TW201500104A - Method of making a hollow fiber using a core including a meltable or sublimable composition - Google Patents

Abstract

The present invention relates to hollow fibers. In some embodiments, the present invention provides a method of forming a hollow fiber. The method can include providing or obtaining a solid core including a core composition that includes about 50 wt% to about 100 wt% of a composition that is at least one of meltable and sublimable. The method can include coating the core with a curable composition. The method can include curing the curable composition. The method can include melting or subliming at least part of the core composition, to provide a hollow fiber. In some examples, the hollow fiber can be an organopolysiloxane hollow fiber. In various embodiments, the present invention provides a hollow fiber made by the method, an organopolysiloxane-coated core, a core coated with a cured organopolysiloxane composition, or a method of separating components in a feed mixture using a hollow fiber membrane provided by the method.

Description

Method of preparing hollow fibers using a core comprising a meltable or sublimable composition

Hollow fibers are available in a variety of materials and have a wide range of applications. For example, a hollow fiber membrane can be used to separate one or more components of a liquid or gas mixture. The hollow fiber membrane has a high surface area to volume ratio and is an effective way to separate the membrane. However, the synthesis, handling and transportation of hollow fibers can be difficult and expensive.

In various embodiments, the present invention provides a method of forming hollow fibers. The method includes providing or obtaining a substantially cylindrical solid core. This core includes core components. The core composition comprises from about 50 weight percent (wt%) to about 100 wt% of a composition that is at least one of fusible and sublimable. The method includes coating the core with a curable composition. The method includes curing the curable composition. The method includes melting or sublimating at least a portion of the core composition. The method includes removing at least a portion of the molten or sublimated portion of the core composition. This method provides hollow fibers.

In various embodiments, the present invention provides a method of forming a polyfluorene hollow fiber. The method includes providing or obtaining a substantially cylindrical solid core. The core has about 100 Μm to a diameter of about 500 μm. The core includes at least one support fiber. The core includes a core composition that coats the support fibers. The core composition comprises from about 50 weight percent (wt%) to about 100 wt% of a fusible or sublimable composition. The fusible or sublimable composition is fusible or sublimable at at least one temperature of from about -200 °C to about 60 °C. The method includes coating the core with a curable composition comprising an organopolyoxane. The method includes curing the curable composition. The method also includes melting or sublimating at least a portion of the core composition. The method also includes removing at least a portion of the molten or sublimated portion of the core composition. The method provides a polyoxynoxy hollow fiber comprising a wall having a thickness of from about 10 [mu]m to about 60 [mu]m.

In various embodiments, the present invention provides a method of forming a polyfluorene hollow fiber. The method includes providing or obtaining a substantially cylindrical solid core. The core has a diameter of from about 100 [mu]m to about 500 [mu]m. This core includes core components. The core composition comprises from about 50% by weight to about 100% by weight of a composition having a zero shear viscosity of about 100 cP or less at at least one temperature from 0 °C to 60 °C. The method includes coating the core with a curable composition comprising an organopolyoxane. The method includes curing the curable composition. The method includes melting or sublimating at least a portion of the core composition. The method includes removing at least a portion of the molten or sublimated portion of the core composition. The method provides a polyoxynoxy hollow fiber comprising a wall having a thickness of from about 10 [mu]m to about 60 [mu]m.

In various embodiments, the present invention provides an organopolyoxane coated core. The cladding core includes a substantially cylindrical solid core. The core has a diameter of from about 10 [mu]m to about 2000 [mu]m. This core includes core components. The core composition comprises from about 50 weight percent (wt%) to about 100 wt% of a fusible or sublimable composition. The fusible or sublimable composition is fusible or sublimable at at least one temperature of from about -200 °C to about 60 °C. The cladding core includes a cladding A curable composition on the core. The curable composition includes an organopolyoxane.

In various embodiments, the present invention provides a core coated with a cured organopolyoxane composition. The cladding core includes a substantially cylindrical solid core. The core has a diameter of from about 10 [mu]m to about 2000 [mu]m. The core includes a core composition comprising from about 50 weight percent (wt%) to about 100 wt% of a fusible or sublimable composition. The fusible or sublimable composition is fusible or sublimable at at least one temperature of from about -200 °C to about 60 °C. The coated core includes an at least partially cured curable composition overlying the core. The curable composition includes an organopolyoxane and includes a wall having a thickness of from about 1 μm to about 200 μm.

In various embodiments, the invention provides a method of separating components of a feed mixture. The method includes contacting a first side of the membrane with a feed gas or liquid mixture. The feed mixture includes at least a first component and a second component. The contact creates a penetrating mixture on the second side of the film and creates a retention mixture on the first side of the film. The penetrating mixture is enriched in the first component. The retention mixture depletes the first component. The film comprises hollow fibers provided by a method comprising providing or obtaining a solid core. The solid core includes at least one support fiber and a core composition. The core composition coats the support fibers. The core composition is at least one of fusible and sublimable. The method includes coating the core with a curable composition. The method includes curing the curable composition. The method also includes melting or sublimating at least a portion of the core composition to provide hollow fibers.

Compared to other methods of forming hollow fibers, hollow fibers produced by the method, polyoxyalkylene coated cores, cores coated with a cured curable polyoxyalkylene composition, or using the hollow fibers to separate the mixture Methods, different embodiments have certain advantages, at least some of which are unexpected. In some examples, the method is compared to other hollow fibers The method provides hollow fibers in a manner that is more efficient, less costly, or more resistant to damage during synthesis, handling, or transportation. In some instances, the method can be used to produce a wider variety of hollow fibers than other methods, for example because the core stabilizes the coating prior to curing, the meltable or sublimable temperature range of the core composition At least one or by avoiding the use of a soluble solvent. Different embodiments may be a useful alternative or a more efficient method than other methods for making hollow microfibers, such as the inability to form hollow fibers directly from a melt or solution.

For example, in some embodiments, the removal of the core by melting or sublimation is simpler and more efficient than removing the core with dissolution. In some instances, melting or sublimation may be faster or simpler than dissolution, as the entire core may be melted or sublimated at about the same time, however in some instances, the dissolution may only dissolve or primarily dissolve through the opening of the hollow fiber. Contact with the core end, or take time to allow water to pass through the membrane before dissolution can occur. In some embodiments, the method may result in a more complete removal of the core than other methods such as relying solely on dissolution. In some embodiments, the method can result in less waste, such as when the melted or sublimated material is recovered for reuse. In some embodiments, the method allows for a higher variety of shapes of the hollow fibers produced.

In some embodiments, the method may provide hollow fibers or provide hollow fibers having at least one of a more uniform diameter and a smaller diameter than hollow fibers produced using an extrusion technique. In some embodiments of the invention, the core may be allowed to remain in the hollow fiber during handling, transportation or other activities, thus facilitating stabilization of the hollow fiber and helping to prevent collapse or other injury. Thus, in some instances, the method can provide for the synthesis, processing, transportation, or other hollow fibers produced by other techniques, such as extrusion techniques. Hollow fibers that do not collapse during the activity. Thus, in some embodiments, the present method can provide hollow fibers that are easier to handle and easier to transport than hollow fibers produced using other techniques, such as extrusion techniques.

In some instances, the method can provide hollow fibers using a core that can be melted or sublimed at a temperature that is more convenient than the temperatures used in other methods of making hollow fibers. In some embodiments, the method uses a core that is easier to synthesize than other methods. In some instances, the method can be used to produce a wider variety of hollow fibers than other methods, for example because of the stabilizing effect of the core and at least one of the melting or sublimation temperatures of the core.

Certain embodiments of the disclosed subject matter are described in detail below. It is to be understood that the subject matter of the disclosure is to be construed as being limited by the scope of the invention.

Numerical values expressed in the form of ranges are to be interpreted in a manner that is not limited to the numerical value of the range, and all individual values or sub-ranges within the range, as well as the various values or sub-ranges. For example, the range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted as not only including a concentration of about 0.1% to about 5%, but also individual within the range indicated. Concentrations (eg, 1%, 2%, 3%, and 4%) and sub-ranges (eg, 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%). The description of "about X to Y" has the same meaning as "about X to about Y" unless otherwise stated. Similarly, the description "about X, Y or about Z" has the same meaning as "about X, about Y or about Z" unless otherwise stated.

In this document, the terms "a", "an" or "the" are used to mean one or greater than one unless the context clearly dictates otherwise. The term "or" is used to mean a non-exclusive "or" unless the contrary is indicated. In addition, the words and phrases used herein are not intended to be limiting, and are not intended to be limiting. The use of paragraph headings is used to assist in reading the document and should not be construed as being restrictive; information relating to the paragraph heading may appear within or outside the particular paragraph. In addition, all of the documents, patents, and patent documents mentioned in this specification are hereby incorporated by reference in their entirety in their entirety herein in their entirety In the event of inconsistencies between this document and the documents incorporated by reference, the terms incorporated in the referenced document shall be deemed to be in addition to the terms used in this document; in the event of inconsistencies, the terminology of this document shall prevail.

Where a manufacturing method is referred to herein, the various steps may be performed in any order without departing from the principles of the invention, unless the order of time or operation is explicitly mentioned. In addition, multiple specific steps can be performed simultaneously, unless the request text is clearly documented separately. For example, the requested step of performing X and the requesting step of performing Y may be performed simultaneously in a single operation, and the process will fall within the scope of the claimed process.

The term "about" as used herein refers to a value or range that has a degree of variability, such as within 10%, within 5%, or within 1% of the stated value of the stated value or range.

As used herein, the term "substantially" means the majority or the vast majority, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99. %, 99.5%, 99.9%, 99.99% or at least about 99.999% or more.

The term "organic group" as used herein means, but is not limited to, any carbon-containing functional group. Examples include fluorenyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl or heteroarylalkyl, straight-chain and/or branched groups such as alkyl, fully or partially halogen-substituted halane Base, alkenyl, Alkynyl, acrylate, and methacrylate functional groups; and other organic functional groups such as ether groups, cyanate groups, ester groups, carboxylate groups, and concealed isocyano groups.

The term "substituted" as used herein means that one or more hydrogen atom bonds contained in an organic group or molecule as defined herein are replaced by one or more non-hydrogen atom bonds. The term "functional group" or "substituent" as used herein refers to a group which may be substituted onto a molecule or an organic group. Examples of substituents or functional groups include, but are not limited to, any organic group, halogen (e.g., F, Cl, Br, and I); such as thiol groups, alkyl sulfide groups, aryl sulfide groups, fluorenylene groups, fluorenyl groups a sulfur atom in a group of a sulfonyl group and a sulfonamide group; a nitrogen atom in a group such as an amine, a hydroxylamine, a nitrile, a nitro group, an N-oxide, a hydrazine, an azide, and an enamine; Other heteroatoms in other groups.

As used herein, the term "hydrocarbyl" refers to a functional group derived from a linear hydrocarbon, a branched hydrocarbon or a cyclic hydrocarbon such as an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a cycloalkyl group, a decyl group or the like. combination. The hydrocarbyl group can be unsubstituted or substituted.

The term "alkyl" as used herein, refers to a straight-chain alkyl, branched alkyl group having from 1 to about 20 carbon atoms, usually from 1 to 12 carbon atoms or, in some embodiments, from 1 to 8 carbon atoms. And cycloalkyl. Examples of the linear alkyl group include those having 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, isobutyl, secondary butyl, tert-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl. As used herein, the term "alkyl" embraces all branched forms of alkyl. A representative substituted alkyl group can be substituted one or more times by, for example, any functional group.

The term "alkenyl" as used herein, refers to a straight-chain alkyl group, a branched alkyl group, and a cycloalkyl group, as defined herein, except that at least one double bond is present between two carbon atoms. Thus, alkenyl groups have from 2 to about 20 carbon atoms, typically from 2 to 12 carbon atoms or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to, vinyl, -CH=CH(CH ₃ ), -CH=C(CH ₃ ) ₂ , -C(CH ₃ )=CH ₂ , -C(CH ₃ )=CH(CH ₃ ), -C(CH ₂ CH ₃ )=CH ₂ , cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, hexadienyl and the like.

As used herein, the term "resin" refers to any viscosity polyoxyalkylene material that includes at least one siloxane single bond bonded to three or four other siloxane monomers via a Si-O-Si bond. body. In one example, the polyoxyalkylene material comprises a T or Q group as defined herein.

The term "number average molecular weight" as used herein refers to the general arithmetic mean of the molecular weight of individual molecules in a sample. It is defined as the total weight of all molecules in the sample divided by the total number of molecules in the sample. Experimentally, a number average molecular weight (M _n) is divided by analyzing having a molecular weight M _i n _i of the measured sample molecular weight component of the molecules of species i, the use of the formula _{M n = ΣM i n i /} Σn i is calculated. The number average molecular weight can be measured by a variety of well-known methods, including gel permeation chromatography, spectral end group analysis, and osmotic pressure measurement.

The term "weight average molecular weight" as used herein refers to (M _w ) which is equal to ΣM _i ² n _i /ΣM _i n _i , where n _i is the number of molecules of molecular weight M _i . In various examples, the weight average molecular weight can be determined using light scattering, small angle neutron scattering, X-ray scattering, and sinking velocity.

The term "radiation" as used herein refers to energy particles that traverse through a medium or space. Examples of radiation are visible light, infrared light, microwaves, radio waves, very low frequency waves, very low frequency waves, thermal radiation (heat), and black body radiation.

As used herein, the term "light" refers to electromagnetic radiation in and around wavelengths visible to the human eye, including ultraviolet (UV) light and infrared light having a wavelength of from about 10 nm to about 300,000 nm.

As used herein, the term "curing" means exposure to any form of spoke. Shot, heat or allow to experience physical or chemical reactions that result in hardening, gelation, solidification or increased viscosity.

As used herein, the term "hole" refers to a depression, slit or hole of any size or shape in a solid article. The aperture can pass through the object through the entire object or portion. One hole can intersect with other holes.

As used herein, the terms "stand-alone" or "unsupported" refer to a film on the major faces of the major faces of the film that are not in contact with the substrate, whether the substrate is porous or not. In some embodiments, the "stand-alone" or "unsupported" film can be 100% unsupported for the two major faces. The "stand-alone" or "unsupported" film can be supported at the edges or supported on a smaller (e.g., less than about 50%) surface area on either or both major faces of the film.

As used herein, the term "supported" means that the majority of the surface area on at least one of the two major faces of the film is in contact with the substrate, whether or not the substrate is porous or not. In some embodiments, the "supported" film can be 100% supported on at least one side. The "supported" film can be supported at any suitable location on the major surface of either or both of the major faces of the film (e.g., greater than about 50%).

The term "enrich" as used herein refers to an increase in the amount or concentration of a liquid, gas or solute. For example, if the mixture of gases A and B has an increased concentration or amount of gas A, such as by gas A selectively penetrating through the membrane to increase gas A to the mixture, or selectively penetrating through the membrane, for example by gas B. To remove gas B from the mixture, gas A can be enriched.

The term "depletion" as used herein refers to a decrease in the amount or concentration of a liquid, gas or solute. For example, if the mixture of gases A and B has a reduced concentration of gas B Or amount, for example, by gas B selectively penetrating through the membrane to remove gas B from the mixture, or for example, by gas A selectively penetrating through the membrane to increase gas A to the mixture, depleting gas B .

The term "solvent" as used herein refers to a liquid that dissolves a solid, liquid or gas. Non-limiting examples of solvents are polyoxo, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.

As used herein, the terms "selective" or "ideal selectivity" refer to the ratio of the penetration of a relatively slow penetrating gas that is measured at room temperature to a relatively slow penetrating gas.

As used herein, the term "penetrability" refers to the permeability coefficient (P _x ) of a substance X through a membrane, where q _mx =P _x * A * Δp _x * (1/δ), where q _mx The volumetric flow rate of the substance X through the membrane, the surface area of one major surface of the membrane through which the A-based substance X flows, the partial pressure difference of the Δp _x- based substance X on both sides of the membrane, and δ is the thickness of the membrane. P _x can also be V. δ / (A.t. Δp) represents the permeability of the P _x -based gas X to the film, V is the volume of the gas X penetrating through the film, δ is the thickness of the film, and A is the film The area, the t-time, and the pressure difference between the Δp-based gas X on the retention surface and the penetration surface. Penetration is measured at room temperature unless otherwise stated.

As used herein, the term "penetration" refers to the normalized permeability (M _x ) of a substance X through a membrane, where M _x = P _{x /} δ = V / (A.t. Δp _x ), where The permeability of the P _x gas X to the film, the V system penetrates the volume of the gas X passing through the film, δ is the thickness of the film, A is the area of the film, t is the time, Δp _x is the substance X The difference in partial pressure on both sides of the membrane. Penetration is measured at room temperature unless otherwise stated.

As used herein, the term "Barrer or Barrers" means a unit of penetration, where 1 bar = 10 ^-11 (cm ³ gas) cm cm ^-2 s ^-1 mmHg ^-1 , or 10 ^-10 (cm ³ gas) cm cm ^-2 s ^-1 cm Hg ^-1 , where "cm ³ gas" represents the amount of gas occupying one cubic centimeter at standard temperature and pressure.

As used herein, the term "total surface area" with respect to a membrane refers to the total surface area of the membrane that is exposed to that side of the feed gas mixture.

As used herein, the term "air" means a gas mixture that is approximately the same as the natural composition of a gas taken from the atmosphere at approximately ground level. In some instances, the air is taken from a surrounding environment. The composition of the air includes about 78% nitrogen, 21% oxygen, 1% argon, and 0.04% carbon dioxide, as well as small amounts of other gases.

The term "room temperature" as used herein refers to a temperature of from about 15 °C to 28 °C.

The term "coated" as used herein refers to a continuous or discontinuous layer of material on the coated surface, wherein the layer of material can pass through the surface and can fill areas such as pores, wherein the substance The layer can have any three-dimensional shape, including flat or curved planes. In one example, the coating can be formed by immersing in a bath of cladding material on one or more surfaces, either of which may be porous or non-porous.

The term "surface" as used herein refers to a boundary or face of an object, wherein the boundary or face may have any surrounding shape and may have any three-dimensional shape, including flat, curved or angular, wherein the boundary or face may It is continuous or discontinuous. Although the term surface generally means that the object does not have the outermost boundary of the hidden depth, the term "hole" is used when referring to a surface, which refers to the surface opening and the depth at which the hole extends into the substrate below the surface.

Hollow fiber

In various embodiments, the present invention provides a method of forming hollow fibers. The method can include providing or obtaining a substantially cylindrical solid core. The core can include core groups Adult. The core composition may comprise from about 50 weight percent (wt%) to about 100 wt% of a composition that is at least one of fusible and sublimable. The method can include coating the core with a curable composition. The method can include curing the curable composition. The method can include melting or sublimating at least a portion of the core composition. The method can include removing at least a portion of the molten or sublimated portion of the core composition. This method provides hollow fibers. Different embodiments of the invention provide hollow fibers made by the method. In some embodiments, the method is a continuous method. In other embodiments, the method is a batch method.

Any suitable step can be incorporated into the method of making hollow fibers. In some examples, the core or support fibers are obtained commercially or otherwise, although in other examples, the core or support fibers are synthesized. In some embodiments, the melting or sublimating at least a portion of the core composition can include dissolving at least a portion of the core composition using a solvent. The method can include any suitable number of steps prior to providing the hollow fiber. For example, in embodiments including support fibers, the method can include removing the support fibers from the hollow fibers after at least partial melting or sublimation of the core composition. This removal can be performed using any suitable method. In some examples, the removing includes physically pulling the support fibers from the hollow fibers, completely or partially dissolving the support fibers in a suitable solvent, melting or sublimating the support fibers, or any combination thereof.

The hollow fiber can be any suitable hollow fiber. In some embodiments, the hollow fiber can comprise a cured polyoxyalkylene composition, such as can be used in different separation processes. The hollow fiber can have any suitable composition, length, diameter or shape consistent with the method of making the fibers described herein. In some examples, the wall of the hollow fiber has a thickness, such as an average thickness or a majority of the thickness of the hollow fiber (eg, equal to or greater than 50% of the length) of about 1 μm or less, or about 5 μm, 10 μm, 15 μm, 20 μm. , 25μm, 30μm, 35μm, 40μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 80 μm, 100 μm, 150 μm or about 200 μm or more. In some examples, the wall of the hollow fiber has a thickness of from about 1 μm to 200 μm, from 5 μm to 120 μm, or from about 10 μm to 60 μm.

In some embodiments, the method can be used to initiate a continuous procedure in which the fiber system is formed without a core.

Solid core

In some embodiments, the method of making a hollow fiber can include providing or obtaining a solid core. In some embodiments, the solid core can include at least one support fiber and a core composition that coats the support fiber; in other embodiments, the solid core includes a core composition but does not include a support fiber. The solid core is substantially solid so that no liquid or no significant liquid is included in the solid core. The core's solidity can be any suitable solidity, including substantially hard or soft solids such as pastes or gels. The solid can be any suitable solid such that the core is substantially non-flowable (e.g., having a viscosity greater than about 10,000 cP) under the coating and curing conditions of the solid core. For example, the solid core can comprise a core composition of a high viscosity liquid. In other embodiments, the solid core can comprise a core composition of crystalline or amorphous solids; for example, a liquid having a temperature below the melting point of the core composition. The solid core can have any suitable shape, for example the solid core can be about or substantially cylindrical. As used herein, "substantially cylindrical" includes any cylindrical shape, including a cylindrical shape having a substantially smooth or unpatterned surface, or a cylindrical shape having a patterned or patterned surface, wherein the pattern or pattern is any suitable pattern. Or pattern. The surface feature of the cylinder may extend away from the outer surface of the cylinder by less than about 10% of the radius of the cylinder, or from the outer surface of the cylinder to extend less than about 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or less than about 1% of the radius of the cylinder. In some embodiments, the pattern or pattern may appear uniformly on the core; in other embodiments, the pattern or pattern may be non-uniform, such as having different patterns or patterns at different locations, or may be interlaced with the smooth core. The substantially cylindrical core may be a circular cylinder or a flat cylinder. In some examples, the core has a diameter of about 10 μm or less, or about 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 1000 μm, 1500 μm, 2000 μm, 1 cm, or about A diameter of 5 cm or more. In some embodiments, the core has a diameter of from about 5 μm to 5 cm, from 10 μm to 2000 μm, from 50 μm to 800 μm, or from about 100 μm to 400 μm.

In embodiments including support fibers, the support fibers can be coated with the core composition such that the one or more fibers are in any suitable location within the core composition. For example, the one or more support fibers can be located approximately midway between the composition that coats the support fibers. In other examples, the one or more support fibers can be located at or near the edge of the solid core. In some examples, the one or more support fibers can have a location within the cladding core that varies along the length of the cladding core. In other embodiments, the one or more support fibers can have a position within the core composition that varies substantially along the length of the solid core. In some examples, the solid core comprises a support fiber, or 2, 3, 4, 5, 6, 7, 8, 9, or 10 or more support fibers. In some examples, the solid core includes a support fiber that is centered at the core composition and that varies substantially along the length of the solid core. In some examples, the core composition can substantially cover a substantial portion of the length of the support fibers.

In some embodiments, the solid core is obtained commercially or otherwise; in other embodiments, the method can include making the solid core. For example, in some implementations In one example, providing or obtaining the core can include coating the support fiber with the core composition. The coating can occur in any suitable manner. For example, the coating can occur by dipping or otherwise immersing the support fibers in the core composition. In some embodiments, the support fibers overlying the core composition material can be coated onto the support fibers by a suitable mold, stencil, needle or other suitable size adjustment or forming apparatus to result in a consistent amount of material. In other embodiments, the support fibers that cover the core composition material can be directly cured without any mold or other sizing or forming equipment. In some embodiments, coating the support fibers with the core composition can include at least one of immersion coating, die coating, extrusion, dipping, spraying, brushing, roller coating, and inkjet applications.

In some embodiments, providing or obtaining the core can include curing the core composition on the support fibers, or curing the core composition without the support fibers. This curing can occur in any suitable manner. In some embodiments, the curing occurs by sufficiently cooling the core composition of the coated support fibers or the core composition without the support fibers to cure the core composition. The curing can be from a liquid or semi-liquid to a solid frozen state, for example the curing can be to freeze the core composition. In some embodiments, the curing can be a transition of the thermoplastic material from a liquid or flowable state to a solid or no flow state. In some examples, the curing can include curing the core composition, such as hydrazine hydrogenation cure, condensation cure, free radical cure, amine epoxy cure, radiation cure, cooling, or any combination thereof. The curing can include any combination of freezing, thermoplastic transformation into a solid, non-flowing state, or curing.

Cooling of the core composition can include cooling to any suitable temperature such that the core composition becomes substantially solid or non-flowable. The cooling may include cooling the core composition until the core composition becomes a crystalline solid, an amorphous solid or is coated on the solid at the curable material The temperature of a high viscosity liquid having low or substantially no flow properties on the core of the body and then curing. The cooling may include cooling to about -250 ° C or lower, or about 200 ° C, 190 ° C, 180 ° C, 170 ° C, 160 ° C, 150 ° C, 140 ° C, 130 ° C, 120 ° C, 110 ° C, 100 ° C, 90 °C, 80°C, 70°C, 60°C, 50°C, 40°C, 30°C, 20°C, 10°C, 0°C, or about 10°C or higher. The cooling can include cooling to about -250 ° C to 10 ° C, -250 ° C to -10 ° C, or about -196 ° C to -30 ° C. This cooling can occur for any suitable amount of time, such as from about 0.001 s to about 1 min, from 0.01 to about 10 s, or from about 0.1 s to about 5 s. In some embodiments, the cooling is performed by immersing the support fibers covering the core composition in a liquid gas such as liquid nitrogen (e.g., about 196 ° C) for a suitable amount of time.

After curing the core composition, the solid core can be subjected to any suitable processing steps prior to coating with the curable composition. In some embodiments, no further processing steps occur. In other embodiments, the solid core can be transported through a die or another suitable size adjustment or forming apparatus, the core can be heated, the solid core can be crimped and stored for short or long periods of time, or any combination thereof. .

Support fiber

The solid core can include at least one support fiber and a core composition that coats the support fiber. The support fibers can be any suitable support fibers and can have any suitable shape, diameter, and length such that they can be used to form a solid core as used herein. In some examples, the support fibers can be provided on, for example, a reel or drum. In some examples, the support fibers may have a hollow core. In some examples, the support fibers have a diameter of about 5 μm or less, or about 10 μm, 20 μm, 50 μm, 75 μm, 100 μm, 125 μm, 150 μm, 175 μm, 200 μm, 225 μm, 250 μm, 275 μm, 300 μm, 325 μm, or about 350 μm. Or larger diameter. In some embodiments, the support fibers have a diameter of from about 5 μm to 1000 μm, from 10 μm to 600 μm, or from about 20 μm to 350 μm.

In some embodiments, the support fibers can have a higher melting point or sublimation point than the core composition. In other embodiments, the support fibers can have a lower melting point or sublimation point than the core composition. In some examples, the support fibers are substantially insoluble in at least one solvent that dissolves the core composition. In some examples, the support fibers are substantially soluble in at least one solvent that dissolves the core composition. In some embodiments, the support fibers are substantially soluble in at least one solvent that is insoluble or only minimally soluble in the cured curable composition coated on the solid core.

In some examples, the support fibers comprise an organic polymer or copolymer. In some examples, the support fiber comprises at least one of polyoxymethylene, a polyoxymethylene copolymer containing ethylene oxide and other structural units, polymethyl methacrylate (PMMA), PMMA copolymer, polystyrene, poly Styrene copolymer, cellophane, vinyl acetate, cyclic olefin copolymer, ethylene vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), fluorescent plastic, PTFE, acrylonitrile butadiene styrene (ABS) , polyacrylates, polyamines, polyamines, quinones, polyimines, polyethers, polybenzazoles, polyether oximes, polyketones, polyarylamines, polyetheretherketones (PEEK) , polycarbonate, polyester, polycaprolactone, polybutylene terephthalate, polyurethane, polyurea, polyurethane-urea copolymer, polyethylene terephthalate, polylactic acid, polyphenylene ether, polyphenylene sulfide, thermoplastic polyurethane-, Kevlar ^TM, polyvinyl acetate (PVA), polyvinyl chloride (PVC), poly-dichloro-vinylene (PVDC) and styrene acrylonitrile (SAN) copolymer. In some embodiments, the support fibers comprise at least one of polypropylene, polyvinyl alcohol, and monoterpene wettable fibers such as nylon 6,6, nylon 6,12 or polyethylene terephthalate. By.

Core composition

The solid core can include a core composition. In some embodiments, the core composition encapsulates the at least one support fiber; in other embodiments, the core composition does not have support fibers. The core composition can be any suitable core composition that can be suitably cured for the curable composition to coat the solid core, followed by curing, and the appropriate core composition can be cured after curing At least partially melted or sublimed. In various embodiments, the core composition can be formed from unsupported fibers or coated onto the support fibers in any suitable thickness and shape such that the cured core or the support fibers and the cured core form a solid having a suitable diameter. core. In some embodiments, the solid core comprises a frozen liquid. In some embodiments, the solid core comprises a solid that is sublimable below its sublimation temperature. In some embodiments, the solid core comprises a volatile solvent, such as a hydrogel or gelled organic solvent, or a gelled organooxane liquid, which gels the polymer or polymer network by a small amount of colloid.

The core composition can include any suitable ratio of sublimable or fusible material; the core composition need not be sublimable or fusible as a whole. In some embodiments, the core composition is substantially fully fusible or sublimable. In other embodiments, about 50 wt% or less of the core composition is a fusible or sublimable composition, or about 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt% 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or about 100% by weight of the core composition is a fusible or sublimable composition (eg at least one of fusible or sublimable). In some examples, from about 50 to 100 wt%, or from about 90 to 100 wt%, or from about 95 to 100 wt% of the core composition is fusible or sublimable. In some embodiments, a component can be described as being The fixed temperature is fusible if the component has about 10,000 cP or less at the temperature, or about 1000 cP, 500 cP, 400 cP, 300 cP, 200 cP, 100 cP, 90 cP, 80 cP, 70 cP, 60 cP, 50 cP, 40 cP, 30 cP, 20 cP. Or a zero shear viscosity of about 10 cP or less, or a zero shear viscosity of about 1 to 10,000 cP, 1 to 1,000 cP, 1 to 100 cP, 1 to 50 cP, or about 1 to 10 cP at this temperature.

In some embodiments, the fusible or sublimable composition can have a melting point or sublimation point above the support fiber. In other embodiments, the fusible or sublimable composition can have a melting point or sublimation point below the support fiber. In some examples, the core composition is substantially insoluble in at least one solvent that dissolves the support fibers. In some examples, the core composition is substantially soluble in at least one solvent that dissolves the support fibers. In some embodiments, the core composition is substantially soluble in at least one solvent that is insoluble or only minimally soluble in the cured curable composition coated on the solid core.

In various embodiments, the fusible or sublimable composition is fusible or sublimable at about -200 ° C or lower, or about -190 ° C, -180 ° C, -170 ° C, -160 ° C, -150 ° C, -140 ° C, -130 ° C, -120 ° C, -110 ° C, -100 ° C, -90 ° C, -80 ° C, -70 ° C, -60 ° C, -50 ° C, -40 ° C, -30 °C, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130 °C, 140 ° C, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 190 ° C, or about 200 ° C or higher. In some examples, the fusible or sublimable composition is fusible or sublimable to at least one of: from about -200 ° C to about 200 ° C, or from about -150 ° C to about 150 ° C, or about 0 ° C. To 60 ° C, 0 ° C to 35 ° C, or about -200 ° C to about 50 ° C, 40 ° C, 30 ° C, 20 ° C, 10 ° C, 0 ° C, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 55 ° C, 60 ° C, 65 ° C, 70 ° C, 75 ° C, or to about 80 ° C or higher. In some In an example, the fusible or sublimable composition has about 10,000 at a temperature of from about -200 ° C to -200 ° C, -150 ° C to 150 ° C, 0 to 60 ° C, or from about 0 ° C to 35 ° C. A zero shear viscosity of cP or lower, or about 1000 cP, 500 cP, 400 cP, 300 cP, 200 cP, 100 cP, 90 cP, 80 cP, 70 cP, 60 cP, 50 cP, 40 cP, 30 cP, 20 cP, or about 10 cP or less. In some examples, the fusible or sublimable composition has about 500 cP or less, 400 cP, 300 cP, 200 cP, 100 cP, 90 cP, 80 cP, 70 cP, 60 cP, 50 cP, 40 cP, 30 cP, 20 cP at about 25 ° C. , or a zero shear viscosity of about 10 cP or less. In some embodiments, from about 0 ° C to about 35 ° C, about 100 wt% of the fusible or sublimable composition, or about 95 wt%, 90 wt%, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or about 5 wt% of the fusible or sublimable composition having from about 0 to 10,000 cP, from 0 to 1,000 cP, from 0 to 100 cP , 0 to 50 cP, or a viscosity of about 0 to 10 cP.

In various examples, the core composition can include at least one of water, an organic cyclodecane, a hydrogel polymer, and a curable polyoxynium composition. The curable polyfluorene composition can be any suitable curable composition as described herein, such as an organic rhodium-curable composition, such as a hydrazine-hydrogenated curable polyoxo-oxygen composition, but the cured core composition At least partially fusible or sublimable. In some embodiments, the core composition comprises less than about 30% by weight of the hydrogel polymer, or less than about 25 wt%, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7 6, 6, 5, 3, 2, 1, or less than about 0.1% by weight of the hydrogel polymer; in some instances, the remainder of the core composition or the remainder of the core composition may It is water, such as from about 75 to 99.9 wt% water, from about 85 to 99 wt% water, or from about 93 to 98 wt% water. In some examples, the core composition comprises from about 0 to 30 wt% of the hydrogel polymer, from 1 to 20 wt%, or from about 2 to 10 wt% of the hydrogel polymer. In some embodiments, the core composition comprises less than about 30% by weight Curing the polyoxymethylene composition, or less than about 25 wt%, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 wt%, or less About 0.1% by weight of the curable polyfluorene oxide composition such as a hydrazine hydrogenated cured composition; in some examples, the remainder of the remainder of the core composition may be an organic cyclopolysiloxane such as octamethylcyclotetra A siloxane, such as from about 75 to 99.9 wt% organic cyclopolysiloxane, from about 85 to 99 wt% organic cyclopolysiloxane, or from about 93 to 98 wt% organic cyclopolysiloxane.

In various embodiments, the hydrogel polymer can comprise any suitable hydrogel-forming polymer, such as polyethylene glycol, polyethylene tetrahydro ketone, polyacrylamide, polyhydroxy methacrylate Ester, polyvinyl alcohol, polyethylene glycol, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyhydroxyethyl methacrylate, polyacrylic acid, polyacrylonitrile hydrolysate, polyethyleneimine , a combination of ethoxylated polyethyleneimine, polyallyl alcohol, polyallylamine, polyallylamine, polyethylene vinyl alcohol, gelatin, or a combination thereof.

The organic cyclodecane can be any suitable organic cyclodecane. In various embodiments, the organocyclodecane may comprise from about 3 to 6, 3 to 10, or from about 3 to 12 bis(C _1-5 alkyl) decane repeating units. In some examples, the organocyclodecane can have the formula: Wherein n is from about 3 to about 12 (e.g., the organocyclodecane comprises [R ₂ SiO _2/2 ] units), wherein each R is independently selected from C _1-5 alkyl. In some examples, the organocyclodecanane can have from 3 to 12 dimethyloxetane repeating units. In some embodiments, the organocyclodecane can be a hexa(C _1-5 alkyl)cyclotrioxane, an octa(C _1-5 alkyl)cyclotetraoxane, and a ten (C _1-5 An alkyl)cyclopentaoxane, dodecyl(C _1-5 alkyl)cyclohexaoxane, or any combination thereof, wherein each C _1-5 alkyl group is independently selected or the same each time it is present and It may be substituted or unsubstituted; for example, each C _1-5 alkyl group is independently selected from the group consisting of methyl, ethyl, propyl, butyl and pentyl groups. In various examples, the organic cyclodecane can be hexamethylcyclotrioxane (D3), octamethylcyclotetraoxane (D4), decamethylcyclopentaoxane (D5), ten Dimethylcyclohexaoxane (D6), or any combination thereof.

Wrap the core

A method of making a hollow fiber can include coating the core with a curable composition. The coated core can have any suitable shape, for example the coated core can be about or substantially cylindrical. In some examples, the coated core has a diameter of about 10 μm or less, or about 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 1000 μm, 1500 μm, 2000 μm, 1 cm, Or a diameter of about 5 cm or more. In some embodiments, the coated core has a diameter of from about 5 μm to 5 cm, from 10 to 2000 μm, from 50 to 800 μm, or from about 100 to 400 μm.

The coating can be continuously coated along and around the length of the solid core. The coating may have a substantially average thickness in a direction around the solid core and a length direction of the solid core. The curable composition can substantially uniformly coat a substantial portion of the length of the solid core. For example, the solid core can be located approximately in the middle of the curable composition that coats the solid core. The solid core can have a substantially uniform location within the cladding of the curable composition. In other instances The solid core may be located at or near the edge of the curable composition coating. The solid core can have a location within the curable composition that varies along the length of the cladding core.

The coating can occur in any suitable manner. For example, the coating can occur by dipping or otherwise immersing the solid core in the curable composition. In some embodiments, the solid core overlying the curable composition material can be coated onto the solid core by a suitable mold, stencil, needle or other suitable size adjustment or forming apparatus to cause a consistent amount of material to be coated on the solid core. . In other embodiments, the solid core overlying the curable composition can be directly cured or otherwise removed without the need for any mold or other sizing or forming equipment. In some embodiments, coating the solid core with the curable composition can include at least one of immersion coating, die coating, extrusion, dipping, spraying, brushing, roller coating, and inkjet.

Curable composition

A method of making a hollow fiber can include coating the solid core with a curable composition. The curable composition can be any suitable curable composition such that the curable composition can be used to produce hollow fibers using the methods described herein. In some examples, the core composition can include a suitable curable composition, such as a suitable hydrogenated curable composition, such that the solid core can be used to produce the hollow fibers described herein. In various examples, the curable composition comprises at least one of: a hydrazine hydroformable composition, a condensation curable composition, a free radical curable composition, an amine epoxy curable composition, a radiation curable composition , a curable composition, a vapor curable composition, or any combination thereof. In some embodiments, the curing may occur at any suitable temperature below normal or normal temperature, such as where the fusibility or can be increased The core composition of the Chinese nature is essentially non-meltable and non-sublimable.

In some embodiments, the curable composition is a curable organic bismuth composition. Curing the curable organic bismuth composition produces a cured product of the organic bismuth composition. The curable organic bismuth composition includes suitable ingredients to allow the composition to cure in a suitable manner. In addition to the at least one suitable polyoxyalkylene oxide, the organic bismuth composition may also comprise any suitable other ingredients, including any suitable organic or inorganic ingredients, including bismuth-free ingredients, including poly-aluminoxanes. The composition of the structure. In some examples, the cured product of the organic bismuth composition includes polyoxyalkylene.

The curable organic bismuth composition includes a molecular component having properties that allow the composition to cure. In some embodiments, the property that allows the curable organic bismuth composition to cure is a specific functional group. In some embodiments, the individual compounds contain functional groups or have properties that allow the curable organic bismuth composition to be cured by one or more curing methods. In some embodiments, a compound may comprise a functional group or have the property of allowing the curable organic bismuth composition to cure in one manner, while another compound may comprise a functional group or have the same to allow the curable organic bismuth composition to be the same Or the nature of curing in different ways. The functional group that allows curing can be located at the pendant position of the compound or, if applicable, the end position.

The curable organic bismuth composition includes any suitable organic hydrazine compound. The organoindole compound can be, for example, decane, polydecane, decane or polyoxyalkylene, such as any suitable compound of the art known in the art. The curable organic ruthenium composition can comprise any number of suitable organic ruthenium compounds, as well as any number of other suitable organic compounds. The organic cerium compound may include any functional group that allows curing.

In some embodiments, the organotellurium compound can include a hydrazine-bonded hydrogen atom, such as an organohydrogenane or an organohydrogenoxane. In some embodiments, the organogermanium compound can have Alkenyl group, such as an organic alkenyl decane or an organic alkenyl decane. In other embodiments, the organogermanium compound can include any functional group that allows for curing. The organodecane can be monodecane, dioxane, trioxane or polydecane. Similarly, the organooxane can be a dioxane, a trioxane or a polyoxyalkylene. The structure of the organic ruthenium compound may be linear, branched, cyclic or resinous. The cyclodecane and cyclodecane may have 3 to 12 germanium atoms, or 3 to 10 germanium atoms, or 3 to 4 germanium atoms.

In one example, the organohydrogenane can have the formula HR ¹ ₂ Si-R ² -SiR ¹ ₂ H, wherein R ¹ is a C _1-10 hydrocarbyl group or a C _1-10 halogen-substituted hydrocarbyl group, both of which are free of straight a chain or branched aliphatic unsaturation, and R ² is an alkylene group containing no aliphatic unsaturation, which has a monoaryl group selected from the group consisting of a monoaryl group (such as a 1,4-disubstituted phenyl group, a 1,3-disubstituted group) Phenyl), or a diaryl group (such as 4,4'-disubstituted-1,1'-bisphenyl, 3,3'-disubstituted-1,1'-diphenyl) or having from 1 to 6 A similar bisaryl group of a hydrocarbon chain linking a aryl group to a methylene group of another aryl group.

The organic cerium compound may be an organic polyoxy siloxane compound. In some examples, the organopolyoxyalkylene compound has an average of at least one, two, or more than two functional groups that allow curing. The organopolyoxyalkylene compound may have a linear, branched, cyclic or resinous structure. The organopolyoxyalkylene compound can be a homopolymer or a copolymer. The organopolyoxyalkylene compound may be a dioxane, a trioxane or a polyoxyalkylene.

In one example, the organopolyoxane may comprise a compound of the formula: (a) R ¹ ₃ SiO(R ¹ ₂ SiO) _α (R ¹ R ² SiO) _β SiR ¹ ₃ , or (b) R ⁴ R ³ ₂ SiO(R ³ ₂ SiO) _χ (R ³ R ⁴ SiO) _δ SiR ³ ₂ R ⁴ .

In formula (a), a has an average of from about 0 to about 2000, and beta has an average of from about 2 to about 2,000. Each R ¹ is an independent monovalent functional group. Suitable monovalent functional groups include, but are not limited to, acrylate groups, alkyl groups, halogenated hydrocarbon groups, alkenyl groups, alkynyl groups, aryl groups, and cyanoalkyl groups. Each R ² system is independently a functional group that allows the polyoxymethylene composition or R ^{1 to be} solidified.

In the formula (b), χ has an average value of from 0 to 2,000, and δ has an average value of from 0 to 2,000. Each R ³ is an independent monovalent functional group. Suitable monovalent functional groups include, but are not limited to, acrylate groups, alkyl groups, halogenated hydrocarbon groups, alkenyl groups, alkynyl groups, aryl groups, and cyanoalkyl groups. Each R ⁴ system is independently a functional group that allows the polyoxymethylene composition or R ^{3 to be} solidified.

The organopolyoxyalkylene compound can comprise an average of from about 0.1 mole percent to about 100 mole percent and any mole percent range between the functional groups that allow the polyoxymethylene composition to cure. The percentage of moles of the functional group which allows the ruthenium composition to be solidified in the resin is the number of moles of the oxirane unit in the resin having a functional group which allows the polyfluorene oxide composition to be cured, and the organopolyoxane The ratio of the total number of moles of the siloxane unit is multiplied by 100.

The curable organic bismuth composition may comprise a single organopolyoxane or a combination of two or more organopolyoxynitanes comprising at least one of the following properties: structure, viscosity, average molecular weight, oxane unit and sequence .

Examples of the organic polyoxyalkylene oxide may include a compound having the following average unit formula: (R ¹ R ⁴ R ⁵ SiO _1/2 ) _w (R ¹ R ⁴ SiO _2/2 ) _x (R ⁴ SiO _3/2 ) _y (SiO _4/2 ) _z (I), wherein R ¹ is independently selected from any of the optionally substituted C _1-15 functional groups, including C _1-15 monovalent aliphatic hydrocarbon groups, C _4-15 monovalent a functional group substituted with an aromatic hydrocarbon group and a monovalent epoxy group, and R ⁴ is a functional group which allows the polyfluorene oxide composition or R ⁵ or R ^{1 to be} solidified, and R ⁵ is R ¹ or R ⁴ , , , , And . In some embodiments, R ¹ is a C _1-10 hydrocarbyl group or a C _1-10 halogen-substituted hydrocarbyl group (both free of aliphatic unsaturation), or a C ₄ to C ₁₄ aryl group. In some embodiments, w is 0.01 to 0.6, x is 0 to 0.5, y is 0 to 0.95, z is 0 to 0.4, and .

In the description of the averaging unit formula I, the subscripts w, x, y, and z are the molar fractions. It will be appreciated that those skilled in the art will appreciate that in the case of the averaging unit (I), the variables R ¹ , R ⁴ and R ⁵ may be independently different between individual oxirane units. Alternatively, the variables R ¹ , R ⁴ and R ⁵ may be independently the same between the individual oxirane units. For example, the above average unit formula (I) may include the following average unit formula: (R ¹ R ⁴ R ⁵ SiO _1/2 ) _w (R ^1a R ⁴ SiO _2/2 ) _x1 (R ^1b R ⁴ SiO _2/2 ) _x2 (R ⁴ SiO _3/2 ) _y (SiO _4/2 ) _z

Wherein the subscript x1+x2=x, and wherein R ^{1a is} not equal to R ^1b . Alternatively, R ^1a may be equal to R ^1b .

In some embodiments, the curable composition includes a free radical initiator such as a peroxide, an azo-nitrile or an organoborane based compound. In some embodiments, the curable composition comprises a photoacid generator or a photo-sensitive agent. In some embodiments, the curable composition comprises an organoborane-organic nitrogen. In some embodiments, the curable composition is capable of cooling the cured hot melt composition.

Selective ingredient

Any of the optional ingredients described herein may be present in the hollow fibers and coated in the core In the curable composition of the heart, or in the core composition; or any optional ingredient described herein may be absent from the hollow fibers, the curable composition coated on the core, or the core composition. Without limitation, examples of such optional additional ingredients include surfactants, emulsifiers, dispersants, polymer stabilizers, crosslinkers, combinations of polymers, crosslinkers, and can be used to provide secondary polymerization or particle delivery. Catalysts, rheology modifiers, density modifiers, aziridine stabilizers, curing modifiers such as hydroquinone and hindered amines, free radical initiators, defoamers, polymers, diluents, acid acceptors , antioxidants, heat stabilizers, flame retardants, scavengers, alkylating agents, foam stabilizers, solvents, diluents, plasticizers, fillers, inorganic particles, inorganic pigments, inorganic dyes and inorganic drying agents. The liquid can be optionally used. Examples of the liquid include water, an organic solvent, any liquid organic compound, a polyoxygenated liquid, an organic oil, an ionic fluid, and a supercritical fluid. Other optional ingredients include polyethers having at least one alkenyl group per molecule, thickeners, fillers and inorganic particles, stabilizers, waxes or waxy materials, polyfluorene oxides, organofunctional alkoxynes, alkylmethyl groups The decane, the decane, the polyoxy siloxane, the polyoxymethanol liquid may be an optional component, a water-soluble or water-dispersible polyoxopolyether composition, a polyoxyxene rubber, a hydrazine hydrogenation catalyst inhibitor, Adhesion promoters, heat stabilizers, UV stabilizers, and flow control additives.

Curing the curable composition

A method of making a hollow fiber can include curing a curable composition coated on the core. The curing can be any suitable curing. For example, the curing can include hydrazine hydrocure curing, condensation curing, free radical curing, amine epoxy curing, radiation curing, cooling, or any combination thereof. In various embodiments, curing includes exposing the solid core coated by the curable composition to radiation such as heat or light. In some embodiments, the curing comprises heating the curable composition to about -196 ° C or lower, 150 ° C, 125 ° C, 100 ° C, 75 ° C, 50 ° C, 25 ° C, 0 ° C, 25 ° C, 50 ° C, 75 ° C, 100 ° C, 125 ° C, 150 ° C, 175 ° C, or About 200 ° C or higher. In some embodiments, the curing comprises heating the curable composition to between about -200 ° C to about 200 ° C, -40 ° C to about 35 ° C, or from about 0 ° C to about 25 ° C. Heating can be carried out in any suitable manner. In some embodiments, the coated core passes through the heated zone for a sufficient time to cure the curable composition. In some examples, the coated core is heated for about 0.01 s or less, 1 s, 5 s, 30 s, 1 minute, 5 minutes, 30 minutes, or about 1 hour or longer. In some embodiments, the curable composition coated solid core is heated from about 0.0001 s to about 1 h, from 0.001 to 1 minute, or from about 0.01 s to about 5 s. Heating can be carried out using any conventional method, such as passing the material through an oven, heating tube, or otherwise exposed to any suitable form of radiation.

Different curing methods can be used, including any suitable curing method including, for example, hydrazine hydrocure curing, condensation curing, free radical curing, amine epoxy curing, radiation curing, cooling, or any combination thereof. The composition cured by a curing method can be cured by other curing methods in addition to the one curing method. The curable composition, such as a curable organic ruthenium composition, can include molecules having properties that allow for one curing process, as well as molecules that allow for different curing methods. In some embodiments, the curable organic bismuth composition can include a plurality of characteristics on the same molecule that allow the composition to cure via a curing process and cure via other curing methods, and in some embodiments, the organic bismuth composition The article may include properties that allow it to cure via a curing process on one molecule and properties that allow it to cure via other curing methods on different molecules.

Curable compositions that can be cured by a particular method can include, in addition to the organogermanium compound, other compounds that can be cured via this particular method. In some embodiments, the other can A compound that is cured via this particular curing process can participate in an organogermanium compound that can be cured via the particular curing process during the performance of the particular curing process. In other embodiments, the other compound that is curable via the particular curing process does not participate in the organogermanium compound that can be cured via the particular curing process during the performance of the particular curing process.

In the hydrogenation curing of hydrazine, for example, an organic hydrazine compound including a ruthenium atom having a ruthenium-bonded hydrogen atom is reacted with an unsaturated group such as an alkenyl group, and an addition to the unsaturated group causes the unsaturated group to lose at least one degree of unsaturation. (for example, a double bond is converted into a single bond) such that the ruthenium atom is bonded to one of the carbon atoms of the original unsaturated group, and the hydrogen atom is bonded to another carbon atom of the original unsaturated group. Having an average of at least two unsaturations on one or more molecules and having an average of more than two hydrazine-bonded hydrogen atoms in one or more molecules facilitates cross-linking. In another example, having an average of more than two unsaturated groups on one or more molecules and having an average of at least two hydrazine-bonded hydrogen atoms in one or more molecules facilitates crosslinking. In one example, the curable organic ruthenium composition curable by hydrazine hydrogenation may comprise a compound having an average of at least two unsaturated groups per molecule, an organic ruthenium compound having an average of at least two ruthenium-bonded hydrogen atoms per molecule, and A selective hydrogenation catalyst. In some embodiments, the rhodium hydrogenation catalyst is present. In other embodiments, the rhodium hydrogenation catalyst is absent. In some embodiments, the unsaturated group is an alkenyl group.

In some embodiments, the rhodium hydrogenation catalyst can be any rhodium hydrogenation catalyst comprising a platinum group metal or a platinum group metal containing compound. The platinum group metal may include platinum, rhodium, ruthenium, palladium, osmium, and iridium. Examples of the ruthenium hydrogenation catalyst include chloroplatinic acid and certain vinyl-containing organic oxime-containing complexes such as chloroplatinic acid and 1,3-divinyl-1,1 disclosed in U.S. Patent No. 3,419,593. a reaction product of 3,3-tetramethyldioxane; a microencapsulated ruthenium hydrogenation catalyst comprising a platinum group metal encapsulated in a thermoplastic resin, such as U.S. Patent No. 4,766,176 and U.S. Patent No. 5,017,654 And exemplified by a photoactivated ruthenium hydrogenation catalyst, such as platinum (II) bis(2,4-pentanediester), as exemplified in U.S. Patent No. 7,799,842. An example of a suitable hydrogenation catalyst may include a platinum (IV) complex of 1,3-divinyl-1,1,3,3-tetramethyldioxane. An example of a suitable rhodium hydrogenation catalyst is a Karstedt catalyst.

In another embodiment, the rhodium hydrogenation catalyst can be at least one photoactivated rhodium hydrogenation catalyst. The photoactivated rhodium hydrogenation catalyst can be any of the well-known rhodium hydrogenation catalysts including platinum group metals or platinum group metal containing compounds. The suitability of the specific photoactivated ruthenium hydrogenation catalyst for the organic ruthenium composition of the present invention can be readily determined by routine experimentation.

The concentration of the ruthenium hydrogenation catalyst may be sufficient to catalyze the hydrogenation of the hydrazide of the curable organic ruthenium composition, for example, an organic ruthenium compound sufficient to catalyze an average of at least two ruthenium-bonded hydrogen atoms per molecule and an average of at least two ruthenium linkages per molecule. Addition reaction of an organic polyoxyalkylene group of an alkenyl group (hydrazine hydrogenation). Typically, the rhodium hydrogenation catalyst is present in a concentration sufficient to provide from about 0.1 to about 1000 ppm of platinum group metal, from about 0.5 to about 500 ppm of platinum group metal, and more preferably from about 1 to about 100 ppm of platinum, based on the total weight of the uncured composition. Metal. When the platinum group metal is less than about 0.1 ppm, the curing rate is very slow. It is possible to use more than 1000 ppm of platinum group metal, but it is usually not adopted due to catalyst cost considerations.

In the condensation curing, for example, an organic ruthenium compound including a ruthenium-bonded hydrolyzable group is reacted with water to form a hydrazine-substituted ruthenium atom. The reactive hydroxyl group can then attack other deuterium atoms, including other deuterium atoms having a hydrolyzable group or having a hydroxyl group to form a polyoxyalkylene. In some embodiments, the ruthenium atom attacked by the reactive hydroxyl group can have a protonated hydroxyl group or a hydrolyzable group, wherein the protonated hydroxyl group or hydrolyzable group is a good leaving group. In some embodiments, no water is required to hydrolyze the hydrolyzable groups, but instead is already present in the curable organic bismuth composition The reactive hydroxy group in the organic hydrazine replaces the organic hydrazine to attack other ruthenium atoms, including a ruthenium atom having a hydroxyl group or a ruthenium atom having a hydrolyzable group. The acid or base catalyst is a selective component of the condensable curable organic hydrazine composition, such as any suitable organic or inorganic acid, or any suitable base. In some embodiments, an acid or base catalyst is present. In other embodiments, an acid or base catalyst system is absent.

The condensation-curable organic ruthenium composition may include an organic ruthenium having at least one oxime-substituted hydrolyzable group or having at least one ruthenium-substituted hydroxy group. The organic hydrazine can be decane, polydecane, decane or polyoxyalkylene. The organic oxime may comprise an average of one hydrazine-substituted hydrolyzable group per molecule, an average of two hydrazine-substituted hydrolyzable groups per molecule, or more.

The hydrolyzable group can be reacted with water to form a sterol (Si-OH) group or another hydroxy substituent in any temperature from room temperature to 100 ° C in the absence of a catalyst within a few minutes, for example 30 minutes. The group. Examples of hydrolyzable groups may include, but are not limited to, -Cl, -Br, -OR ⁷ , -OCH ₂ CH ₂ OR ⁷ , CH ₃ C(=O)O-, Et(Me)C=NO-, CH ₃ C (=O) N(CH ₃ )- and -ONH ₂ , wherein R ₇ is a C ₁ to C ₈ hydrocarbon group or a C ₁ to C ₈ halogen-substituted hydrocarbon group. In one example, the condensation-curable organic ruthenium composition comprises one or more of the following: Me ₂ ViSiCl, Me ₃ SiCl, MeSi(OEt) ₃ , PhSiCl ₃ , MeSiCl ₃ , Me ₂ SiCl ₂ , PhMeSiCl ₂ , SiCl ₄ , Ph ₂ SiCl ₂ , PhSi(OMe) ₃ , MeSi(OMe) ₃ , PhMeSi(OMe) ₂ and Si(OEt) ₄ , wherein Me is a methyl group, Et is an ethyl group and Ph is a phenyl group.

Alternatively, the condensation curable composition may include a condensation catalyst. In some embodiments, a condensation catalyst is present. In other embodiments, the condensation catalyst is absent. Examples of the condensation catalyst include, for example, an amine, and lead, tin, zinc, titanium, zirconium, aluminum, and a complex of iron and a carboxylic acid. In one example, the condensation catalyst can be selected from the group consisting of tin (II) and tin (IV) compounds such as February. Tin cinnamate, tin dioctoate and tetrabutyl tin; and titanium compounds such as titanium tetrabutoxide.

In, for example, free radical curing, free radicals are generated. This radical can then attack the free radically polymerizable functional group. The attack group forms a bond with the radical polymerizable group and transfers a radical to the group. The free radically polymerizable functional group can then continue to attack other free radically polymerizable functional groups.

The radically curable organic ruthenium composition may include an organic ruthenium having at least one radical polymerizable group. The organic hydrazine can be decane, polydecane, decane or polyoxyalkylene. The organic oxime may include an average of one radical polymerizable group per molecule, an average of two radical polymerizable groups per molecule, or more. In some embodiments, the radically curable organic ruthenium composition may include an organic compound that does not include ruthenium having at least one radical polymerizable group. The organic compound not including ruthenium may include an average of one radical polymerizable group per molecule, an average of two radical polymerizable groups per molecule, or more. The radical polymerizable group includes, for example, an alkenyl group and an alkynyl group, and a group such as an ether, a ketone, an aldehyde, a carboxylic acid, a ketal, an acetal, a cyano group, a nitro group or a halogen.

The free radicals can be produced by any suitable method. The free radicals can be initiated by, for example, thermal decomposition, photolysis, redox reactions, persulfates, free radiation, electrolysis, plasma, sonic vibration, chemical decoupling, or combinations thereof. In one example, the free radicals are produced using a free radical initiator. The free radical initiator is an optional component. In some embodiments, a free radical initiator is present. In other embodiments, the free radical initiator is absent. In one example, the free radical initiator can be a free radical photoinitiator, an organic peroxide, or a thermally activated free radical initiator. Further, the radical photoinitiator may be any radical photoinitiator capable of initiating curing (crosslinking) of the radical polymerizable functional group when exposed to, for example, radiation having a wavelength of from 200 to 800 nm. In another In one embodiment, the free radical initiator is an organoborane free radical initiator. In one example, the free radical initiator can be an organic peroxide. For example, an increase in temperature can allow the peroxide to decompose and form a highly reactive free radical that can initiate free radical polymerization. In some instances, the decomposed peroxides and their derivatives can be by-products. In some embodiments, the curable composition comprises an organoborane-organic nitrogen capable of forming a free radical that can be activated to initiate free radical curing conditions without heating or radiation, by mixing or exposure to a de-synthesis compound. Complex compound. In some embodiments, the curable compound is cured by exposing the composition to a volatile de-synthesis compound such as acetic acid (liquid or vapor). The free radical photoinitiator can be a single free radical photoinitiator or a mixture comprising two or more different free radical photoinitiators. The concentration of the radical photoinitiator may be 0.1 to 6% (w/w) or 1 to 3% (w/w) based on the weight of the cerium compound in the radically curable organic cerium composition. . An example of a thermally or photoactivatable free radical initiator is VAROX DCBP-50, which comprises 50% bis(2,4-dichlorobenzylidene) in a polyoxyxanic oil. peroxide.

In amine epoxy curing, for example, a primary or secondary amine is reacted with an epoxy compound to produce, for example, an amine alcohol. The epoxy group-containing compound may be an organic cerium compound or an organic compound free of cerium. The compound containing a primary or secondary amine may be an organic hydrazine or an organic compound free of hydrazine. The amine functional compound can be an amine functional organopolyoxane.

In one example, the amine epoxy curable composition comprises an epoxy functional organoruthenium compound and an amine based functional curing agent. In one example, the epoxy-functional organogermanium compound is a polyoxyalkylene compound. The epoxy-functional organogermanium compound may have an average of two or at least two functional groups substituted with a fluorene-bonded epoxy group per molecule, and the curing agent may have an average of at least two nitrogen-bonded hydrogen atoms per molecule.

Radiations that can be used for radiation curing include, for example, visible light, infrared light, microwaves, radio waves, very low frequency waves, very low frequency waves, thermal radiation (heat), and black body radiation. Any of the curing methods disclosed herein can include radiation curing; for example, any of the curing methods disclosed herein can include applying heat or light. For example, any of the hydrazine hydrogenated curable composition, the condensation curable composition, the epoxy amine curable composition, the cooled curable composition, or the free radical curable composition may include one or more of the application of radiation. And the step of applying the radiation to the curable composition initiates, assists, or causes a portion of the chemical or physical reaction of the curing. In some embodiments, either hydroquinone curing, condensation curing, epoxy amine curing, free radical curing, or curing via cooling may also be described as radiation curing because the radiation is applied during the curing process. In other embodiments, either hydroquinone curing, condensation curing, epoxy amine curing, free radical curing, or curing via cooling is not described as radiation curing because no radiation is applied during the curing process.

In some embodiments, the curable composition is a hot melt composition that cures upon cooling. In an example of cooling to produce a cured product of an organic cerium composition, the organic cerium composition having substantially a liquid flowable state is cooled to a temperature at least as low as normal temperature to produce an organic cerium composition having a substantially solid non-flowable state. Things. An organic ruthenium composition comprising a compound which can be used as a thermoplastic is an example of a ruthenium composition which can be cooled to produce a cured product of the ruthenium composition. The compound as a thermoplastic plastic may be a polymer.

Melting or sublimating the core composition

A method of making hollow fibers can include melting or sublimating the core composition. Melting or sublimation may be any suitable melting or sublimation, provided that the melting or sublimation provides at least one step in the hollow fiber membrane or in providing the hollow fiber membrane.

The melting or sublimation may be partially melted or sublimed such that less than 100% of the core composition melts or sublimes. In some embodiments, the melting or sublimation can be substantially completely melting or sublimating the core composition. In some embodiments, less than 100% of the core composition is fusible or sublimable; in some examples, the melting or sublimation is when removing some or substantially all of the fusible or sublimable component. It leaves the infusible or non-sublimable component of the core composition. In some examples, the non-meltable or non-sublimable component of the core composition, or the fusible or sublimable component of the core composition that is not melted or sublimed, may remain in the hollow fiber without removal; In other examples, the remaining material may be partially or substantially completely removed using other techniques. In some examples, removing the support fibers from the hollow fibers can at least partially remove the remaining material from the hollow fibers.

The melting or sublimation can include heating the cladding core or allowing the cladding core to warm to a higher temperature. In some examples, the melting or sublimating can include placing the cladding core in a vacuum. In various embodiments, the melting or sublimation can include placing the coated core in a heated environment such as an oven and allowing the coated core to warm to a temperature at which melting or sublimation occurs, such as about -50 ° C or less, or about 10 ° C, 25 ° C, 35 ° C or about 60 ° C or higher.

Removal of at least a portion of the melted or sublimated portion of the core composition can be carried out in a suitable manner. For example, the molten core composition can be discharged from one end of the hollow fiber; in some examples, air pressure, solvent washing, rolling the hollow fiber between the rollers, or any other suitable method can be used to induce the The molten core composition is discharged from the end of the hollow fiber. In some examples, the melted core composition can be moved through the hollow fibers to the outside of the hollow fibers and then wiped off or washed away. In some examples, a liquid can be in contact with the outer side of the hollow fiber to assist in removing the molten core composition. In some instances, it can be administered a liquid permeable to the film, such as a suitable solvent, which helps to dilute the molten core composition and push it out of the end of the fiber, or it can dissolve the unmelted or partially melted core composition to rinse out the fiber. End or diffuse through the fiber.

In some embodiments, a solvent can be used to dissolve at least a portion of the core composition or the support fibers before, during, or after the melting or sublimation. In some embodiments, a solvent can be used to remove at least a portion of the core composition after it has been at least partially melted or sublimed; in some embodiments, the solvent can be used to assist in blasting from the hollow fiber. The core material of the melt. In some embodiments, the melting or sublimation used with solvent solubilization or rinsing can substantially remove the desired amount of solid core composition from the hollow fiber, as compared to the dissolution alone.

Removal of the molten or sublimated species can be assisted by introducing a sweeping liquid or gas into the pores of the fiber, for example to establish convection.

The removal of the core can be done immediately after the coating is cured, or can be accomplished in the separation operation at any time after the fiber is produced. In some cases, it may be desirable to leave a complete core to provide additional support for the fibers during processing, or otherwise assist in subsequent processing steps, such as module combinations. In some cases, it may be desirable to remove the core to assist in subsequent processing.

Wrapped core

Various embodiments of the present invention provide a curable composition coated core. The curable composition coated core can be any suitable core consistent with the methods, cores, and curable compositions described herein. For example, in some embodiments, the present invention provides an organopolyoxane coated core. The coated core can comprise a substantially cylindrical solid core having a diameter of from about 10 [mu]m to about 2000 [mu]m. The core may also include a core composition. The core composition can include from about 50% to about 100% by weight of a curable or sublimable composition having at least one of fusibility and sublimability at any suitable temperature, such as from about -200 °C to about 60 °C. The coated core can also include a curable organopolyoxane composition coated on the core. In some embodiments, the curable composition coated on the core is at least partially cured.

Various embodiments of the present invention provide a cured curable composition coated core. In some examples, the cured curable composition comprises a cured organopolyoxane composition. The cured composition coated core can comprise any suitable coated core consistent with the methods, cores, and curable compositions described herein. For example, in some embodiments, the present invention provides a core coated with a cured organopolyoxane composition. The coated core can comprise a substantially cylindrical solid core having any suitable diameter, such as a diameter of from about 10 [mu]m to about 2000 [mu]m. The core can include a core composition comprising from about 50% to about 100% by weight of a fusible or sublimable composition having at least one temperature at any suitable temperature, such as from about -200 ° C to about 60 ° C. At least one of fusibility and sublimation. The coated core also includes an at least partially cured curable organopolyoxane composition overlying the core. The wall of the at least partially cured organopolyoxane composition can have any suitable thickness, such as a thickness of from about 1 [mu]m to about 200 [mu]m. In some embodiments, the at least partially cured curable composition can be substantially fully cured.

Method of separating components in a feed mixture

In various embodiments, the invention provides a method of separating a liquid or gas component of a feed gas or liquid mixture. The separation method can be any suitable separation method, the party The method includes hollow fibers provided by any of the methods described herein. In some examples, the method includes contacting a first side of a feed gas or liquid mixture with a membrane, wherein the membrane is a hollow fiber membrane produced by any of the methods described herein. The feed mixture includes at least a first component and a second component. The contact creates a penetrating mixture on the second side of the film and creates a retention mixture on the first side of the film. The penetrating mixture is enriched in the first component and the retention mixture depletes the first component.

In some embodiments, the pressure on both sides of the membrane can be approximately equal. In other embodiments, there is a pressure differential between one side of the membrane and the other side of the membrane. For example, the pressure on the retention side of the membrane can be higher than the pressure on the breakthrough side of the membrane. In other examples, the pressure on the penetrating side of the membrane can be higher than the pressure on the retentate side of the membrane.

The feed gas mixture can include any mixture of gases or liquids. For example, the feed gas mixture can include hydrogen, carbon dioxide, nitrogen, ammonia, methane, water vapor, hydrogen sulfide, or any combination thereof. The feed gas or liquid can include any gas or liquid known to those skilled in the art. The membrane can be any gas or liquid in the feed mixture, or any plurality of gases or liquids in the feed mixture can be selectively penetrated. The membrane may be selectively permeable to all gases or liquids other than any of the gases or liquids in the feed mixture.

Any number of membranes can be used to complete the separation. For example, a single film may be used, or a plurality of films may be used, such as in a hollow fiber module. In some embodiments, one or more hollow fiber strands provided by the methods of the present invention are used in combination with other membranes, wherein the other membranes are any suitable membranes. The other film can be fabricated as a flat sheet or fiber and can be packaged into any suitable type of module, including hollow fibers, sheets or aligned hollow fibers or sheets. Common module forms include hollow fiber modules, spiral surround modules, plate and frame modules, tubular modules and capillary fiber modules.

The invention may be further understood by reference to the examples provided below. The invention is not limited to the examples presented herein.

Example 1. Curable Organic Polyoxane

The curable oxirane is copolymerized by combining 5.000 g of a decane-decane sesquioxane blend (blend 1) with 0.1489 g of polydimethyl methoxy oxane-polyhydromethyl decane. And comprising 1 wt% H (crosslinker 1) in the form of SiH prepared in a polypropylene cup, mixed in a counter-rotating centrifugal mixer at 2900 rpm for 30 s, the blend 1 comprising 73 parts having about 55 Pa at 25 ° C . Dimethyl methoxy oxy-terminated polydimethyl methoxy oxane of s and 27 parts including CH ₂ =CH(CH ₃ ) ₂ SiO _1/2 unit, (CH ₃ ) ₃ SiO _1/2 unit and silicone organopolysiloxane resin alumoxane _4/2 units of SiO, CH _4/2 units wherein the composition of _{SiO 2 = CH (CH 3)} 2 SiO 1/2 units and (CH _{3) 3} SiO _1/2 units of mo The ear ratio is about 0.7, and the resin has a weight average molecular weight of about 22,000, a degree of polymerization distribution of about 5, and contains about 1.8% by weight (about 5.5 mole %) of a vinyl group, the polydimethyl methoxyoxane-multi The hydromethoxane copolymer has 0.03 Pa at 25 ° C. The average viscosity of s. Remove the top cover and scrape off the sample of the side wall of the cup. The lid was covered and the sample was mixed at 2900 rpm for 30 s.

Then, 1-ethynyl-1-cyclohexanol was added to the cup, and then mixed twice at a period of 2900 rpm for 30 s, and manually mixed by a spatula between the second cycles. Next, 0.01 g of a catalyst (catalyst) comprising 1% of 1,3-divinyl-1,1,3,3-tetramethyldioxane platinum (IV) is added to the cup. , 92% dimethylvinyl methoxy-terminated polydimethyl decane (having a viscosity of about 0.45 Pa.s at 25 ° C) and 7% of tetramethyldivinyldioxane Mix the mixture and mix again in the same way. Finally, 1.29 g of hexane was added to the cup and mixed for 30 s at 2900 rpm.

Example 2. Coated core with polypropylene support fibers and D4 core composition

A polypropylene support fiber having an outer diameter of 300 μm was passed through a glass column for fiber coating. The fiber enters the bottom through a blunt-ended stainless steel needle having an inner diameter of 413 μm into a reservoir containing liquid octamethylcyclotetraoxane (D4). The D4 coated fiber is then passed through the center of a 19" high double layer glass condenser containing liquid nitrogen. The fiber is sufficiently cooled as it passes through the condenser to freeze D4 around the fiber. The fiber then passes through the first A second blunt-ended stainless steel needle of the same size as the needle enters the pool of curable oxoxane composition as described in Example 1. The fiber is then passed through a die to remove excess coating and then passed through a package of electric heating. 3/8" stainless steel tube, heated to about 115 °C. The curable oxirane is fully cured as it passes through the device. The finished fiber is then wound onto a spool that connects the motor, which controls the rate at which the fiber moves through the system. The fibers were pulled at a speed of 1 m/min and 2 m/min. The helium oxide coating was completely cured at both speeds.

Example 3. Hollow fiber (hypothetical example)

The frozen core of the sample drawn in Example 2 was melted at a temperature of 25 ° C, and the polypropylene fibers in the cured composition were withdrawn to produce hollow fibers.

Example 4. Coated core with polyvinyl alcohol (PVA) support fibers and D4 core composition

The process described in Example 2 was repeated except that the polypropylene fibers were replaced with hollow polyvinyl alcohol (PVA) fibers having an outer diameter of about 200 μm to support the D4 frozen core. The first and second needles in this example all have an inner diameter of about 337 μm. The surface of the formed fiber is shown on the pull wire Cured oxirane coatings were formed at speeds of 1 m/min and 2 m/min.

Example 5. Hollow fiber (hypothetical example)

The frozen D4 core of Example 4 was removed by thawing at 25 C and allowing D4 to drain from the annular region between the cured coating and the PVA support fibers. This facilitates the removal of the PVA fibers via hot water dissolution or by mechanical extraction to produce hollow fibers.

Example 6. Hollow fiber (hypothetical example)

The removal of the D4 core in Example 4 was carried out by encapsulating a series of fibers in a hollow fiber module using a polyurethane encapsulating adhesive. The adhesive can be cured at ambient temperature, and then the interior of the hollow fiber is exposed by cutting the tip of the package region. The D4 core was then removed by vacuuming the fiber caliber at about 50 Torr at 25 C. This helps to remove the PVA support fibers via hot water dissolution.

Example 6. Single ruthenium support fiber with aqueous core composition (hypothetical example)

Following the procedure of Example 2, polypropylene fibers were replaced with mono-polyamine or polyester fibers and D4 was replaced with deionized water. The sample was pulled in at a line speed of 1 m/min and 2 m/min. Complete curing of the decane coating can occur at two rates, when viewed (after melting or sublimating at least a portion of the chilled water), the polyoxynoxy hollow fibers from which the water wettable support fibers can be withdrawn, To leave a free-standing polyoxyn hollow fiber membrane.

Example 7. Single 缕 support fiber with hydrogel core composition (hypothetical example)

Following the procedure of Example 2, polypropylene fibers were replaced with mono-polyamine or polyester fibers and replaced with a hydrogel-forming aqueous solution containing 95 wt% deionized water and 5% water soluble polymer such as polyacrylic acid or gelatin. D4. The sample was pulled in at a line speed of 1 m/min and 2 m/min. The complete cure of the decane coating can be seen at two speeds, when the inspection shows that the frozen core can be melted or sublimated and the water wettable support fibers can be extracted from the fluorinated hollow fibers to leave a small amount of water. A self-contained polysiloxane hollow fiber membrane with residual gel polymer.

Example 8. Polypropylene Support Fibers with Polyoxane and D4 Core Compositions (hypothetical example)

Following the procedure of Example 2, a 95% liquid D4 and a 5 wt% hydrogenated curable polyoxo-elastic composition which together form a gelled cyclooxyl network were used in place of D4. The sample was advanced at 1 m/min and 2 m/min. The complete curing of the decane coating can be seen at two speeds, when the inspection shows that the frozen core can be melted or sublimated and the water WP can be extracted from the argon hollow fiber to leave a small amount A free-standing polyoxynoxy hollow fiber membrane with a residual aqueous gel polymer. The gelled D4 core can be removed under substantially the same conditions as the ungelatinized D4, but the method can be carried out at a temperature not lower than room temperature because D4 exhibits a soft solid even at room temperature. gel. Thus the D4 can be removed by heating or vacuum.

The words and expressions used are for the purpose of description and not limitation, and the use of such terms and expressions are not intended to exclude any equivalents or parts of the features described and claimed. There may be various modifications in the scope of the invention. Therefore, it is to be understood that the modifications and variations of the presently disclosed subject matter may be apparent to those of ordinary skill in the art, and the It is intended to fall within the scope of the invention as defined by the appended claims.

Additional embodiment

The present invention provides the following illustrative examples, the numbers of which are not to be construed as representative of importance.

Embodiment 1 provides a method of forming a hollow fiber, the method comprising: providing or obtaining a substantially cylindrical solid core comprising a core composition, the core composition comprising from about 50 weight percent (wt%) to about 100 wt% a fusible or sublimable composition; coating the core with a curable composition; curing the curable composition; melting or sublimating at least a portion of the core composition; and removing at least a portion of the core composition The molten or sublimated portion of the material provides a hollow fiber.

Embodiment 2 provides the method of embodiment 1, wherein the core comprises at least one support fiber, wherein the core composition encapsulates the support fiber.

Embodiment 3 provides the method of embodiment 2, wherein providing or obtaining the core comprises: coating the support fiber with the core composition; and curing the core composition on the support fiber.

Embodiment 4 provides the method of any one of embodiments 2 to 3, further comprising removing the support fiber from the hollow fiber after melting or sublimating at least a portion of the core composition.

The method of any one of embodiments 2 to 4, wherein the support fiber comprises at least one of polypropylene, polyvinyl alcohol, and monoterpene wettable fibers.

Embodiment 6 provides the method of any one of embodiments 2 to 5, wherein the support fiber has a diameter of from about 10 μm to about 600 μm.

Embodiment 7 provides the method of any one of embodiments 1 to 6, wherein the core The composition comprises at least one of water, an organic cyclodecane, a hydrogel polymer, and a hydrogenated curable polyoxo composition.

Embodiment 8 provides the method of Embodiment 7, wherein the organocyclodecane comprises from about 3 to 12 bis(C _1-5 alkyl)nonane repeating units.

Embodiment 9 provides the method of any one of embodiments 7 to 8, wherein the core composition comprises less than about 20% by weight hydrogel polymer or less than about 20% by weight of the hydrazine hydrogenated curable polyfluorene composition .

Embodiment 10 provides the method of any one of embodiments 1 to 9, wherein the core composition comprises octamethylcyclotetraoxane, from about 85 wt% to 99 wt% water, and from about 15 wt% to 1 wt% of the hydrogel. a polymer, and at least one of about 85 wt% to 99 wt% octamethylcyclotetraoxane and from about 15 wt% to 1 wt% of a hydrogenated curable polydecane oxide composition.

The method of any one of embodiments 1 to 10, wherein the core composition has a higher fluidity at at least one temperature above a melting point or a sublimation point of the core composition than the cured curable composition.

Embodiment 12 provides the method of any one of embodiments 1 to 11, wherein the fusible or sublimable composition is fusible or sublimable at at least one temperature of from about -200 ° C to about 60 ° C.

Embodiment 13 provides the method of any one of embodiments 1 to 12, wherein the fusible or sublimable composition has a zero of about 100 cP or less at at least one temperature of from about -100 ° C to about 60 ° C. Shear viscosity.

Embodiment 14 provides the method of any one of embodiments 1 to 13, wherein the fusible or sublimable composition has a zero shear viscosity of about 100 cP or less at about 25 °C.

Embodiment 15 provides the method of any one of embodiments 1 to 14, wherein the The cured composition comprises an organopolyoxane.

Embodiment 16 provides the method of any one of embodiments 1 to 15, wherein the curable composition comprises a hydrazine curable composition, a condensation curable composition, a radical curable composition, an amine epoxy At least one of a curable composition, a radiation curable composition, a cooled curable composition, or any combination thereof.

Embodiment 17 provides the method of any one of embodiments 1 to 16, wherein the core is substantially cylindrical.

Embodiment 18 provides the method of any one of embodiments 1 to 17, wherein the core has a diameter of from about 10 μm to about 2000 μm.

Embodiment 19 provides the method of any one of embodiments 1 to 18, wherein the curing comprises hydrazine hydrogenation curing, condensation curing, radical curing, amine epoxy curing, radiation curing, cooling, or any combination thereof.

Embodiment 20 provides the method of any one of embodiments 1 to 19, wherein the hollow fiber comprises a wall having a thickness of from about 1 μm to 200 μm.

Embodiment 21 provides the method of any one of embodiments 1 to 20, wherein the method is continuous.

Embodiment 22 provides a hollow fiber produced by the method of any of Examples 1 to 21.

Embodiment 23 provides a method of forming a polysiloxane hollow fiber, the method comprising: providing or obtaining a substantially cylindrical solid core having a diameter of from about 100 μm to about 500 μm, the core comprising at least one support fiber and one a core composition comprising the support fiber comprising from about 50% by weight to about 100% by weight of a fusible or sublimable composition, wherein the fusible And the sublimable composition is meltable or sublimable at at least one temperature of from about -200 ° C to about 60 ° C; coating the core with a curable composition comprising an organopolyoxane; curing the curable a composition; melting or sublimating at least a portion of the core composition; and removing at least a portion of the molten or sublimated portion of the core composition to provide a polyoxynoxy hollow fiber comprising about 10 μm To a wall of one thickness of about 60 μm.

Embodiment 24 provides a method of forming a polysiloxane hollow fiber, the method comprising: providing or obtaining a substantially cylindrical solid core having a diameter of from about 100 μm to about 500 μm, the core comprising a core composition, The core composition comprises from about 50% by weight to about 100% by weight of a composition having a zero shear viscosity of about 100 cP or less at at least one of 0 ° C to 60 ° C; to comprise one of the organopolyoxanes. Curing the composition to coat the core; curing the curable composition; melting or sublimating at least a portion of the core composition; and removing at least a portion of the molten or sublimated portion of the core composition to provide a polysiloxane hollow The fiber, the polyoxynoxy hollow fiber, comprises a wall having a thickness of from about 10 μm to about 60 μm.

Embodiment 25 provides an organopolyoxane coated core comprising: a substantially cylindrical solid core having a diameter of from about 10 μm to about 2000 μm, the core comprising one comprising from about 50% by weight to about 100% by weight a core composition of a fusible or sublimable composition, wherein the fusible or sublimable composition is fusible or sublimable at at least one temperature of from about -200 ° C to about 60 ° C; A curable composition on the core, the curable composition comprising an organopolyoxane.

Embodiment 26 provides the coated core of embodiment 25, wherein the curable composition coated on the core is at least partially cured.

Example 27 provides a coating of a cured organopolyoxane composition The core, the coated core comprising: a substantially cylindrical solid core having a diameter of from about 10 μm to about 2000 μm, the core comprising a fusible or sublimable composition comprising from about 50% by weight to about 100% by weight a core composition, wherein the fusible or sublimable composition is fusible or sublimable at at least one temperature of from about -200 ° C to about 60 ° C; at least partially cured on the core A curable composition comprising an organopolysiloxane and comprising a wall having a thickness of from about 1 [mu]m to about 200 [mu]m.

Embodiment 28 provides a method of separating a component of a feed mixture, the method comprising: contacting a first side of a film with a feed gas or liquid mixture comprising at least a first component and a second component, Generating a penetrating mixture on a second side of the film and creating a retention mixture on the first side of the film, wherein the penetrating mixture is enriched in the first component and the retention mixture depletes the first A component; wherein the film comprises the hollow fiber provided by the method of any of embodiments 1 to 24.

Embodiment 29 provides an apparatus or method as desired in any one of Examples 1 to 28 or any combination such that all of said elements or options are selected or used.

Claims (10)

A method of forming a hollow fiber, the method comprising: providing or obtaining a substantially cylindrical solid core comprising a core composition, the core composition comprising from about 50 weight percent (wt%) to about 100 wt% a fusible or sublimable composition; coating the core with a curable composition; curing the curable composition; melting or sublimating at least a portion of the core composition; and removing at least a portion of the core composition Melting or sublimating portions to provide a hollow fiber. The method of claim 1, wherein the core comprises at least one support fiber, wherein the core composition encapsulates the support fiber. The method of claim 2, wherein providing or obtaining the core comprises: coating the support fiber with the core composition; and curing the core composition on the support fiber. The method of any one of claims 2 to 3, wherein the support fiber comprises at least one of polypropylene, polyvinyl alcohol, and monoterpene wettable fibers. The method of any one of claims 1 to 4, wherein the core composition comprises at least one of water, an organic cyclodecane, a hydrogel polymer, and a hydrogenated curable polyfluorene composition. By. The method of any one of claims 1 to 5, wherein the core composition has a higher fluidity at at least one temperature above a melting point or a sublimation point of the core composition than the cured curable group Adult. The method of any one of claims 1 to 6, wherein the fusible or sublimable composition has a zero shear of about 100 cP or less at at least one temperature of from about -100 ° C to about 60 ° C. Force viscosity. The method of any one of claims 1 to 7, wherein the curable composition comprises an organopolyoxane. A method of forming a polysiloxane hollow fiber, the method comprising: providing or obtaining a substantially cylindrical solid core having a diameter of from about 100 μm to about 500 μm, the core comprising at least one support fiber and a cladding support The fiber comprises from about 50% to about 100% by weight of a core composition of a fusible or sublimable composition, wherein the fusible or sublimable composition is at least one of: at about -200 ° C to about At least one temperature of 60 ° C can be melted or sublimable, and has a zero shear viscosity of about 100 cP or less at at least one temperature of 0 ° C to 60 ° C; to form a curable composition comprising one organopolyoxane Coating the core; curing the curable composition; melting or sublimating at least a portion of the core composition; and removing at least a portion of the molten or sublimated portion of the core composition to provide a polyoxyn hollow fiber, The polyoxynoxy hollow fibers comprise walls having a thickness of from about 10 [mu]m to about 60 [mu]m. An organopolyoxane coated core comprising: a substantially cylindrical solid core having a diameter of from about 10 μm to about 2000 μm, the core comprising a fusibility comprising from about 50% by weight to about 100% by weight or a core composition of a sublimable composition, wherein the fusible or sublimable composition is fusible or sublimable at at least one temperature of from about -200 ° C to about 60 ° C; A curable composition coated on the core, the curable composition comprising an organopolyoxane.