CN103533998A - High-performance fibrous products - Google Patents
High-performance fibrous products Download PDFInfo
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- CN103533998A CN103533998A CN201280012258.2A CN201280012258A CN103533998A CN 103533998 A CN103533998 A CN 103533998A CN 201280012258 A CN201280012258 A CN 201280012258A CN 103533998 A CN103533998 A CN 103533998A
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- Prior art keywords
- fiber
- polymer
- emulsion
- fleece
- fibers
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/30—Polyamides; Polyimides
Abstract
The invention relates to formulations and methods for coating a fibrous web, comprising an emulsion capable of deposition on the fibrous web, the emulsion comprising an aqueous continuous phase and a discontinuous internal phase comprising a surface-modifying agent. The fibrous web may comprise a population of fibers that are pretreated with a pretreatment polymer, such as a polycationic polymer. The fibrous web may contain cellulose fibers, or two populations of dissimilar fibers. The surface- modifying agent may contain a polymeric system that forms a coating polymer on fibers of the fibrous web following evaporation of the aqueous continuous phase of the emulsion.
Description
Related application
The application requires the U.S. Provisional Application the 61/450th of submitting on March 8th, 2011, the rights and interests of No. 407.More than whole instructions of application are incorporated to herein by reference.
Technical field
The application is usually directed to high-performance fiber product.
Background of invention
Need the filtration application of working medium under the condition of work of product, to there is durability and dimensional stability.For performance application, filter medium can meet with extreme condition, for example high temperature, contact oil or other solvent or be exposed to hydraulic oil or water.For demand application, such as most of filter medium of inlet filter, serial fluid filter, engine oil filter etc., be the nonwoven products that uses cellulose to make in conjunction with synthetic fibers.The firm synthetic fibers of the cheap cellulose fiber peacekeeping of this type of composite utilization are to give desired function.Desired function comprises as the character in wet or dry strength, durability, dimensional uniformity and the stability of nonwoven products and consistent engineering thickness, fiber and aperture.This type of is functional also satisfies the demand in other high-performance fiber product.
Can effectively form and comprise natural and non-woven composites synthetic fibers by traditional paper technology cost.Although to use traditional papermaking to form natural-during synthetic composite material, may introduce performance limitations.The synthetic fibers that add in cellulose fibre during tradition papermaking can bunch up in head box, disturb evenly to mix between the fiber required with producing durable net to be connected.In addition, the different surfaces of two types of fibers (that is, natural and synthetic) can hinder it to interconnect.Therefore, typical combination possibility performance in filtration natural in fibrous composite and synthetic fibers is not good.
For strengthening intensity and the solvent resistance of high-performance nonwoven products, as can be used for filter application, can make synthetic polymer solution that these dielectric soaks can be curing between wet net dry period so that additional strength and solvent resistance to be provided.Thermosetting high-performance polymer (for example phenolic resins) is such example of the current impregnating resin using.Water insoluble and therefore need organic solvent with can coated fiber for many fluoropolymer resin systems of flooding.The thickness that these impregnation technologies controls are deposited on the polymer coating on fiber is not good yet, causes changeability and the inaccuracy in aperture.And, for inflammable, the insalubrity conventionally of the dicyandiamide solution that makes fluoropolymer resin deposition, costliness, and need special disposal.
The premium quality product that this area need to be used traditional paper technology to be made by fleece, wherein said product is firm and heat-resisting and oily.For example, this series products can be used in filter medium.Also need to be suitable for non woven fibre product, give product required character, for example make peace and stablize the coating process of dimension in fire resistance, aperture one.This type of coating process will comprise Aquo System satisfactorily, so that will avoid harmful feature of the system based on solvent.
Summary of the invention
In embodiments, herein disclosed is the preparation for coated fiber net, described preparation comprises the emulsion that can be deposited on described fleece, the discontinuous interior phase that described emulsion comprises water continuous phase and comprises surface modifier.In embodiments, described fleece comprises a class through the pretreated fiber of pretreatment polymer.Described pretreatment polymer can be polycation.In embodiments, described fleece comprises cellulose fibre.In embodiments, described fleece comprises the dissimilar fiber of two classes.In embodiments, described surface modifier is included in after the described water continuous phase evaporation of described emulsion, forms the polymeric system of coated polymeric on described fibroreticulate fiber.Described surface modifier further comprises additive.Described additive can be given described fleece for example fire resistance, anti-flammability, lubricity, hydrophobicity and plastic character.In embodiments, described polymeric system comprises polymer precursor.In embodiments, the crosslinking agent that described surface modifier comprises crosslinked described coated polymeric.In embodiments, described pretreatment polymer has affinity to described coated polymeric.
In embodiments, the method that makes the fiber surface modification in fleece is further disclosed herein, comprise the following steps: some fibers that can be arranged in fleece are provided, by the emulsion of the discontinuous interior phase that comprises water continuous phase and comprise surface modifier, apply described some fibers, wherein said surface modifier comprises the polymeric system that can make polymer be deposited on fiber surface, before applying the step of described fiber, arrange during this time or afterwards described some fibers and form described fleece, evaporate the described continuous water of described emulsion, coalescent described discontinuous phase is to form the uniform coating of the fiber surface that is placed in described some fibers, and use described polymeric system so that described polymer is deposited on the fiber surface of described some fibers, thereby make described fiber surface modification.In embodiments, described polymeric system comprises polymer precursor and uses the step of described polymeric system to comprise that the described polymer precursor of activation can be deposited on the described polymer of described fiber surface with formation.In embodiments, described surface modifier further comprise with described fiber surface on the additive of described interpolymer interaction.In embodiments, described method further comprises the step of the described polymer on crosslinked described fiber surface.In embodiments, described method is further included in the initial step that some or all in some fibers described in the pretreatment of carrying out before the step of described some fibers are provided.
Detailed Description Of The Invention
In embodiments, herein disclosed is based on using the surface modification for fiber of moisture O/w emulsion so that surface modifier is deposited on system and the method on fibre structure or fleece.As used herein, term " fibre structure " or " fleece " refer to the single fiber of insertion mutually or any arrangement of filament.In some embodiments, fibre structure or netting gear have non-woven feature.In some embodiments, fiber or filament form disorderly pattern (for example, form in fact at random or structure, the pattern of its tissue can not be distinguished completely).Be known in the art the technology that some manufacture fibre structures, comprise paper technology and for the manufacture of other technology of non-woven material.
As used herein, term " fiber " can refer to natural or synthetic to have aspect than any thread entity of (for example,, for example, than the much bigger dimensions length of its sectional dimension (, diameter)).For example, in embodiments, the length-width ratio of fiber is greater than approximately 10,20,30,50 or 100.Term " fiber " comprises larger fiber and microfibre.The small bore width (that is, diameter) that can be not more than by having in some embodiments 100 μ m is identified microfibre.In embodiments, the averga cross section width of microfibre is between 0.5 and 50 μ m.In other embodiments, the averga cross section width of microfibre is between 4 and 40 μ m.In embodiments, the averga cross section width of microfibre is less than 30 μ m.Also can characterize according to denier unit the size of microfibre.In some embodiments, on average, microfibre is less than about 10D, or is less than about 5D, or is less than about 2D, or is less than about 1D.The fiber larger than microfibre can be described as " larger fiber ".As used herein, term " larger fiber " refers to any synthetic or natural fiber of and/or wide (that is, have larger cross-section length) longer than microfibre.In some embodiments, when using together with less microfibre, the cross-sectional length of larger fiber (for example, diameter) is 3-50 μ m, 7-70 μ m or 150-600 μ m.An example of larger fiber is the cellulose fibre of being combined with typical wood pulp preparation.In some embodiments, the averga cross section size of larger fiber (for example, diameter) is greater than approximately 5,10,20,50,100,500,1000,5000 or 10000 with the ratio of microfibre.Fiber can have some possibility separated fibrillation (that is, fibrillating fibre).During fiber process, can generate fibrillating fibre by fiber, wherein precursor fiber wearing and tearing or machinery are nervous.For example, technique (for example, papermaking) can fortifying fibre the inside and outside filtration of element paper pulp.Although the cross-sectional width of fibrillating fibre may not be greater than approximately 100 μ m, fibrillating fibre can comprise that cross-sectional width is less than the part of approximately 100 μ m.Fibrillation can have nanostructured, for example shows between about 1nm and 1 μ m, or the averga cross section width between about 50nm and about 500nm.In some embodiments, microfibre shows as nanofiber, and it can be derived from the fibrillation of microfibre.
Term " fiber " can refer to synthetic fibers or natural fiber.As used herein, term " synthetic fibers " comprises fiber or the microfibre of all or part of production.Synthetic fibers comprise staple fibre, wherein natural precursor material through modification to form fiber.For example, can make cellulose (being derived from natural material) form staple fibre for example Rayon or Lyocell.Also can make cellulose modified to generate cellulose acetate fibre.These staple fibres are examples of synthetic fibers.Can form synthetic fibers by inorganic or organic synthetic material.As used herein, term " natural fiber " refers to be derived from natural origin, without artificial modification's fiber or microfibre.Natural fiber comprises plant source fiber, animal sources fiber and mineral source fiber.Plant source fiber can be mainly cellulose, such as cotton, jute, flax, hemp, sisal, ramie etc.Plant source fiber can comprise the fiber that is derived from seed, pericarp, for example cotton or kapok.Plant source fiber can comprise and be derived from leaf, for example the fiber of sisal and American aloe.Plant source fiber can comprise plant-derived stem crust or the fiber of bast, for example flax, jute, mestha, hemp, ramie, rattan, fibre and soya, vine fiber, jute, mestha, industrial hemp, ramie, rattan, fibre and soya and banana fiber around.Plant source fiber can comprise the fiber of plant-derived fruit, for example cocoanut fiber.Plant source fiber can comprise the fiber of plant-derived stalk, for example wheat, paddy rice, barley, bamboo and grass.Plant source fiber can comprise wood fibre.Animal sources fiber generally comprises protein, such as wool, silk, mohair yarn etc.Animal sources fiber can be derived from animal hair, such as sheep's wool, goats hair, alpaca fibre, horse-hair etc.Animal sources fiber can be derived from animal body part, such as gutstring, tendon etc.Can by dried saliva or other excreta or its cocoon collection animal sources fiber of insect, for example, from silk cocoon, obtain silk.Animal sources fiber can be derived from the feather of bird.Mineral source natural fiber is obtained by mineral.Mineral source fiber can be derived from asbestos.Mineral source fiber can be glass or ceramic fibre, such as glass wool fiber, quartz fibre, aluminium oxide, carborundum, boron carbide etc.
In embodiments, the surface modifier for fiber disclosed herein comprises polymer or polymer precursor (for example, monomer, comonomer, oligomer etc.) and composition thereof.Term " polymer " system " should refer to can be used for polymer, polymer precursor or its mixture for the fiber coated polymer coating in fleece.In embodiments, emulsion interior mutually in portability polymeric system.As used herein, term " emulsion " refers to the heterogeneous system consisting of two kinds of dissimilar liquid, and wherein a kind of liquid is drop form and is dispersed in another kind of liquid.Emulsion matrix is called to foreign minister or the continuous phase of emulsion, and the droplet by disperseing is formed be called mutually interior phase or discontinuous phase.The existence that is called the surfactant of emulsifying agent or demulsifier can make emulsion-stabilizing or unstable.For example, emulsifying agent can form interfacial film around to produce the coalescent barrier of interference emulsion droplet by the drop in decentralized photo.If make emulsion unstable, drop trends towards gathering into large-size, causes that phase place is because of gravitational settling separation.On the contrary, in stable emulsion, two kinds of components keep mixing.As described herein, the water continuous phase support belt of emulsion is useful on surface modifier (for example, the discontinuous phase of polymeric system (monomer, comonomer, oligomer, polymer etc. and initator (free radical, ion etc.)) of coated fiber.Discontinuous oil phase can contain multiple other surface modifier, for example plasticizer (for example, polyalcohol), fire retardant (for example, bromination or phosphate molecule), crosslinking agent (difunctional or multi-functional) etc.
In embodiments, for example, polymeric system can make to pass on the coating of advantageous property to be deposited in fiber surface to the fleece forming thus.For example, can use suitable surfactants/emulsifiers that the polymeric system that comprises reactive monomer/initator or monomer/crosslinking agent or oligomer/crosslinking agent or polymer/crosslinking agent is emulsifiable in water.In emulsion, contained surface modifier can comprise other material except polymeric system, cooperate with polymeric system or with fiber interaction to give the additive of desirable properties.For example, emulsion can contain and comprise as the monomer of main species and the polymeric system of comonomer, is then curing agent or the crosslinking agent that is mixed with the various additives such as hydrophobicity, anti-flammability etc. that can give the different polishing agents of net (finishes).These compositions can all mix and add in water under high-speed stirred with a small amount of surfactant.Then the resulting stable emulsion that comprises polymeric system and other additive is coated onto on fleece.
After emulsion is coated with on the net, emulsion is coated fiber relatively equably.Because process net by drier, shearing and hot combination cause the water evaporation of emulsion, leave the residual drop of oil phase.Pass in time these identical power and force droplet coalescence.Because droplet coalescence, polymeric system is used.Because be used, polymeric system provides the intact coated polymeric of coated fiber network fiber.Using polymeric system only to involve makes the intact coated polymeric having contained in emulsion droplet be deposited on fiber surface.Use polymeric system to relate to and cause and expand the polymerization by polymer precursor, to form coated polymeric at fiber surface.
Because the polymeric system in oil phase is subject to the temperatures involved of drying equipment, polymeric system sclerosis, forms coated polymeric and is incorporated to the additive (such as lubricant, fire retardant, water-repelling agent etc.) existing in oil phase drop.Result is the hardening polymer system that comprises coated polymeric and additive to network fiber continuously coating.Be hardened in and in dry run, complete and all additives that exist in drop are incorporated to coating.
In certain embodiments, for example, pretreatment candidate fiber before coated surfaces modifier, thus fiber carries positive charge.For example, available polycation carries out pretreatment.As used herein, term " polycation " can comprise any polymer (for example, copolymer) with clean positive charge, for example polyamine.As used herein, term " polyamine " can comprise at least having it containing any polymer or the copolymer of a part for amine (quaternary amine, tertiary amine, secondary amine or primary amine) repetitive.In embodiments, due to the reactivity of primary amine, polyamine may make us desirably containing the repetitive that some have primary amine.The average molecular weight range of as used herein polymer (for example, polycation) can from 1,000 to 10,000,000, but is preferably between 10,000 to 500,000.
In embodiments, as pretreated polyamine, can be the polymer that comprises shitosan or polymine.In embodiments, chitosan polymer can comprise certain part of higher molecular weight shitosan, and viscosity is the shitosan of 800cp at least when in 1% acetum.In embodiments, the amount of higher molecular weight shitosan can be greater than 10%, be greater than 20% or be greater than 30%.Person of skill in the art will appreciate that, for some polymer, shitosan for example, because this class formation is subject to viscosity, molecular weight limits, so may can not get accurate molecular weight.
As pretreated example, can directly to the fibre blend being scattered in slurry, add polycation, for example polyamine or some other adhesives or wet strength component.Can polycation be invested on fiber by covalent bond or by static, Hydrogenbond or hydrophobic interaction, or polycation spontaneously self assembly is to fiber surface, for example, or polycation is precipitable to surface.For example, shitosan is precipitable to fiber surface.Because shitosan only dissolves in acid solution, thus can it be deposited on the fiber or microfibre in solution by adding alkali to polyamine-fiber/microfiber dispersion body, until shitosan is deposited on the fibroreticulate fiber of formation.
In embodiments, the available cationics with special properties carries out providing the pretreatment of fiber functionalization before being exposed to surface modification emulsion.For example, can be by making selected polymer for example invest surface chemical property that fiber surface changes cellulose and synthetic fibers, so that it has more hydrophily or hydrophobicity (, shitosan analog).For example, for filter membrane and essential other of low protein combination application (biological applications and medical application), synthetic and natural fiber can have more multi-surface modification, such as the polymer (Jeffamines, Pluronics, Tectonics, shitosan analog etc.) using containing PEG sample part.
With after polycation functional fiber, the available emulsion impregnated web carrying through the stable surface modifier of anion surfactant (that is, polymeric system and any desired additives).Can use anion surfactant well-known to those skilled in the art, surfactants such as sodium laureth sulfate, neopelex, sodium lauroyl sarcosine, lauryl sodium sulfate, myristyl alcohol polyethers sodium sulphate, palmitoleic acid sodium, alkanol polyethers sodium sulphate, odium stearate.Electrostatic attraction between emulsion droplet and fiber makes emulsion be deposited on fiber to unify mode, has guaranteed that the coating of net is even.Along the mobile emulsion droplet of fibre length, cause polymeric system deposition, then, due to the combination of shearing and dry run, polymeric acceptor ties up to the dry rear thin uniform coating that forms.
In embodiments, during drying or during thermmohardening can activate crosslinking agent contained in emulsion droplet.Crosslinked is favourable, and this is to help to keep the dimensional stability by the thin slice of web production because of crosslinked, and helps the in the same size and constant pore-size of maintenance, together with extra durability is provided to fleece.For example, the polymeric system that comprises acrylate monomer can comprise multifunctional comonomer, and CN975 six functional polyurethanes acrylate (Sartomer LLC, Exton PA) for example, to provide high crosslink density and therefore abrasion resistance is provided to coating.
In embodiments, the polymeric system (for example, monomer/crosslinking agent system) in can through engineering approaches emulsion droplets to be to provide different functionalities to fleece, this functional crosslinked behavior or the feature that is derived from polymeric system itself.For example, can be polymeric system and select polyfunctional monomer, so that hard, the resistance to solvent of gained coating and damage resistant and be suitable for hot environment.In the application that needs heat-resisting quantity, this type of aromatic series reactive compounds can be incorporated in fleece.The aromatic structure of this type of resonance stabilized (for example, aromatic series acrylate for example CN2601 (Sartomer LLC, Exton PA)) provides high-temperature stability and solvent resistance.In needing another embodiment of film flexibility, can use reactive polyalcohol to provide flexible for coated fiber net.In another embodiment, in polymeric system in being suspended in aqueous emulsion, can use brominated aromatic acrylate (Sartomer LLC, Exton PA) together with acrylate monomer as comonomer, with a step, give heat-resisting quantity and anti-flammability.In embodiments, the aromatic structure of giving the resonance stabilized of advantageous property (for example, heat-resisting quantity and/or anti-flammability) can be incorporated in cross-linked network.In other embodiments, this class formation can be incorporated to curing polymer itself, for example, by free radical, cause itself and most monomer polymerization.
In certain embodiments, the interior phase of emulsion can contain the character of giving except polymeric system itself, produces other additive of other required character.For example, emulsion droplet can contain as the fire retardant that can be incorporated to the additive of curing coating.For another example, emulsion droplet can contain biocide to kill target biology in the situation that microorganism can grow on fiber, it is removed from filtering solution, or keep the life-span of filter.
If while particularly needing hydrophobicity for fleece, polymeric system entrained in aqueous emulsion can comprise reactive silicon.For example, polymeric system can comprise silicon monomer or oligomer peroxide cure or that platinum is curing.
Embodiment
Material
● hexa, Aldrich, USA
● D.E.N.439 epoxy phenolics (phenol, formaldehyde glycidol ether polymer), Dow Chemicals, Midland, MI, USA
● sodium laureth sulfate, Spectrum Chemicals, NJ, USA
● poly-(propane diols) diglycidyl ether (Mn=640), Aldrich, USA
● shitosan cg110, Primex, Siglufjodur, Iceland
● gather (diallyldimethylammonium chloride) 20 % by weight in water, molecular weight 400,000-500,000, Aldrich
● Arofene8426-ME-63 resin, phenolic resins in methanol/ethanol, Ashland Chemicals, Covington, KY, USA
embodiment 1: with poly-DADMAC cationic functional fleece
The fleece that the weak solution functionalization of available diallyl dimethyl ammoniumchloride (poly-DADMAC) comprises cellulose fibre.The intrinsic ionic nature of cellulose fibre can be easily with poly-DADMAC on quaternary amine base compound, produce permanent cationic fleece.
embodiment 2: preparation comprises the paper through cation-modified cellulose fibre
By a piece of paper (650g/m
2) be immersed in the solution that is contained in 0.1% chitosan solution in acid water (pH4).Once paper is full of solution completely, just slow instillation 0.1M NaOH, monitors pH simultaneously and is increased to pH8.This can be precipitated out and be combined with cellulose paper shitosan from solution.Then paper is shifted out from solution, be placed between water suction sofa plate and use steel handwheel to press to remove excessive water, then dry at 110 ℃ on high speed drier.
embodiment 3: preparation is containing the emulsion of reactive polymer (polymeric system)
Reactive modified phenolic resin solution in methanol/ethanol (Arofene8426-ME-63 resin) is as dipping solution.Under agitation in this solution, make an addition to the sodium laureth sulfate of 10% concentration in water until solution becomes muddy.Gained turbid solution is further diluted as for 10% denseness in water to prepare the aqueous emulsion of phenolic aldehyde solution.Make stable containing the emulsion droplet of reactive polymer resin this moment and anionic charge is provided in aqueous emulsion by anion surfactant.
embodiment 4: the phenol resin preparation feedback emulsion of using epoxides modification
Epoxy phenolics (D.E.N.439 epoxy phenolics) is dissolved in methyl alcohol by 10 % by weight.To the crosslinking agent hexa that adds resin 3 % by weight in this solution.Under agitation in this mixture, add 10% solution of sodium laureth sulfate until observe muddy stable suspension.It is 1% solution that water further dilutes this emulsion.Use gained emulsion as dipping solution.Make stable containing the emulsion droplet of reactive polymer resin this moment and anionic charge is provided in aqueous emulsion by anion surfactant.
embodiment 5: use plasticizing crosslinking agent preparation feedback emulsion
Epoxy phenolics (D.E.N.439 epoxy phenolics) is dissolved in methyl alcohol by 10 % by weight.To the crosslinking agent hexa that adds resin 3 % by weight in this solution.To poly-(propane diols) diglycidyl ether as plasticizer that adds resin 10 % by weight in this solution.By under agitation adding 10% emulsifying soln gained settled solution of sodium laureth sulfate, until obtain muddy still stable emulsion.Make stable containing the emulsion droplet of reactive polymer resin this moment and anionic charge is provided in aqueous emulsion by anion surfactant.
embodiment 6: use reactive solution impregnated paper
As embodiment 3,4 and 5 preparation dipping solutions and emulsion for the preparation of paper/phenol composite.For each experiment, according to the paper slip through cation-modified of embodiment 2 preparations, be immersed in and be equipped with in the beaker of cation-modified reactive emulsion, use the composite that steel handwheel presses to remove excessive emulsion and the 120s that hardens hardens completely with acquisition at 160 ℃.The reactive emulsion of describing in embodiment 3 and 4 produces hard and solid composite.Owing to being incorporated to the plastication of poly-(propane diols) diglycidyl ether in crosslinked matrix, but the emulsion of describing in embodiment 5 produces solid flexible composite.
embodiment 7: use amine-reactive silicon emulsion impregnated web
Available emulsification epoxidation silicon polymer dipping amino-functionalization fleece (for example,, according to embodiment 1 or 2 preparations).For example, available anion surfactant is the difunctional or multi-functional Silmer EP of lauryl sulfate emulsification C50, Silmer EPC C50, Silmer EP J10, Silmer EP Di-50, Silmer EP Di-100, Silmer EPC Di-50 epoxy SiClx (SilTech Corp for example, Ontario, CA) to produce dipping solution.Then fleece is immersed in the bath containing these silicon.Can make siliceous net harden to cause and complete the cross-linking reaction between amine and epoxides by dry, produce the extremely conformal nano coating of opposing water suction.
embodiment 8: use reactive acroleic acid fat liquor impregnated web
Can use the silicon polymer impregnated web of the emulsion acrylic ester end-blocking that is mixed with radical initiator (for example azo isobutyronitrile) or peroxide (for example benzoyl peroxide).Available anion surfactant (for example lauryl sulfate) and radical initiator (for example peroxide initiator Photostab100) emulsion acrylic ester function SiClx for example Silmer ACR D208, Silmer ACR D2, Silmer ACR Di-10, Silmer ACR Di-50, Silmer ACR Di-1508 (SilTech Corp., Ontario, CA) to produce dipping solution.Then fleece is immersed in the bath containing reactive silicon, then under the baking temperature (170 ℃ of >) of net, hardens to complete the cross-linking reaction between acrylate group.Or can be by coating being exposed to UV source sclerosis net coating.
embodiment 9: use fire retardant impregnated web
Can in the water-base emulsion that contains polymeric system, add phosphine flame retardant for example phosphate, phosphine-derivatives and phosphonate ester.These reagent can physical property be absorbed in the cross-linked structure of polymeric system formation, thus the anti-flammability of giving.For example, can use phosphate as triethyl phosphate or trioctyl phosphate or triphenyl phosphate.The dosage level of fire retardant is generally a few percent of solid in emulsion.
embodiment 10: high crosslink density
SR9008 (Sartomer USA, Exton PA), trifunctional acrylate can be used for providing high crosslink density and high-dimensional stability for coating.In exemplary composition, 25%SR9008 can be mixed with EB767 urethane acrylate coating resin (UCB Chemical Corp, Smyrna GA) and suitable initiator system can have the acrylic acid ester emulsion of high crosslink density with generation.Variable SR9008 content is to change the crosslink density of gained coating.
embodiment 11: add plasticizer
SR344 (Sartomer USA, Exton PA) (polyethylene glycol oxide acrylate reactions plasticizer) can be mixed with EB767 urethane acrylate coating resin (UCB Chemical Corp, Smyrna GA) and suitable initiator system to produce very pliable and tough coating for needing the application of toughness.
Equivalent
As described herein, embodiment provides overall understanding open and principle, structure, function, production and/or the purposes of further disclosed system and method in the embodiment providing below herein.Those skilled in the art will recognize, specifically described materials and methods is non-limiting embodiments herein.The feature that connects same embodiment explanation or describe can be combined with the feature of other embodiment.Within being intended to that this modifications and variations are included in to the scope of the invention.Equally, those skilled in the art will recognize more feature and advantage of the present invention based on above-mentioned embodiment.Correspondingly, the present invention is not subject to the content constraints that has illustrated especially and described, but limited by the scope of claims.All publications of quoting herein and list of references clearly by reference integral body be incorporated to herein.Word " a kind of (a) " and " a kind of (an) " available phrase " one or more " replace.
Claims (16)
1. for a preparation for coated fiber net, comprise:
Can be deposited on the emulsion on described fleece, the discontinuous interior phase that described emulsion comprises water continuous phase and comprises surface modifier.
2. preparation according to claim 1, wherein said fleece comprises a class through the pretreated fiber of pretreatment polymer.
3. preparation according to claim 2, wherein said pretreatment polymer is polycation.
4. preparation according to claim 1, wherein said fleece comprises cellulose fibre.
5. preparation according to claim 1, wherein said fleece comprises the dissimilar fiber of two classes.
6. preparation according to claim 1, wherein said surface modifier is included in after the described water continuous phase evaporation of described emulsion, forms the polymeric system of coated polymeric on described fibroreticulate fiber.
7. preparation according to claim 6, wherein said surface modifier further comprises additive.
8. preparation according to claim 7, wherein said additive is given the character that described fleece selects the group that free fire resistance, anti-flammability, lubricity, hydrophobicity and plasticity forms.
9. preparation according to claim 6, wherein said polymeric system further comprises the crosslinking agent of crosslinked described coated polymeric.
10. preparation according to claim 6, wherein said polymeric system comprises polymer precursor.
11. preparations according to claim 2, wherein said pretreatment polymer has affinity to described coated polymeric.
12. 1 kinds of methods that make the fiber surface modification in fleece, comprising:
Some fibers that can be arranged in fleece are provided,
By the emulsion of the discontinuous interior phase that comprises water continuous phase and comprise surface modifier, apply described some fibers, wherein said surface modifier comprises the polymeric system that can make polymer be deposited on fiber surface,
Before applying the step of described fiber, during or arrange afterwards described some fibers to form described fleece,
Evaporate the described continuous water of described emulsion,
Coalescent described discontinuous phase forms the uniform coating of the fiber surface that is placed in described some fibers, and
Use described polymeric system so that described polymer is deposited on the fiber surface of described some fibers, thereby make described fiber surface modification.
13. methods according to claim 12, wherein said polymeric system comprises polymer precursor and uses the step of described polymeric system to comprise that the described polymer precursor of activation can be deposited on the described polymer of described fiber surface with formation.
14. methods according to claim 12, wherein said surface modifier further comprise with described fiber surface on the additive of described interpolymer interaction.
15. methods according to claim 12, further comprise the step that is cross-linked the described polymer on described fiber surface.
16. methods according to claim 12, are further included in the initial step that some or all in some fibers described in the pretreatment of carrying out before the step of described some fibers are provided.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161450407P | 2011-03-08 | 2011-03-08 | |
| US61/450,407 | 2011-03-08 | ||
| PCT/US2012/028054 WO2012122257A2 (en) | 2011-03-08 | 2012-03-07 | High-performance fibrous products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103533998A true CN103533998A (en) | 2014-01-22 |
Family
ID=46798766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280012258.2A Pending CN103533998A (en) | 2011-03-08 | 2012-03-07 | High-performance fibrous products |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP2683460A4 (en) |
| JP (1) | JP2014510847A (en) |
| CN (1) | CN103533998A (en) |
| AU (1) | AU2012225524A1 (en) |
| BR (1) | BR112013022741A2 (en) |
| CA (1) | CA2829373A1 (en) |
| CL (1) | CL2013002576A1 (en) |
| RU (1) | RU2013144846A (en) |
| WO (1) | WO2012122257A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371479A (en) * | 2014-10-11 | 2015-02-25 | 江苏常州酞青新材料科技有限公司 | Production method of B-naphthol modified phenolic resin |
| CN106466596A (en) * | 2015-08-20 | 2017-03-01 | 吉林化工学院 | A kind of preparation method of the overall needle type extraction device with Zylon fiber coat as medium |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022055886A1 (en) * | 2020-09-09 | 2022-03-17 | The Chemours Company Fc, Llc | Silicone polyether polymer additives in coatings |
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| US2855374A (en) * | 1950-01-31 | 1958-10-07 | Consortium Elektrochem Ind | Crotonic acid modified polyvinyl emulsions and process for preparing same |
| US20020152630A1 (en) * | 2001-04-20 | 2002-10-24 | Lindsay Jeffrey Dean | Systems for tissue dried with metal bands |
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| US2553154A (en) * | 1945-10-03 | 1951-05-15 | Paper Patents Co | Method of waterproofing and flameproofing paper |
| US2568850A (en) * | 1951-04-11 | 1951-09-25 | Carey Philip Mfg Co | Vapor barrier paper and the manufacture thereof |
| US3878019A (en) * | 1970-05-19 | 1975-04-15 | Ici Ltd | Process of producing spot bonded non-woven webs using ultra-violet radiation |
| US4224169A (en) * | 1978-10-19 | 1980-09-23 | Promotora De Tecnologia Industrial, S.A. | Flame retardant compositions and method of preparing same |
| US4481250A (en) * | 1983-07-29 | 1984-11-06 | Air Products And Chemicals, Inc. | Vinyl acetate-ethylene binder composition having good wet tensile strength and low heat seal temperature for nonwoven products |
| JPH06341063A (en) * | 1990-09-19 | 1994-12-13 | E I Du Pont De Nemours & Co | Flame-retardant nonwoven fabric |
| BRPI0911004B1 (en) * | 2008-07-18 | 2022-05-17 | Quick-Med Technologies, Inc | Method of preparation of an antimicrobial article and antimicrobial article |
| WO2011019811A1 (en) * | 2009-08-12 | 2011-02-17 | Nanopaper, Llc | High strength paper |
-
2012
- 2012-03-07 CN CN201280012258.2A patent/CN103533998A/en active Pending
- 2012-03-07 CA CA2829373A patent/CA2829373A1/en not_active Abandoned
- 2012-03-07 EP EP12755436.8A patent/EP2683460A4/en not_active Withdrawn
- 2012-03-07 BR BR112013022741A patent/BR112013022741A2/en not_active IP Right Cessation
- 2012-03-07 JP JP2013557826A patent/JP2014510847A/en active Pending
- 2012-03-07 WO PCT/US2012/028054 patent/WO2012122257A2/en active Application Filing
- 2012-03-07 AU AU2012225524A patent/AU2012225524A1/en not_active Abandoned
- 2012-03-07 RU RU2013144846/05A patent/RU2013144846A/en not_active Application Discontinuation
-
2013
- 2013-09-06 CL CL2013002576A patent/CL2013002576A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2855374A (en) * | 1950-01-31 | 1958-10-07 | Consortium Elektrochem Ind | Crotonic acid modified polyvinyl emulsions and process for preparing same |
| US20020152630A1 (en) * | 2001-04-20 | 2002-10-24 | Lindsay Jeffrey Dean | Systems for tissue dried with metal bands |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371479A (en) * | 2014-10-11 | 2015-02-25 | 江苏常州酞青新材料科技有限公司 | Production method of B-naphthol modified phenolic resin |
| CN106466596A (en) * | 2015-08-20 | 2017-03-01 | 吉林化工学院 | A kind of preparation method of the overall needle type extraction device with Zylon fiber coat as medium |
| CN106466596B (en) * | 2015-08-20 | 2018-10-30 | 吉林化工学院 | It is a kind of using Zylon fiber coats as the preparation method of the whole needle type extraction device of medium |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012122257A2 (en) | 2012-09-13 |
| CA2829373A1 (en) | 2012-09-13 |
| WO2012122257A3 (en) | 2012-11-08 |
| CL2013002576A1 (en) | 2014-06-27 |
| RU2013144846A (en) | 2015-04-20 |
| EP2683460A4 (en) | 2014-11-12 |
| JP2014510847A (en) | 2014-05-01 |
| AU2012225524A1 (en) | 2013-10-31 |
| BR112013022741A2 (en) | 2019-09-24 |
| EP2683460A2 (en) | 2014-01-15 |
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Application publication date: 20140122 |