ) of from 25°C to 500°C.
  • the fibers may also be connected to each other by any means known in the art.
  • the fibers may be fused together in places where they overlap or may be physically separate such that the fibers merely lay upon each other in the article.
  • the fibers, when connected may form a web or mat having pore sizes of from 0.01 to 100 ⁇ m.
  • the pore sizes range in size from 0.1-100, 0.1-50, 0.1-10, 0.1-5. 0.1-2, or 0.1-1.5, microns. It is to be understood that the pore sizes may be uniform or not uniform. That is, the article may include differing domains with differing pore sizes in each domain or between domains.
  • the fibers may have any cross sectional profile including, but not limited to, a ribbon-like cross-sectional profile, an oval cross-sectional profile, a circular cross-sectional profile, and combinations thereof.
  • "beading" of the fibers can be observed, which may be acceptable for most applications.
  • the presence of beading, the cross-sectional profile of the fiber (varying from circular to ribbonous), and the fiber diameter are functions of the conditions of a method in which the fibers are formed, to be described in further detail below.
  • the fibers may also be fire resistant, as introduced above.
  • Fire resistance of the fibers, particularly the non-woven mat including the fibers, is tested using the UL-94V-0 vertical burn test on swatches of the non-woven mat deposited onto aluminum foil substrates.
  • a strip of the non-woven mat is held above a flame for about 10 seconds. The flame is then removed for 10 seconds and reapplied for another 10 seconds. Samples are observed during this process for hot drippings that spread the fire, the presence of afterflame and afterglow, and the burn distance along the height of the sample.
  • intact fibers are typically observed beneath those that burn.
  • the fire resistance is typically attributable to a low ratio of organic groups to silicon atoms in the fibers.
  • the low ratio of organic groups to silicon atoms is attributable to the absence of organic polymers and organic copolymers in the fibers.
  • the fire resistance may be due to factors other than the low ratio of organic groups to silicon atoms in the fibers.
  • the fibers are formed from a dispersion.
  • dispersions include one phase of matter that is immiscible with, and dispersed in, another phase of matter, i.e., a dispersed phase in a continuous phase.
  • the dispersion includes a liquid and a curable compound, described in greater detail below.
  • the liquid is a non-polar liquid.
  • the liquid is a polar liquid such as an alcohol, an ionic liquid, or water.
  • the liquid is water.
  • the water may be tap water, well water, purified water, deionized water, and combinations thereof and may be present in the dispersion in varying amounts depending on the type of dispersion.
  • the liquid may be either the dispersed phase or the continuous phase.
  • the dispersion includes solid particles as the dispersed phase and the liquid as the continuous phase.
  • the dispersion includes a non-polar liquid as the dispersed phase and a polar liquid as the continuous phase.
  • the liquid may be present in amounts of from 20 to 80, of from 30 to 70, of from 40 to 60, or in an amount of about 50, parts by weight per 100 parts by weight of the dispersion, so long as a total amount of the dispersion does not exceed 100 parts by weight.
  • the dispersion may be further defined as a "colloid" or "colloid dispersion,” terminology which can be used interchangeably.
  • colloids typically include particles of less than 100 nanometers in size dispersed in the continuous phase.
  • Colloids may be classified in numerous ways.
  • the colloid may also be classified as a gel (a liquid dispersed phase and a solid continuous phase), an emulsion (a liquid dispersed phase and a liquid continuous phase), and/or a foam (a gas dispersed phase and a liquid continuous phase).
  • the colloid may be reversible (i.e., exist in more than one state) or irreversible. Further, the colloid may be elastomeric or viscoelastic.
  • the dispersion is further defined as an emulsion, as first introduced immediately above.
  • Emulsions are typically classified into one of four categories according to a chemical nature of the dispersed and continuous phases.
  • a first category is an oil-in-water (OAV) emulsion.
  • OAV emulsions typically include a non-polar dispersed phase (e.g., oil) in an aqueous continuous phase (e.g. water) which forms droplets, which are typically referred to as emulsion particles.
  • OAV emulsions typically include a non-polar dispersed phase (e.g., oil) in an aqueous continuous phase (e.g. water) which forms droplets, which are typically referred to as emulsion particles.
  • the terminology "oil” includes non-polar molecules and may include the curable compound.
  • a second category of emulsion is a water-in- oil (W/O) emulsion.
  • W/O emulsions typically include a polar dispersed phase in a non-polar continuous phase thereby forming an inverted emulsion.
  • a third category is a water-in-oil-in-water (W/OAV) emulsion. These types of emulsions include a polar dispersed phase in a non-polar continuous phase which is, in turn, dispersed in a polar continuous phase.
  • W/OAV emulsions may include water droplets entrapped within larger oil droplets that in turn are dispersed in a continuous water phase.
  • a fourth category is a water-in-water (WAV) emulsion.
  • emulsions include aqueous solvated molecules in a continuous aqueous solution wherein both the aqueous solvated molecules and the continuous aqueous solution include different molecules that are water-soluble.
  • the aforementioned types of emulsions depend on hydrogen bonding, pi stacking, and/or salt bridging of both the dispersed and continuous phases.
  • the dispersion may be further defined as any one of these four types of emulsions.
  • dispersions are, to a certain degree, unstable.
  • there are three types of dispersion instability including (i) flocculation, where particles of the dispersed phase form clumps in the continuous phase, (ii) creaming, where the particles of the dispersed phase concentrate towards a surface or bottom of the continuous phase, and (iii) breaking and coalescence, where the particles of the dispersed phase coalesce and form a layer of liquid in the continuous phase.
  • the instant dispersion may exhibit one or more of these types of instability.
  • the dispersion of the instant invention may include particles of varying sizes.
  • the dispersion includes particles of from 1 nm to 10 ⁇ m, more typically of from 1 nm to 1 ⁇ m, and most typically of from 1 to 100 nm.
  • the dispersion may be classified as a nanoemulsion.
  • the dispersion may include particles smaller or larger than the sizes described immediately above, depending on the desire of those of skill in the art.
  • the dispersion also includes the curable compound.
  • the curable compound may any organic or inorganic compound known in the art that can be cured. Non-limiting examples of suitable curable compounds include compounds that cure by free-radical mechanisms, hydrosilylation, condensation, addition reactions, ultraviolet light, microwaves, and heat.
  • curable compounds include, but are not limited to, peroxides, amides, acrylates, esters, ethers, imides, oxiranes, sulfones, ureas, urethanes, compounds with ethylenically unsaturated bonds, and combinations thereof.
  • the curable compound is selected from the group of silanes, siloxanes, silazanes, silicones, silicas, silenes, silsesquioxanes, and combinations thereof.
  • the curable compound typically cures via free radical, condensation, and/or hydrosilylation mechanisms.
  • the curable compound may be present in amounts of from 20 to 80, of from 30 to 70, of from 40 to 60, or in an amount of about 50, parts by weight per 100 parts by weight of the dispersion, so long as a total amount of the dispersion does not exceed 100 parts by weight.
  • the curable compound may be further defined as a condensation curable compound.
  • condensation curable compounds cure via condensation reactions. Condensation reactions are chemical reactions in which two molecules combine to form a new single molecule, together with the loss of a small molecule, such as water. When water is lost, the condensation reaction may also be known as a dehydration reaction.
  • a general condensation (dehydration) reaction scheme is set forth below:
  • the condensation reaction is not limited to loss of water and instead may include a loss of an organic or inorganic compound or a molecule of hydrogen.
  • the condensation reaction may also occur where one or more Si atoms in the reaching scheme is replaced by a carbon (C) atom.
  • the condensation curable compound may include monomers, dimers, oligomers, polymers, pre -polymers, co-polymers, block polymers, star polymers, graft polymers, random co-polymers, macromonomers, telechelic oligomers, nanoparticles, and combinations thereof.
  • oligomer as used herein includes identifiable chemical groups, including dimers, trimers, tetramers and/or pentamers, linked together through reactive moieties capable of condensation.
  • preferred organic reactive moieties capable of condensation include, but are not limited to, hydrolyzable moieties, hydroxyl moieties, hydrides, isocyanate moieties, amine moieties, amide moieties, acid moieties, alcohol moieties, amine moieties, acrylate moieties, carbonate moieties, epoxide moieties, ester moieties, and combinations thereof.
  • the condensation curable compound may also include inorganic moieties including, but not limited to, silicones, siloxanes, silanes, transition metal compounds, and combinations thereof.
  • articles of the instant invention can also be formed by various addition reactions such as free radical additions, Michael reactions, hydrosilylation reactions, and/or Diels Alder reactions. Ring opening polymerizations can also be used.
  • the condensation curable compound may be any compound of U.S. Provisional Application Number 61/003726 filed on 11/20/07, which is expressly incorporated herein by reference.
  • the condensation curable compound may include organic and inorganic polymers such as polyesters, polyamides, polyimides, polyureas, polyethers, polyamines, polyurethanes, aramides, polycarbonates, carbonates, and combinations thereof.
  • the condensation curable compound may cure to form a compound selected from the group of polyesters, nylons, polyurethanes, aramides, carbonates, and combinations thereof.
  • the (condensation) curable compound may be substantially free of silicon (i.e., silicon atoms and/or compounds containing silicon atoms). It is to be understood that the terminology “substantially free” refers to a concentration of silicon of less than 5,000, more typically of less than 900, and most typically of less than 100, parts of compounds that include silicon atoms, per one million parts of the condensation curable compound. It is also contemplated that the (condensation) curable compound may be totally free of silicon.
  • the (condensation) curable compound may include a polymerization product of at least a silicon monomer and an organic monomer. It is contemplated that the organic monomer and/or silicon monomer may be present in the (condensation) curable compound in any volume fraction. In various embodiments, the organic monomer and/or silicon monomer are present in volume fractions of from 0.05-0.9, 0.1-0.6., 0.3-0.5, 0.4-0.9, 0.1- 0.9, 0.3-0.6, or 0.05-0.9. [0026] The organic monomer may include any organic moiety described above.
  • silicon monomer includes any monomer that includes at least one silicon (Si) atom such as silanes, siloxanes, silazanes, silicones, silicas, silenes, silsesquioxanes, and combinations thereof. It is to be understood that the silicon monomer may include polymerized groups and remain a silicon monomer so long as it retains an ability to be polymerized. In one embodiment, the silicon monomer is selected from the group of silanes, silsesquioxanes, siloxanes, and combinations thereof.
  • the (condensation) curable compound is selected from the group of an organosilane, an organopolysiloxane, and combinations thereof.
  • the organopolysiloxane may be selected from the group of a silanol terminated siloxane, an alkoxylsilyl-terminated siloxane, and combinations thereof.
  • the (condensation) curable compound may be linear or non-linear and may include hydroxyl and/or organosiloxy groups (-SiOR) and may include hydroxyl terminated polydimethylsiloxane.
  • the (condensation) curable compound may include the general structure:
  • each of R 1 and R 2 independently include one of a hydrogen, a hydroxyl group, an alkyl group, a halogen substituted alkyl group, an alkylenyl group, an aryl group, a halogen substituted aryl group, an alkaryl group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an acid amido group, an amino-oxy group, a mercapto group, and an alkenyloxy group, and n may be any integer.
  • the (condensation) curable compound may include hydrocarbylene and/or fluorocarbylene groups.
  • Hydrocarbylene groups include a divalent moiety including carbon and hydrogen.
  • Fluorocarbylene groups include a hydrocarbylene moiety with at least one of the hydrogens replaced with at least one fluorine atom.
  • Typical fluorocarbylene groups include partially or wholly fluorine substituted alkylene groups.
  • the (condensation) curable compound may also include olefinic moieties including acrylate moieties, methacrylate moieties, vinyl moieties, acetylenyl moieties, and combinations thereof.
  • the (condensation) curable organopolysiloxane may include siloxanes having at least one terminal silanol group or one hydrogen atom bonded to silicon or a hydrolyzable group which, upon exposure to moisture, forms silanol groups. Terminal or pendant silanol groups, or their precursors, allow for condensation.
  • the (condensation) curable compound may be further defined as an elastomer or as a curable elastomer.
  • elastomers are compounds that exhibit elasticity, i.e., an ability to deform under stress and return to an approximately original shape.
  • the terminology “elastomer” is not limited to polymer or monomers and may include one or both.
  • the elastomer may include any of the aforementioned (condensation) curable compounds.
  • the curable elastomer is commercially available from Dow Corning Corporation of Midland, MI under the trade name of Dow Corning 84 Additive.
  • the curable compound has a number average molecular weight (M n ) of greater than 5,000 g/mol and more typically of greater than 10,000 g/mol.
  • M n number average molecular weight
  • the curable compound is not limited to such a number average molecular weight.
  • the curable compound has a number average molecular weight of greater than about 100,000 g/mol.
  • the curable compound has number average molecules weights of from 100,000-5,000,000, from 100,000-1,000,000, from 100,000-500,000, from 200,000- 300,000, of higher than about 250,000, or of about 150,000, g/mol.
  • the curable compound has a number average molecular weight of greater than 50,000 g/mol, and more typically of greater than 100,000 g/mol.
  • the curable compound may have a number average molecular weight of at least about 300 g/mol, of from about 1,000 to about 2,000 g/mol, or of from about 2,000 g/mol to about 2,000,000 g/mol.
  • the curable compound may have a number average molecular weight of greater than 350 g/mol, of from about 5,000 to about 4,000,000 g/mol, or of from about 500,000 to about 2,000,000 g/mol.
  • the dispersion may also include one or more surfactants.
  • the dispersion includes a (first) surfactant and a second surfactant or multiple surfactants.
  • the surfactant may be combined with the liquid, with the curable compound, or with both the liquid and the curable compound, prior to formation of the dispersion. Typically, the surfactant is combined with the liquid before the dispersion is formed.
  • Surfactants are also known as surfactant active agents, surface active solutes, emulsifiers, emulgents, and tensides.
  • surfactants reduce a surface tension of a liquid by adsorbing at a liquid-gas interface. Surfactants also reduce interfacial tension between polar and non-polar molecules by adsorbing at a liquid-liquid interface. Without intending to be bound by any particular theory, it is believed that surfactants act at these interfaces and are dependent on various forces including, excluded volume repulsion forces, electrostatic interaction forces, van der waals forces, entropic forces, and steric forces. In the instant invention, the surfactant may be chosen or manipulated based on one or more of these forces.
  • the surfactant, first and second surfactants, or first/second/and multiple surfactants may independently be selected from the group of non-ionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and combinations thereof.
  • Suitable non-ionic surfactants include, but are not limited to, alkylphenol alkoxylates, alcohol ethoxylates including fatty alcohol ethoxylates, glycerol esters, sorbitan esters, sucrose and glucose esters, including alkyl polyglucosides and hydroxyalkyl polyglucosides, alkanolamides, N-alkylglucamides, alkylene oxide block copolymers such as block copolymers of ethylene oxide, propylene oxide and/or butylene oxide, polyhydroxy and polyalkoxy fatty acid derivatives, amine oxides, siloxane based polyethers, and combinations thereof.
  • Suitable cationic surfactants include, but are not limited to, interface- active compounds including ammonium groups such as alkyldimethylammonium halides and compounds having the chemical formula RR'R"R"'N + X " wherein R, R , R", and R are independently selected from the group of alkyl groups, aryl groups, alkylalkoxy groups, arylalkoxy groups, hydroxyalkyl (alkoxy) groups, and hydroxyaryl(alkoxy) groups and wherein X is an anion.
  • Suitable anionic surfactants include, but are not limited to, fatty alcohol sulfates.
  • anionic surfactants include alkanesulfonates, linear alkylbenzenesulfonates, and linear alkyltoluenesulfonates. Still further, the anionic surfactant may include olefinsulfonates and di-sulfonates, mixtures of alkene- and hydroxyalkane- sulfonates or di- sulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glyceryl sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, olefin sulfonates, paraffinsulfonates, alkyl phosphates, acyl isothionates, acyl taurates, acyl methyl taurates, alkylsuccinic acids, sulfosuccinates, al
  • the surfactant and/or first and second surfactants may independently include aliphatic and/or aromatic alkoxylated alcohols, LAS (linear alkyl benzene sulfonates), paraffin sulfonates, FAS (fatty alcohol sulfates), FAES (fatty alcohol ethersulfates), alkylene glycols, trimethylolpropane ethoxylates, glycerol ethoxylates, pentaerythritol ethoxylates, alkoxylates of bisphenol A, and alkoxylates of 4-methylhexanol and 5-methyl-2-propylheptanol, and combinations thereof.
  • LAS linear alkyl benzene sulfonates
  • paraffin sulfonates fatty alcohol sulfates
  • FAES fatty alcohol ethersulfates
  • alkylene glycols trimethylolpropane ethoxylates
  • the surfactant is present in an amount of from 0.1 to 100, more typically of from 0.01 to 5, even more typically of from 0.5 to 5, and most typically of from 1.5 to 5, parts by weight per 100 parts by weight of the dispersion.
  • the dispersion may also include a thickener.
  • thickeners increase a viscosity of the dispersion at low shear rates while maintaining flow properties of the dispersion at higher shear rates.
  • Suitable thickeners for use in the instant invention include, but are not limited to, polyalkylene oxides such as polyethylene oxide, polypropylene oxide, polybutylene oxide, and combinations thereof.
  • the thickener is selected from the group of algenic acid and its derivatives, polyethylene oxide, polyvinyl alcohol, methyl cellulose, hydroxypropylmethyl cellulose, alkyl and hydroxyalkyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, guar gum, gum arabic, gum ghatic, polyvinylpyrrolidone, starch, modified starch, tamarind gum, xanthan gum, polyacrylamide, polyacrylic acid, and combinations thereof.
  • the thickener may also include a nanoparticle such as titanium dioxide and/or a nanoclay such as betonite.
  • the thickener may also be conductive, semi-conductive, insulating, magnetic, or light-emitting.
  • the thickener may include a conductive polymer such as polypyrrole, polyaniline, and/or polyacetylene.
  • the thickener may also include biological components such as proteins or DNA.
  • the thickener may be combined with the liquid, with the curable compound, or with both the liquid and the curable compound before the dispersion is formed. Typically, the thickener is combined with the liquid before the dispersion is formed.
  • the thickener is typically present in an amount of from 0.001 to 25, more typically of from 0.05 to 5, and most typically of from 0.1 to 5, parts by weight per 100 parts by weight of the dispersion.
  • dispersions typically have two different types of viscosities, a total viscosity and a viscosity of the dispersed phase.
  • the dispersion of the instant invention typically has a total viscosity of at least 20 centistokes at a temperature of 25 0 C.
  • the dispersion has a viscosity of at least 20 centistokes, more typically from about 30 to about 100 centistokes, most typically from about 40 to about 75 centistokes at a temperature of 25 0 C using a Brookfield rotating disc viscometer equipped with a thermal cell and an SC4-31 spindle operated at a constant temperature of 25 0 C and a rotational speed of 5 rpm.
  • the viscosity of the dispersed phase is not limited and is not believed to affect the total viscosity.
  • the dispersed phase is solid and has an infinite viscosity.
  • the dispersion may also have a zero shear rate viscosity of from 0.1 to 10, from 0.5 to 10, from 1 to 10, from 5 to 8, or about 6, PaS. Further, the dispersion may have a conductivity of from 0.01- 25 mS/m. In various embodiments, the conductivity of the dispersion ranges from 0.1-10, from 0.1-5, from 0.1-1, from 0.1- 0.5, or is about 0.3, mS/m.
  • the dispersion may also have a surface tension of from 10-100 niN/m. In different embodiments, the surface tension ranges from 20-80, or from 20-50, mN/m. In one embodiment, the surface tension of the dispersion is about 30 mN/m.
  • the dispersion may also have a dielectric constant of from 1-100. In various embodiments, the dielectric constant is between 5-50, 10-70, or 1-20. In one embodiment, the dielectric constant of the dispersion is about 10. [0041]
  • the dispersion may also include an additive.
  • the additive may include, but is not limited to, conductivity-enhancing additives, salts, dyes, colorants, labeling agents, and combinations thereof. Conductivity-enhancing additives may contribute to excellent fiber formation, and may further enable diameters of the fibers to be minimized, especially when the fibers are formed through electro spinning. In one embodiment, the conductivity-enhancing additive includes an ionic compound.
  • the conductivity-enhancing additives are generally selected from the group of amines, organic salts and inorganic salts, and mixtures thereof.
  • Typical conductivity-enhancing additives include amines, quaternary ammonium salts, quaternary phosphonium salts, ternary sulfonium salts, and mixtures of inorganic salts with organic ligands.
  • More typical conductivity-enhancing additives include quaternary ammonium-based organic salts including, but not limited to, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, phenyltrimethylammonium chloride, phenyltriethylammonium chloride, phenyltrimethylammonium bromide, phenyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, tetradecyltrimethylammonium iodide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and he
  • the additive may be present in either the continuous or dispersed phase of the dispersion in any amount selected by one of skill in the art so long as the amount of the additive allows the curing of the curable compound to occur.
  • the amount of the additive is typically of from about 0.0001 to about 25 %, more typically from about 0.001 to about 10%, and more typically from about 0.01 to about 1 % based on the total weight of the fibers.
  • the additive includes methylaminomethylpropanol.
  • the method includes the step of adding the condensation curable compound and the liquid together and mixing.
  • the step of mixing may include mechanical mixing using ribbon mixers, plow mixers, fluidizing paddle mixers, sigma blade mixers, tumble blenders, vortex mixers, feed mixers, vertical mixers, horizontal mixers, rotor-stator mixers, sonicators, Speedmixers ® , and combinations thereof.
  • the instant invention is not limited to any particular order of addition.
  • the dispersion is formed by combining the thickener and water to form a mixture and adding the mixture to the curable compound. Alternatively, the dispersion may be formed by any method known in the art.
  • the method also includes the step of electro spinning the dispersion.
  • this step reduces a content of the liquid (e.g. water) such that the condensation curable compound cures.
  • electro spinning causes at least partial evaporation of the liquid, such as water, such that the condensation curable compound cures.
  • Loss of solvent may allow the curable compounds to blend, i.e. come into intimate contact, allowing for cure.
  • the force of an electric field, used in electrospinning may align functional groups such that they are more readily in contact.
  • the step of electrospinning may be conducted by any method known in the art.
  • a typical electrospinning process includes use of an electrical charge to form the fibers.
  • the dispersion used to form the fibers is loaded into a syringe, the dispersion is driven to a tip of the syringe with a syringe pump, and a droplet is formed at the tip of the syringe.
  • the pump enables control of flow rate of the dispersion used to form the fibers to the spinning head. Flow rate of the dispersion used to form the fibers through the tip of the syringe may have an effect on formation of the fibers.
  • the flow rate of the dispersion through the tip of the syringe may be from about 0.005 ml/min to about 0.5 ml/min, typically from about 0.005 ml/min to about 0.1 ml/min, more typically from about 0.01 ml/min to about 0.1 ml/min, and most typically from about 0.02 ml/min to about 0.1 ml/min. In one specific embodiment, the flow rate of the dispersion through the tip of the syringe may be about 0.05 ml/min.
  • the droplet is then typically exposed to a high-voltage electric field.
  • the droplet exits the tip of the syringe in a quasi- spherical shape, which is the result of surface tension in the droplet.
  • Application of the electric field results in the distortion of the spherical shape into that of a cone.
  • the generally accepted explanation for this distortion in droplet shape is that the surface tension forces within the droplet are neutralized by the electrical forces.
  • Narrow diameter jets of the dispersion emanate from the tip of the cone. Under certain process conditions, the jet of the dispersion undergoes the phenomenon of "whipping" instability. This whipping instability results in the repeated bifurcation of the jet, yielding a network of fibers.
  • the fibers are ultimately collected on a collector plate.
  • the liquid such as water
  • the collector plate is typically formed from a solid conductive material such as, but not limited to, aluminum, steel, nickel alloys, silicon wafers, Nylon ® fabric, and cellulose (e.g., paper).
  • the collector plate acts as a ground source for the electron flow through the fibers during electro spinning of the dispersion. As time passes the number of fibers collected on the collector plate increases and the non-woven fiber mat is formed on the collector plate.
  • the fibers may be collected on the surface of a liquid that is not part of the dispersion, thereby achieving a free-standing non-woven mat.
  • liquid that can be used to collect the fibers is water.
  • the step of electro spinning comprises supplying electricity from a DC generator having generating capability of from about 10 to about 100 kilovolts (KV).
  • KV kilovolts
  • the syringe is electrically connected to the generator.
  • the step of exposing the droplet to the high- voltage electric field typically includes applying a voltage and an electric current to the syringe.
  • the applied voltage may be from about 5 KV to about 100 KV, typically from about 10 KV to about 40 KV, more typically from about 15 KV to about 35 KV, most typically from about 20 KV to about 30 KV. In one specific example, the applied voltage may be about 30 KV.
  • the applied electric current may be from about 0.01 nA to about 100,000 nA, typically from about 10 nA to about 1000 nA, more typically from about 50 nA to about 500 nA, most typically from about 75 nA to about 100 nA. In one specific embodiment, the electric current is about 85 nA.
  • the dispersion is at a temperature within 60°C of ambient temperature. More typically, when electro spinning, the dispersion is at a temperature within 60°C of a processing temperature.
  • the step of electro spinning is believed to at least partially cure the condensation curable compound.
  • the step of electro spinning completely cures the condensation curable compound.
  • the step of electrospinning does not completely cure, or even partially cure, the curable compound such that an additional curing step is needed.
  • the method may include the step of drying to more completely cure the curable compound.
  • the curable compound is further defined as the condensation curable compound, it is hypothesized that the step of drying removes the liquid (e.g. water) and drives the condensation reaction to the right, i.e., towards completion.
  • the method may also include the step of curing the curable compound, as first introduced above.
  • the step of curing may be implemented independent of, or in combination with, the step of electrospinning.
  • This step may include any curing step known in the art including, but not limited to, those related to free-radical curing, hydro silylation curing, condensation curing, UV light curing, microwave curing, heat curing, and combinations thereof.
  • the method may also include the step of annealing the fibers. This step may be completed by any method known in the art. In one embodiment, the step of annealing may be used to enhance the hydrophobicity of the fibers. In another embodiment, the step of annealing may enhance a regularity of microphases of the fibers.
  • the step of annealing may include heating the article. Typically, to carry out the step of annealing, the article is heated to a temperature above ambient temperature of about 20 0 C. More typically, the article is heated to a temperature of from about 40 0 C to about 400 0 C, most typically from about 40 0 C to about 200 0 C.
  • Heating of the article may result in increased fusion of fiber junctions within the article, creation of chemical or physical bonds within the fibers (generally termed "cross-linking"), volatilization of one or more components of the fiber, and/or a change in surface morphology of the fibers.
  • a series of fibers and a non-woven mat are formed according to the present method.
  • the non-woven mat includes the fibers formed from the dispersion including a silicone elastomer as a condensation curable compound.
  • Dow Corning Additive 84 includes a mix of silica and cross-linked silicone rubber including functional groups that can undergo a condensation cure.
  • the polyethylene oxide and the dispersion are stirred to form a translucent white dispersion.
  • the dispersion is then delivered by a syringe/syringe pump to a stainless steel tube with inner diameter of 0.040 inches in preparation for electro spinning. An electric field is applied between the stainless steel tube and a piece of grounded aluminum foil.
  • a droplet at a tip of the stainless steel tube is electrospun into thin white fibers which are deposited onto the grounded aluminum foil.
  • the step of electro spinning is performed at a plate gap of 30 cm, a tip protrusion of 3 cm, an applied voltage of 22 kV, and a flow rate of 1 mL/hr.
  • the electro spinning is performed for one hour.
  • the resultant fibers are one to five microns in diameter and tend to have fiber- fiber junctions. Spherical defects are present within the fibers, as shown in Figure 1. [0052] After electro spinning for one hour, the fibers form an opaque white membrane with a thickness of approximately 200 microns.
  • the membrane is peeled off the aluminum foil and tested to determine tensile properties (stress/strain) at a breaking point using an Alliance RT/5 Tensile Tester commercially available from RTS. More specifically, a "dog-bone" shaped sample of the membrane having a width of 0.1 inches is tested in a 10 N maximum load cell at a pull rate of 100 mm/min. A stress-strain curve is also generated. The peak stress measurement of the fibers is approximately 19 psi and the strain measurement is approximately 120 percent. Additionally, the stress-strain curve is approximately linear suggesting that the fibers are elastomeric at the breaking point.
  • the fibers formed in the aforementioned Example evidence that electro spinning a dispersion allows fibers to be formed that exhibit characteristics of the dispersed phase, i.e., the condensation curable compound, as opposed to the continuous phase.
  • the fibers formed in this Example exhibit elastomeric stress and strain properties and an elastomeric stress-strain curve.
  • the formation of these types of fibers allows for more efficient and accurate production of a variety of materials to be used in medical, scientific, and manufacturing industries.
  • the use of the dispersion also allows for a variety of types of curable compounds to be utilized thus forming new products.
  • a dispersion in which a continuous phase is water allows for an electro spinning process to be done through evaporation of a non- hazardous volatile liquid.
  • an active material for example a bacteria, in the continuous phase, may allow for the creation of biologically functionalized fibers that are curable in a one-step process.

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  • 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)
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MX2011002221A (es) 2011-08-03
TW201016909A (en) 2010-05-01
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US20110165811A1 (en) 2011-07-07
KR20110058827A (ko) 2011-06-01
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CN102187022A (zh) 2011-09-14
WO2010025381A3 (en) 2010-07-22

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