CN101484630A - Stable suspensions containing microcapsules and methods for the preparation thereof - Google Patents

Stable suspensions containing microcapsules and methods for the preparation thereof Download PDF

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Publication number
CN101484630A
CN101484630A CNA2007800252886A CN200780025288A CN101484630A CN 101484630 A CN101484630 A CN 101484630A CN A2007800252886 A CNA2007800252886 A CN A2007800252886A CN 200780025288 A CN200780025288 A CN 200780025288A CN 101484630 A CN101484630 A CN 101484630A
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suspension
microcapsules
polymer
solvent
phase
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R·考克斯
M·哈特曼
A·艾亚尔
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Latent Heat Solutions LLC
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Outlast Technologies LLC
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/345—Nitriles
    • D06M13/348—Nitriles unsaturated, e.g. acrylonitrile
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Colloid Chemistry (AREA)
  • Artificial Filaments (AREA)

Abstract

A stable suspension used for the production of temperature regulating fabrics. The suspension preferably comprises microcapsules comprising at least one phase-change material. A method for manufacturing the stable suspension that includes providing microcapsules containing a phase-change material, providing a solvent capable of dissolving a fabric-forming component selected from the group consisting of at least one of said polymer and precursors thereof, and mixing said solvent and said microcapsules to form said first suspension.

Description

Contain stable suspension of microcapsules and preparation method thereof
The cross reference of priority request and related application
[001] the application requires the rights and interests of the Israel patent application No.176693 of submission on July 4th, 2006, and its disclosure is introduced by reference in its entirety at this.
Technical field
[002] relate generally to temperature adjustment fabric of the present invention.More particularly, the present invention relates to produce the employed steady suspension of this fabric, described suspension comprises the microcapsules that contain at least a phase-change material.
Background technology
[003] human body is kept its temperature under constant level by utilizing cooling of perspiration process and chaeta as spacer medium.
[004] yet, natural human body temperature regulation ability is limited to, and disturbs by clothes.
[005] thermal control material, phase-change material for example, in the time of near placing health, but auxiliary adjustment skin and micro climate temperature.When body temperature raise, phase transition temperature phase-change material within the required range absorbed energy from skin, and when health cools off release heat.This causes less, the bigger comfort of fluctuation of human skin and micro climate temperature, less perspiration and lower micro climate relative humidity.
[006] phase-change material also can serve as energy-saving appliance, for example if indoor be furnished with the element that contains phase-change material, for example paint, carpet, furniture finish coat, furniture fabric or furniture coating, then this element absorbs excessive heat and release heat in the colder time in the relatively warmer time.In a comparable manner, it also can for example use in insulator, roof, wallboard, wallpaper, ceiling material, floor and the floor covering etc. at building and building material.In addition, phase-change material is temperature adjustment therein also, or temperature buffer can have many other markets of advantage, for example health care, clothes, electrical equipment, transportation, shipping, cosmetic/personal nursing, Food ﹠ Drink packing, apparatus, disposable product and many-sided in use.
[0007] usually, thermal control material can comprise can absorb or discharge heat energy, at temperature stabilization scope place or with interior reduction or eliminate any material (or mixture of material) of hot-fluid.The temperature stabilization scope can comprise specific transition temperature or transformetion range.If phase-change material is positioned at the words of end product suitably, then in the time period process of phase-change material absorption or release heat, it is (for example liquid and solid-state typically to work as two states of phase-change material experience, liquid state and gaseous state, solid-state and gaseous state, or two solid-state) between transformation the time, phase-change material can suppress heat energy and flow.This effect is interim typically, and for example up in heating or process for cooling process, the latent heat of phase-change material is absorbed or just takes place when discharging.Heat energy can store in phase-change material or therefrom remove, and phase-change material typically can replenish (recharge) by heat or low-temperature receiver effectively again.
[008] seals phase-change material usually.Owing to some following reasons, it is desirable sealing: prevent that after phase-change material becomes liquid state phase-change material from leaking; Avoid polluting with the protection phase-change material; Increase durability; Product sensation etc.
[009] for some application, cloth for example, preferred capsule is the micrometer/nanometer size range.In these size ranges, the capsule of phase-change material can be incorporated in the product and not change the production technology of outward appearance, texture or product.Capsule in the micrometer/nanometer size range is called microcapsules herein.Be called microencapsulated phase change material (mPCM) with micro-encapsulated phase-change material.
[0010] microencapsulated phase change material can be incorporated in the commercial product by variety of way.According to some industrial practices, mPCM, typically with adhesive and possibly other components combine and be coated on the commercial product.Coating can be used known method, for example knife-over-roll coating, roller coat, slot coated, screen printing, foaming coating, lamination, dye to the greatest extent, spray, pad, extrude, embossing or flocking etc., as described in United States Patent (USP) 5366801,6207738,6217993,6503976,6514362 and 6660667, its relevant teachings at this by with reference to introducing.
[0011] many commercial products are made by fiber.Can be before changing into final commercial product or after it, the phase-change material of coating microencapsulation on fiber.Perhaps, can in its preparation process, mPCM be incorporated in the fiber.
[0012] routinely, use two kinds of methods to prepare synthetic fiber: solvent spinning technology and melt spinning technology.Usually use solvent spinning technology, form acrylic compounds or regenerated celulose fibre, and generally use melt spinning technology to form the fiber of nylon fiber, polyester fiber, polypropylene fibre and other similar type.Solvent spinning technology is divided into two kinds of main spining technologies: dry-spinning and wet spinning.In wet spinning process, spinneret be immersed in the chemical bath or maintenance with chemical bath is very approaching and when long filament comes out, their contact chemical baths also precipitate from solution and harden.In dry-spinning technology,, in the air or inert gas stream that can heat or cool off, realize sclerosis by evaporating solvent with different by dilution or chemical reaction precipitation polymers
[0013] developed several methods so that phase-change material and microencapsulated phase change material are incorporated in the fiber, just for example in United States Patent (USP) 6855422,6689466 and 4756958 and U.S. Patent application 20050208300,20040126555,20020054964 and in Acrylic Fibers, R.Cox is at Synthetic Fibers:Nylon, Polyester, Acrylic, Polyolefins, described in the Woodhead Publishing ISBN 1 85,573 588 1, its relevant teachings is introduced by reference at this.Many these methods exist and relate to the common difficult problem that microencapsulated phase change material (mPCM) disperses.In the fiber preparation process process, the microcapsules of introducing tend to form the aggregation of larger particles.This aggregation can cause preparation and production problem, and causes producing the not fiber of the attractive mPCM of containing.The physical property of especially affected fiber, for example intensity, fiber number change thick and thin spot etc.If microcapsules are assembled, the production problem of pressure and flow variation and spinneret hole retardance (blockage) and so on then can appear depositing on tube wall such as plugged filter.
[0014] in some preparation methods, produce the mPCM suspension in solution, then its solution with polymer or polymer-precursor (for example monomer) is mixed for spinning.If with before polymer (or precursor) mixes, feasiblely can store the time period of growing and do not assemble significantly or the mode that is separated forms the suspension of mPCM with enough stable, then preparation technology is simplified.In addition, after mixing, should in mixture, disperse mPCM equably, make to produce to have the fiber that required mPCM distributes.In many cases, be difficult to realize this required stable suspension and uniform dispersion, for example this is because the high ionic strength of this solution causes.In many cases, observe " missible oil is separated out (creaming) ".Use the two-layer formation of this term description, wherein microcapsules are mainly in top layer.Separate out if missible oil takes place in the pipeline workpiece, then it forms cortex or the coating that is very difficult to remove on the pipeline workpiece.
Summary of the invention
[0015] therefore, according to an aspect of the present invention, provide the first stable suspension to be used to produce the temperature adjustment fabric that contains polymer, described suspension comprises solvent and contains a plurality of microcapsules of at least a phase-change material, wherein said microcapsules are incorporated in the described fabric that contains polymer, be characterised in that with the wherein said first stable suspension described solvent can dissolve fabric and form component, described fabric forms component and is selected from least a described polymer and precursor and described effect suspension stabilization thereof at least about 20 hours.
[0016] in a preferred embodiment of the invention, not only effect suspension stabilization this means and observes not significant the gathering at least about 20 hours, and the also stable anti-degraded of the microcapsules in suspension.This degraded can cause the non-required leakage of phase-change material, if it is the words of liquid form.
[0017] therefore, in preferred embodiments, the microcapsules at least about 95% in suspension were kept perfectly in suspension at least about 20 hours.According to particularly preferred embodiment, the microcapsules at least about 98% in suspension were kept perfectly in suspension at least about 20 hours.In the most preferred embodiment, in suspension, in suspension, be kept perfectly at least about 40 hours at least about 98% microcapsules.
[0018] in other embodiment preferred of the present invention, forms described fabric by at least one base polymer fiber.
[0019] preferably, described polymer is selected from acrylonitrile based polymer, cellulose-based polymer, polyester based polymer, polyamide-based polymers and polyolefin based polymer.
[0020] in embodiment preferred more of the present invention, described solvent is the aqueous solution.
[0021] preferably, the described aqueous solution comprises at least a further component that is selected from soda (sodium base), sodium sulfocyanate, zinc chloride, positive methyl morpholine oxide, ammonia, copper sulphate, nitric acid, acetone, dimethyl formamide (DMF) and the positive methyl pyrrolidone (NMP).
[0022] in other preferred embodiments of the present invention, described first suspension further comprises at least a further component that is selected from defoamer, flow control agent, wetting agent, dispersant and the surfactant.
[0023] preferably, the described aqueous solution comprises at least a further component that is selected among soda, sodium sulfocyanate, zinc chloride, positive methyl morpholine oxide, ammonia, copper sulphate, nitric acid, acetone, DMF and the NMP.
[0024] in other aspects of the present invention, described microcapsules comprise that shell and nuclear and described shell are by being selected from acrylic acid and derivative thereof, methacrylic acid and derivative thereof, formaldehyde, at least a component in isocyanates, urea, carboxylic acid derivates, silica precursor and the gelatin forms.
[0025] microcapsules can comprise shell and nuclear, and wherein said nuclear comprises the straight-chain hydrocarbons that is selected from octadecane, has 15-25 carbon atom, have the phase-change material in the branched-chain hydrocarbons of 15-25 carbon atom.
[0026] according to another embodiment of the invention, the melting range of at least a phase-change material is about 20 ℃-Yue 50 ℃.According to an embodiment more of the present invention, the melting enthalpy scope of at least a phase-change material is the about 400J/g of about 80J/g-.
[0027] in a preferred embodiment of the invention, described microcapsules comprise that the weight ratio of shell and nuclear and described shell and nuclear is in about 0.5:9.5 arrives about 4:6 scope.
[0028] this weight ratio also can be at about 1:9 in about 3:7 scope.
[0029] microcapsules can form the about 40wt% of about 5-of described suspension.
[0030] microcapsules can form the about 30wt% of about 10-of described suspension.
[0031] microcapsules can have various rules or irregular shape (for example, spherical, oval or the like) and various sizes.Independent microcapsules can have identical or different shape or size.According to embodiment of the present invention, the max line size range of microcapsules is about 20 microns of about 0.1-.Preferably, the max line size range of microcapsules is about 2 microns of about 0.3-.
[0032] in another aspect of this invention in, polymer is an acrylonitrile based polymer, solvent in the steady suspension comprises water and sodium sulfocyanate, and the concentration range of sodium sulfocyanate is the about 60wt% of about 40-of solvent and the about 30wt% of about 5-that microcapsules form described suspension.According to relevant embodiment, polymer is an acrylonitrile based polymer, solvent in the steady suspension comprises water and sodium sulfocyanate, the concentration range of sodium sulfocyanate is the about 55wt% of about 45-of solution, form the about 20wt% of about 8-of described suspension with microcapsules, and this suspension keeps at ambient temperature.
[0033] in other aspects of the present invention, described polymer is a cellulose-based polymer, wherein said solvent comprises water and NaOH, wherein concentration sodium hydroxide in about 5% scope of about 1%-and wherein said microcapsules form about 5-about 30% of described suspension.
[0034] in another aspect of this invention in, provide by first suspension of above definition and in conjunction with at least a polymer fiber that is selected from polymer and the precursor thereof and form second suspension that component forms.
[0035] described microcapsules can be evenly dispersed in described second suspension.
[0036] basis on the other hand, second suspension contains the microcapsules that mix at least a functional compounds, and that described function is selected from is fire-retardant, biologically active, antimicrobial acivity, anti-smell, UV Absorption, moisture monitoring and water-fast, grease, dirt and/or spot.
[0037] according to various other embodiments, before described combination, this microcapsules are present in the described stable suspension, and this microcapsules are introduced with the polymer or the precursor of combination, introduce after any combination of described combination or these selections.According to embodiment preferred, all types of microcapsules are evenly dispersed in second suspension.
[0038] steady suspension is used to produce under the situation of the temperature adjustment fabric that contains polymer therein, and preferred selective solvent is so that the precursor of its energy dissolve polymer and/or formation polymer.According to one embodiment of the invention, solvent is the aqueous solution.For example, be under the situation of acrylonitrile based polymer at polymer, the aqueous solution of sodium sulfocyanate is suitable solution, and if polymer is when being cellulose-based polymer, the aqueous solution of NaOH is suitable solution.According to one embodiment of the invention, provide solvent at ambient temperature.Mixed solvent and multiple microcapsules form steady suspension.According to one embodiment of the invention, when mixing, solvent is joined in the microcapsules with low shear mixer.
[0039] in another aspect of this invention in, provide the preparation described previously defined first suspension method, this method comprises the steps: to provide the microcapsules that contain phase-change material; Provide to dissolve and be selected from the solvent that fabric at least a in described polymer and the precursor thereof forms component; With described solvent of mixing and described microcapsules, form described first suspension.
[0040] in one embodiment, provide the described solvent of temperature range under about environment to 120 ℃.
[0041] in one embodiment, described first suspension is maintained at about in the temperature range of environment to 120 ℃.
[0042] in one embodiment, described first suspension remains under the low shear-mixed.
[0043] can in container, provide described microcapsules and in described container, described solvent is joined in the described microcapsules, form described first suspension.Described solvent can be an aqueous solvent.
[0044] can provide described microcapsules can be in a water-bearing media as the 3rd suspension and described the 3rd suspension of microcapsules in fluid.
[0045] in the 3rd suspension, the weight ratio scope of microcapsules and water can be about 30-80%.In any known fashion, for example by mixing microcapsule and water or and the aqueous solution, generate the 3rd suspension.In some cases, in containing the technology of microcapsules of phase-change material, preparation generates suspension.In this case, this suspension former state ground or certain modification after, be used as the 3rd suspension.
[0046] in one aspect of the invention, the range of viscosities of described the 3rd suspension is about 3000 centipoises of about 100-.
[0047] in another aspect of the present invention, the range of viscosities of described the 3rd suspension is about 2000 centipoises of about 1000-.
[0048] preferably, providing temperature range is described the 3rd suspension of about environment to 120 ℃.
[0049] in these other embodiments on the one hand of the present invention, described method further comprises the steps: to add at least a further component that is selected from defoamer, wetting agent, flow control agent, dispersant and the surfactant in described first suspension.
[0050] in another embodiment preferred of the present invention, the method of described second suspension of the above definition of preparation is provided, this method comprises the steps: to provide at least a fabric that is selected from polymer and the precursor thereof to form component, and, form described second suspension in conjunction with described component and described first suspension.
[0051] provides any form, for example the polymer of solution form and/or precursor.Any solvent of energy dissolve polymer and/or precursor is suitable for this polymer and/or precursor solution.According to one embodiment of the invention, this solvent is made up of the component that is used as solvent in forming first suspension.According to another embodiment, the composition of the solvent in polymer and/or the precursor solution is similar to the solvent in first suspension, when polymer is acrylonitrile based polymer, all is the aqueous solution of sodium sulfocyanate for example, with when polymer is cellulose-based polymer, be the aqueous solution or NaOH.Binding operation can use known method, for example mixes.According to one embodiment of the invention, microcapsules are evenly dispersed in second suspension.
[0052] in this one side of the present invention, described method further comprises wet spinning or described second suspension of dry-spinning.
[0053] the invention still further relates to the fiber for preparing according to one of described spinning step.
[0054] in a preferred embodiment of the invention, described microcapsules are evenly dispersed in the middle of the described fiber.
[0055] in this one side of the present invention, described fiber preferably combines with other fibers, forms fabric.
[0056] in other embodiment preferred of the present invention, provides the commercial product that contains the fiber of producing by described method.
Description of drawings
[0057] Fig. 1 is the size distribution schematic diagram of stable suspension of the fresh formation of the microcapsules produced according to embodiment 3; With
[0058] Fig. 2 is after 24 hours, the schematic diagram of the size distribution of the stable suspension of the microcapsules of producing according to embodiment 3.
The specific embodiment
[0059] term as used herein " stable suspension " can be meant the suspension that a plurality of microcapsules that for example wherein contain phase-change material are suspended in the solvent and wherein most of these microcapsules disperse equably.This term can also refer to generation wherein most of microcapsules not have the significantly suspension of gathering.This term can also refer to the generation wherein most of microcapsules do not float on solvent or sink to its bottom suspension.This term can also refer to for the suspension that missible oil is separated out does not wherein take place.
[0060] term " polymer " precursor as used herein " be meant and for example pass through to change into the compound of polymer randomly with other compound polymerizations.Monomer is the example of polymer precursor.
[0061] term as used herein " disperses equably " to be meant that for example wherein most of microcapsules do not have the state of assembling.
[0062] term as used herein " can dissolve ... solvent " for example be meant wherein polymer or the soluble solvent of its precursor, its degree makes to prepare and contains the solution of 1wt% solute at least.
[0063] term as used herein " latent heat " is meant for example by the material absorption of experience state variation or the energy that discharges.
[0064] term as used herein " phase-change material " for example is meant and can absorbs or release energy, and regulates the material that conducts heat at temperature stabilization scope place or in it.The temperature stabilization scope can comprise concrete transition temperature or transformetion range.In some cases, when phase-change material absorption or release heat, typically during the time period when the transformation between two states of phase-change material experience, phase-change material may be able to suppress to conduct heat.This effect is temporary transient typically, and just takes place when absorbing or discharging the latent heat of phase-change material in heating or process for cooling process.Can store or therefrom remove heat and phase-change material in phase-change material typically can replenish effectively by heat or low-temperature receiver again.For some device for carrying out said (implementation), phase-change material can be two or more mixtures of material.By selecting two or more different materials and forming mixture, can regulate the temperature stabilization scope at any required application.According to following article, when introducing, the gained mixture can demonstrate the transition temperature of two or more different transition temperatures or single modification:
Farid, M.M. wait the people at Energy Conversion and Management 45, the ＂ A Review on Phase-change Energy Storage:Materials and Applications among (2004) 1597-1615 (summary that phase transition energy stores: material and application) ＂;
Zalba, B., Deng the people at Applied Thermal Engineeringl 23 (2003), ＂ Review on Thermal Energy Storage with Phase-change:Materials among the 251-283, Heat Transer Analysis and Applications (summary of material thermal energy storage and phase transformation: material, analysis of Heat Transfer and application) ＂;
Kenisarin, M., Deng the people at NATO Advanced Study Institute SummerSchool on Thermal Energy Storage for Sustainable EnergyConsumption (TESSEC), Cesme, Izmir, Turkey, June, the paper ＂ Actual Problems in Using Phase-Change Materials to StoreSolar Energy that submits on 2005 (using phase-change material to store the practical problem of solar energy) ＂.
[0065] according to various embodiments of the present invention, the phase-change material that can be benefited from stable comprises various organic substances.Be restriction as an example and not, the phase-change material that exemplifies comprises hydrocarbon (for example linear paraffin or alkane, branched paraffin, unsaturated hydrocarbons, halogenated hydrocarbons, and alicyclic), aliphatic acid, fatty acid ester, binary acid, dibasic acid ester, 1-halide, primary alconol, aromatic compounds, acid anhydrides (for example stearic anhydride), ethylene carbonate, dihydroxylic alcohols, polyalcohol is (for example, 2,2-dimethyl-1, ammediol, 2-methylol-2-methyl isophthalic acid, ammediol, polyethylene glycol, pentaerythrite, dipentaerythritol, five polyglycereol), polymer, poly-dihydric alcohol, metal and composition thereof.
[0066] selection of phase-change material can be depending on the latent heat and the transition temperature of phase-change material.The latent heat of phase-change material is typically relevant with the ability that its reduction or elimination are conducted heat.In some cases, the latent heat of phase-change material can be at least about 40J/g, for example at least about 50J/g, at least about 60J/g, at least about 70J/g, preferably at least about 80J/g, especially preferably at least about 90J/g with most preferably at least about 100J/g.Therefore, for example, the latent heat scope of phase-change material can be the about 400J/g of about 40J/g-, the about 400J/g of preferably about 60J/g-, the about 400J/g of especially preferably about 80J/g-and the about 400J/g of 100J/g-most preferably from about.The transition temperature of phase-change material typically with can be relevant by the temperature required or temperature required scope that phase-change material is kept.In some cases, the transformetion range of phase-change material can be-10 ℃-Yue 110 ℃ approximately, for example about 0 ℃-Yue 100 ℃, about 0 ℃-Yue 50 ℃, about 10 ℃-Yue 50 ℃, preferred about 15 ℃-Yue 45 ℃, preferred about 22 ℃-Yue 40 ℃ and most preferably 22 ℃-Yue 28 ℃ especially.The selection of phase-change material can be dependent on other factors, and for example it is to the reactive of the material that forms shell or lack reactivity, its anti-degradability, its biological degradability and its toxicity under environment or processing conditions.
[0067] table 1 provides can be used as and has exemplified enumerating of alkane according to the stable phase-change material of various embodiments of the present invention.
Table 1
Figure A200780025288D00151
[0068] phase-change material can be the mixture of two or more materials (for example two or more discussion exemplify phase-change material).By selecting two or more different materials (for example two kinds of different alkanes) and forming its mixture, can in wide scope, regulate the temperature stabilization scope at required application.According to embodiments more of the present invention, phase-change material can comprise the copolymer of two or more materials (for example two or more discussion exemplify phase-change material).
[0069] selection of phase-change material typically depends on the required transition temperature or the required application of gained multicomponent fibre.For example, be incorporated into to keeping the application in the clothes that user's comfort temperature designs for gained multicomponent fibre wherein, desirable can be the phase-change material of transition temperature near room temperature.
[0070] according to embodiments more of the present invention, the phase-change material that is particularly useful comprises that the alkane with 10-44 carbon atom (is C 10-C 44Alkane).Table 1 provides can the interior C that exemplifies as phase-change material of described herein silica capsule 13-C 28Enumerating of alkane.Carbon number is typically relevant with its fusing point in the alkane.For example, to contain the fusing point of the positive octacosane of 28 straight chain carbon atoms be 61.4 ℃ to each molecule.As a comparison, each molecule fusing point of containing the n-tridecane of 13 straight chain carbon atoms is-5.5 ℃.According to embodiment of the present invention, it be that 28.2 ℃ n-octadecane uses for cloth is especially required that each molecule contains 18 straight chain carbon atoms and fusing point.
[0071] other useful phase-change materials comprise that transition temperature is suitable for the polymer phase-change material of the required application of multicomponent fibre (for example, use for cloth, be about 22 ℃-Yue 40 ℃).The polymer phase-change material can comprise having and contains a class or the polymer of the various chain structures of multiclass monomeric unit (or mixture of polymers) more.Especially, the polymer phase-change material can comprise straight chain polymer, branch polymer (for example star shape branch copolymer, comb-branched polymers, or dentation branched polymer), or its mixture.The polymer phase-change material can comprise homopolymers, copolymer (for example ter-polymers, statistical copolymer, random copolymer, alternate copolymer, periodic copolymer, block copolymer, radially copolymer, or graft copolymer) or its mixture.It will be understood by those skilled in the art that can be by adding functional group, and for example amine, acid amides, carboxyl, hydroxyl, ester, ether, epoxy radicals, acid anhydrides, isocyanates, silane, ketone and aldehyde change the reactivity and the degree of functionality of polymer.In addition, the polymer that contains the polymer phase-change material can be crosslinked, entanglement or hydrogen bonding, so that increase its toughness or heat resistance, moisture-proof or chemical resistance.
[0072] according to embodiments more of the present invention, with respect to non-polymer phase-change material (for example alkane), the polymer phase-change material with higher molecular weight, big molecular dimension or viscosity higher can be required.The result of this big molecular dimension or viscosity higher is, the polymer phase-change material can demonstrate less tendency and leak from its shell, and for example bigger molecular dimension or higher viscosity can prevent polymer phase-change material the flowing of the shell element that forms the shell outside or potted component of flowing through.
[0073] for example, in some embodiments of the present invention, polyethylene glycol can be used as phase-change material.The mean molecule quantity of polyethylene glycol is typically relevant with its fusing point.For example, average molecular weight range is that the fusing point of the polyethylene glycol (for example Carbowax 600) of 570-630 is 20 ℃-25 ℃.Can in other temperature stabilization scopes, comprise Carbowax400 (4 ℃-8 ℃ of fusing points), Carbowax 1500 (44 ℃-48 ℃ of fusing points) and Carbowax6000 (56 ℃-63 ℃ of fusing points) by other useful polyethylene glycol.In some embodiments of the present invention, melting range is that 60 ℃-65 ℃ poly(ethylene oxide) also can be used as phase-change material.Further required phase-change material comprises that melting range is 0 ℃-40 ℃ a polyester, and it can for example form by polycondensation dihydroxylic alcohols (or derivatives thereof) and binary acid (or derivatives thereof).Table 2 has been listed the various fusing points that exemplify polyester that form that combine that can adopt binary acid and dihydroxylic alcohols.
Table 2
Figure A200780025288D00181
[0074], can form polymer phase-change material by making phase-change material (phase-change material that exemplifies for example discussed above) and polymer (or mixture of polymers) reaction with required transition temperature according to embodiments more of the present invention.Therefore, for example, n-octadecane acid (being stearic acid) can be reacted or esterification with polyvinyl alcohol, obtains polyvinyl stearate, and perhaps dodecylic acid (being laurate) can react or esterification with polyvinyl alcohol, obtains the polyoxyethylene lauryl vinyl acetate.(for example can make phase-change material, has one or more functional group, the phase-change material of amine, carboxyl, hydroxyl, epoxy radicals, silane, sulfur-containing group groups such as (sulfuric) for example), obtains having the polymer phase-change material of required transition temperature with the bond reaction of polymer.
[0075] phase-change material can comprise the mixture of two or more materials (for example, the phase-change material that exemplifies of two or more discussion).By selecting two or more different materials (for example, two kinds of different alkanes) and forming its mixture, can in wide scope, regulate the temperature stabilization scope at any application-specific.According to embodiments more of the present invention, the mixture of two or more different materials can demonstrate the transition temperature of two or more different transition temperatures or single modification.
[0076] according to one embodiment of the invention, microcapsules comprise shell and nuclear.According to another embodiment, nuclear comprises phase-change material.Shell provides and seals, comprises, surrounds and absorb at least a in the phase-change material.This shell can help to handle phase-change material, provides in the preparation process of fiber phase-change material protection (for example, avoiding high temperature or shearing force) to a certain degree simultaneously.Various materials are suitable for microcapsule shell, comprising synthetic polymer, and carboxaldehyde radicals polymer for example, isocyanates, amine, carboxylic acid derivates, natural material, for example gelatin or cellulose and acrylic polymer, and other, silica for example.Shell polymeric can be thermoplasticity or thermosetting, crosslinked or uncrosslinked, and is soft or hard, the polymer of flexibility or hard.According to one embodiment of the invention, by the carboxaldehyde radicals polymer, silica dioxide granule, or acrylic polymer, precursor, for example acrylic acid, methacrylic acid, formaldehyde and silica precursor form shell, just for example described in patent EP1321182 and US6716526 and patent application WO2004092299 and the WO2005105291, its details is incorporated in the disclosure of the present invention by reference in its entirety at this.
[0077] stable suspension of the present invention comprises and can be dissolved in polymer that comprises in the temperature adjustment fabric or the solvent that can dissolve the precursor of this polymer.Any polymer is suitable for the present invention, if it is incorporated into the words in this temperature adjustment fabric.According to another embodiment of the present invention, polymer is at least a in acrylonitrile based polymer and the cellulose-based polymer.The polymer that the energy dissolving is to be mixed or any solvent of its precursor are suitable.According to one embodiment of the invention, solvent is the aqueous solution.According to another embodiment of the invention, the aqueous solution comprises at least a solute, soda for example, sodium sulfocyanate, zinc chloride, acetone, DMF, NMP and nitric acid.According to another embodiment of the invention, not contain microcapsules, the solute concentration scope is the about 90wt% of about 0.5%-in solvent.According to another embodiment of the invention, not contain microcapsules, the solute concentration scope is the about 70wt% of about 1%-in solvent.
[0078] stable suspension of the present invention comprises described solvent and the microcapsules that contain described phase-change material.According to one embodiment of the invention, microcapsules form the about 50wt% of about 5-of suspension.According to one embodiment of the invention, microcapsules form the about 30wt% of about 10-of suspension.
[0079] feature that contains the stable suspension of the present invention of described solvent and described microcapsules be it stable at least 20 hours.According to one embodiment of the invention, stable at least 40 hours of stable suspension.Term as used herein " stable suspension " can be meant the suspension that wherein most of microcapsules disperse equably.Term as used herein " disperses equably " to be meant that wherein most of microcapsules do not have the state of assembling.Term " stable suspension " also can refer to the suspension that wherein most of microcapsules do not have gathering.This term also can be meant wherein most of microcapsules do not float on solvent or sink to its bottom suspension.This term also can refer to and wherein not observe the suspension that missible oil is separated out.
[0080] according to an embodiment more of the present invention, stable suspension comprises the additive that is selected from defoamer, wetting agent, flow control agent, dispersant and the surfactant.Suitable additive comprises:
A) flow control and rheological agent, for example water-soluble polymer, insoluble polymer, clay, microcrystalline cellulose aerosol;
B) dispersant, for example anion, CATION, both sexes and non-ionic surface active agent, polyacrylic derivative, the polycarboxylic acids polyester of the unsaturated acids of low or high molecular, poly quaternary ammonium compound, polycarboxylic acids, the salt of long-chain polyamines acid amides and have the alkanol ammonium salt of the block copolymer of acidic-group;
C) wetting agent, for example polyether-modified dimethyl silicone polymer (for example available from Byk Chemie BYK-348, BYK-346, BYK-333).
[0081] usually, wetting agent can be selected from silicon compound, fluorine compounds, poly-dihydric alcohol, aliphatic acid, fatty acid amide, fatty alcohol and ester thereof and ether.Suitable reagent also can comprise various mixtures, blend and the copolymer of enumerating from above.
[0082] in a preferred embodiment of the invention, described first suspension further comprises at least a compound with some functional characters, and that described function can comprise is for example fire-retardant, biologically active, antimicrobial acivity, anti-smell, UV absorb, moisture monitoring and water-fast, grease, dirt and/or dyeing.According to one embodiment of the invention, those that functional compounds and function are selected from that table 3 lists and any similar or relevant function.
Table 3 provides the properties of textile and the material of a certain advantage
Figure A200780025288D00211
[0083], functional compounds is dissolved in the steady suspension according to one embodiment of the invention.According to another embodiment, functional compounds is encapsulated in the shell.According to related embodiment, the performance classes of shell is similar to the shell in the microcapsules of phase-change material.According to another embodiment, the shell of functional compounds microcapsules is by making with the shell identical materials of phase-change material micro-capsule.According to relevant embodiment, the encapsulated and microcapsules of functional compounds are evenly dispersed in the stable suspension of the present invention.
[0084] according to one embodiment of the invention, stable suspension remains under the temperature of control.According to relevant embodiment, this temperature range is about 15 ℃-Yue 120 ℃.According to another embodiment, temperature is maintained at about under 20 ℃-Yue 50 ℃.According to another embodiment, stable suspension remains under the low shear-mixed.According to an embodiment of this solution, low shear-mixed is to adopt slurry or screw at 1-100s -1, preferred 1-10s -1Shear rate under mix or stir.
[0085] according to the present invention, the stable suspension that contains solvent and a plurality of microcapsules is used to produce the temperature adjustment fabric that contains polymer.
[0086] according to another embodiment of the invention, this polymer is a cellulose-based polymer, solvent in the stable suspension comprises water and NaOH, and the concentration sodium hydroxide scope is the about 8wt% of about 1%-of solvent and the about 50wt% of about 15%-that microcapsules form described suspension.According to relevant embodiment, polymer is a cellulose-based polymer, solvent in the stable suspension comprises water and NaOH, the concentration sodium hydroxide scope is about 1.5%-about 3% of solvent, the about 30wt% of about 15%-and the suspension that form described suspension with microcapsules keep at ambient temperature.
[0087] one aspect of the present invention also provides the fabric of producing by the method for using stable suspension.More specifically, the fabric that is provided is a commercial product.According to one embodiment of the invention, fabric or commercial product comprise a kind of fiber or multiple fiber.
[0088] according to another embodiment of the present invention, stable suspension comprises at least a additive that is selected from defoamer, flow control agent, wetting and dispersant and the surfactant, for example listed above those.Randomly, suitable additive is present in the 3rd suspension, when using it that microcapsules are provided.For example, in producing the method for microcapsules, use additive, and in the suspension that keeps producing in process of production, described suspension former state ground or certain modification after, be used as the 3rd suspension.According to another embodiment, before mixing, former state ground perhaps with any combining form, for example with the solution form, joins the component that is provided with additive, for example in the 3rd suspension or the solvent, and/or interpolation after mixing.
[0089] embodiment again according to the present invention, in mixed process and/or afterwards, stable (first) suspension is maintained at about in the temperature range of environment-Yue 120 ℃.According to another embodiment, in mixed process and/or afterwards, stable suspension remains under the low shear-mixed.
[0090] according to one embodiment of the invention, also provide preparation to contain the method for the temperature adjustment fabric of polymer, described method comprises provides and mixes at least a functional compounds with the following function of being selected from, and described function is selected from anti-flammability, biologically active, antimicrobial, anti-smell and UV Absorption hereinafter described.According to one embodiment of the invention, functional compounds and function are selected from those that list in the table 3.According to one embodiment of the invention, functional compounds provides with dissolved form.According to another embodiment, functional compounds is encapsulated in the shell.According to related embodiment, the performance classes of shell is similar to the performance of the shell of phase-change material micro-capsule.According to another embodiment, the shell of functional compounds microcapsules is by making with the shell identical materials of phase-change material micro-capsule.Before such mixing or after it, any form of the functional material that is provided and/or its microcapsules is suitable, the first for example stable solution or have polymer and/or the first stable solution of precursor.Mix functional compounds and/or its microcapsules and can use any known method, for example mix.According to one embodiment of the invention, encapsulated and its microcapsules of functional compounds are evenly dispersed in second suspension.According to one embodiment of the invention, formed second suspension comprises the two microcapsules of phase-change material and functional compounds, and these two kinds of microcapsules are evenly dispersed in second suspension.According to another embodiment, in containing the microcapsules of phase-change material, provide functional material.
[0091] according to another embodiment of the invention, the preparation method of temperature adjustment fabric that contains polymer comprises the steps: second suspension former state or that have additional component is transformed on the described fabric.For example,, be coated with second suspension from the teeth outwards, wherein further handle them, evaporating solvent for example, the component that precipitation and/or polymerization comprise within it by known method.Also second suspension can be changed into the polymeric aggregate that microcapsules disperse equably within it, then described pellet be changed into commercial product.The method that preparation contains the temperature adjustment fabric of polymer also can comprise the step that second suspension is changed into fiber.According to one embodiment of the invention, the phase-change material that contains microcapsules is evenly dispersed in the fiber of described preparation.
[0092] prepares many fabrics by synthetic fiber.Routinely, use two kinds of methods to prepare synthetic fiber: solution spinning and melt spinning process.Usually use solution spinning, form acrylic fiber or regenerated celulose fibre, and use melt spinning process usually, form the fiber of nylon fiber, polyester fiber, polypropylene fibre and other similar type.According to one embodiment of the invention, contain the fiber of microcapsules by melt spinning process production, molten polymer and microcapsules wherein are provided, spinning and cooling are for sclerosis.The polymeric aggregate that microcapsules disperse within it equably can be used for producing this fiber by melt spinning.According to related embodiment, the shell of the employed microcapsules of this melt spinning process is prepared by silica.
[0093] according to one embodiment of the invention, prepare fiber by solution spinning, described solvent spinning involves the material solution that spinning contains above-described polymer and/or polymer precursor, phase-change material micro-capsule and randomly at least a reagent, surfactant or functional compounds.According to another embodiment of the invention, material solution can comprise above-described second solution.According to one embodiment of the invention, prepare steady suspension as mentioned above, and in the temperature range of above regulation and under the mixing of above regulation, be stored in the first suitable container.The consumption of the stable suspension of being produced is suitable at least 20 hours, preferred at least 40 hours fiber production.Also produce the solution of polymer and/or precursor and remain in second container.Generate material solution by mixing, then by at least one spinneret spinning and for example further handle by randomly polymerization, dry-spinning or wet spinning from the suspension of described first container and solution from described second container.In wet spinning technology, spinneret is immersed in the chemical bath or keeps being in close proximity to chemical bath and when long filament came out, they contacted chemical bath, and they precipitate from solution and harden.In the dry-spinning spinning technique, realize sclerosis by evaporating solvent in the logistics of air or inert gas, rather than by dilution or chemical reaction precipitation polymers.About more details, referring to Acrylic Fibers, R.Cox is at Synthetic Fibers:Nylon, Polyester, Acrylic, Polyolefins, Woodhead PublishingISBN 1 85,573 488 1 and United States Patent (USP) 5686034,6258304,6333108 and 6538130, BP 2412083 and WO0231236, its relevant teachings is introduced by reference at this.
[0094] according to one embodiment of the invention, fiber is the acrylonitrile group fiber.According to described embodiment, the solution in second container preferably is made up of the solute of the about 20wt% of about 5-in solvent.In particularly preferred embodiment of the present invention, the solution in container is included in the solute of the about 15wt% of about 10-in the solvent.Based on dry weight, solute is preferably by the about 100wt% acrylonitrile monemer of about 80-, the about 20wt% neutral monomer of about 0-, the about 2wt% of at least a and about 0-acid comonomer in methyl acrylate, vinyl acetate, methyl methacrylate and the acrylamide for example, for example Sodium styrene sulfonate, methallylsulfonic acid sodium, 2-methyl-2-acrylamido propane sulfonic acid sodium and itaconic acid are made.
[0095] in particularly preferred embodiment of the present invention, based on dry weight, solute is made by about 95wt% acrylonitrile monemer of about 90-and the described neutral monomer of the about 14wt% of about 0-.
[0096] according to another embodiment, fiber is modacrylic (modacrylic) fiber, and its ratio is that less and solute also contains another comonomer at solute inner propene nitrile, typically the unsaturated molecule of halo ethylenic.According to one embodiment of the invention, the solvent in the solution in second container is the aqueous solution of sodium sulfocyanate, and for example the sodium sulfocyanate concentration range is the sodium thiocyanate water solution of the about 60wt% of about 40-.According to another embodiment of the invention, for example under the situation of modacrylic fibre, solvent is an acetone soln.By known method, for example under agitation, in cold solvent, elevated temperature with dissolve polymer, thereby prepares this solution to dissolving fully then by slow interpolation polymer, and the solution in second container remains on roughly under the environment temperature.
[0097] according to one embodiment of the invention, the steady suspension in first container comprises that sodium thiocyanate water solution is as solvent.The concentration of sodium sulfocyanate is the about 60wt% of about 40-in this solution.This stable suspension comprises the microcapsules with shell and nuclear, and wherein hull shape becomes the about 40wt% of about 5-of microcapsules.Shell is made by the compound such as silica and yuban.Nuclear comprises phase-change material, for example has the straight or branched hydrocarbon of 15-25 carbon atom.Typically, microcapsules have about 2 microns size (full-size) at most.Microcapsules form that about 5-of suspension weight is about 30%, and described suspension also randomly contains viscosity modifier, for example listed above those.When leniently mixing, by adding solvent gradually in the suspension of about 50% microcapsules in water-bearing media, the preparation stable suspension.Stable suspension remains in first container under the low shear-mixed in gentleness under environment temperature roughly.
[0098] according to an embodiment more of the present invention, by based on the polymer dry weight, be suitable for obtaining 2-50%, more preferably under the relative ratios of 5-20% concentration mPCM (rate), mixing is from the solution of second container and suspension (randomly filtering) from first container, raw materials for production solution.By dry-spinning or wet spinning, this material solution of spinning (for example, wherein spinneret is immersed in the relative dilute aqueous or keeps being in close proximity to relative dilute aqueous) forms the microcapsules that contain acrylic fiber with phase-change material then.According to one embodiment of the invention, fiber contains the microcapsules that the about 20wt% of the 5-that has an appointment disperses equably.These fibers are used to produce the commercial product that adapts to all temps then, for example Woven fabric, knit goods and supatex fabric, and for example enthalpy is those of the about 50J/g of about 1J/g-.
[0099] according to another embodiment of the invention, fiber is a cellulose-based fiber.According to this embodiment, the solution in second container is by the solute of the about 15wt% of about 5-in solvent, and the about 11wt% of preferably about 8-forms.The composition of solute is about 5-about 15% of sodium hydrate aqueous solution solvent based on dry weight.According to one embodiment of the invention, the solvent in second container in the solution is the aqueous solution of NaOH, and for example the naoh concentration scope is the sodium hydrate aqueous solution of the about 10wt% of about 4-.By known method, for example dissolved hydrogen sodium oxide molybdena in water, and interpolation cellulose prepares this solution.Preferably, under agitation add the dried fibres element in the NaOH of suitable quantity of water and dissolving, adhere to and form agglomerate to prevent cellulose powder.Stir then, get limpid up to cellulose dissolution and solution becomes.Solution in second container remains on roughly under the environment temperature.
[00100] according to one embodiment of the invention, the stable suspension in first container comprises that the aqueous solution of NaOH is as solvent.Concentration sodium hydroxide is the about 5wt% of about 1-in this solution.According to one embodiment of the invention, the pH of solvent is at least 10, preferably at least 11.5.Stable suspension comprises the microcapsules with shell and nuclear, and wherein hull shape becomes the about 40wt% of about 5-of microcapsules.Shell is by at least a compound, and for example silica, acrylic acid, its derivative, methacrylic acid and derivative thereof are made.Nuclear comprises phase-change material, for example has the straight or branched hydrocarbon of 15-25 carbon atom.Typically, microcapsules are of a size of about 2 microns (full-sizes) at most.Microcapsules form the about 50wt% of about 10-of suspension, and described suspension also randomly contains viscosity modifier, for example cellulose, cellulose derivative, polymer, poly-dihydric alcohol, polysaccharide and the polyvinyl alcohol of sour official's energy.When leniently mixing, by adding solvent gradually in about 50% microcapsule suspensions in water-bearing media, the preparation stable suspension.This stable suspension remains in first container under the low shear-mixed of gentleness at ambient temperature.
[00101] according to one embodiment of the invention, by being suitable under the relative ratios who obtains required %mPCM on the cellulose (rate), mixing is from the solution of second container and suspension (randomly cross and filter) from first sample, preparation material solution.By dry-spinning or wet spinning (for example by in acid, for example flooding or keep being in close proximity to its spinneret in the solution of sulfuric acid), this material solution of spinning forms the artificial silk or the viscose that contain the microcapsules with phase-change material then.According to one embodiment of the invention, fiber contains the microcapsules that the about 40wt% of the 5-that has an appointment disperses equably.Use these fiber production to be suitable for the commercial product of all temps then, for example Woven fabric, knit goods and supatex fabric, for example enthalpy is those of the about 50J/g of about 1J/g-.
[00102] although,, do not plan the present invention is limited on these specific embodiments so that each side of the present invention can be understood more fully and understand in the following embodiments in conjunction with some embodiment preferred and the present invention has been described with reference to the drawings.On the contrary, plan to cover all substitute, modification and equivalence because they can be included in the scope of the present invention of claims definition.Therefore, the following embodiment that comprises preferred embodiment plays the effect of setting forth the present invention's practice, specific detail shown in being appreciated that only is for illustrative discussion the preferred embodiments of the invention with purpose as an example, and thinks the most useful and understand the explanation of preparation process easily and the mode of principle of the present invention and notion is listed these details providing.
[00103] embodiment 1-is used for the stable suspension of the mPCM of acrylic fiber
Under agitation, in 100.0kg carboxaldehyde radicals shell microcapsules (50% microcapsules are available from Ciba Specialty Chemical Co., Bradford, Britain for the positive hydrocarbon of microencapsulation, 115J/g latent heat), add 121.5kg water, add the 178.5kg sodium sulfocyanate then.This obtains containing 12.5% and has sodium sulfocyanate: the ratio of water is the stable suspension of 51/49 microcapsules.The effect suspension stabilization of these microcapsules is anti-assembles〉21 hours.
[00104] embodiment 2-is used for the stable suspension of the mPCM of acrylic fiber
Under agitation, in 100.0kg carboxaldehyde radicals shell microcapsules (50% microcapsules are available from Ciba Specialty Chemical Co., Bradford, Britain for the positive hydrocarbon of microencapsulation, 115J/g latent heat), add the premixed solution of 121.5kg water and 178.5kg sodium sulfocyanate.This obtains containing 12.5% and has sodium sulfocyanate: the ratio of water is the stable suspension of 51/49 microcapsules.The effect suspension stabilization of these microcapsules is anti-assembles〉21 hours.
[00105] embodiment 3-is used for the stable suspension of the mPCM of artificial silk, viscose or cellulose fibre
Under agitation, to 100.0kg polyacrylic shell microcapsules (octadecane of microencapsulation, 175J/g latent heat, 45% microcapsules are available from Ciba Specialty ChemicalCo., Bradford, Britain) add 100.0kg water in, add the 5.2kg 50%NaOH/ aqueous solution then.This obtains pH is 12.8 the stable suspension that contains 21.95% microcapsules.The effect suspension stabilization of these microcapsules is anti-assembles〉24 hours, this by initial slurry size distribution (Fig. 1) and after 24 hours (Fig. 2) show.Just as noted, distribution when at first forming suspension and the distribution after 24 hours do not have marked difference.This stable suspension provides good spinning properties, does not have production line downtime after many days, does not have plugged filter or retardance, and is used for the viscose of spinning 1.7dtex.
[00106] embodiment 4-is used for the unstable suspension of the mPCM of artificial silk, viscose or cellulose fibre
Under agitation, to 100.0kg polyacrylic shell microcapsules (octadecane of microencapsulation, 175J/g latent heat, 45% microcapsules are available from Ciba Specialty ChemicalCo., Bradford, Britain) add 81.8kg water in, add the 1.8kg50%NaOH/ aqueous solution then.This obtains pH is 9.5 the unstable suspension that contains 25.0% microcapsules.That this unstable suspension causes is pressure accumulated, plugged filter and production line downtime after 20 minutes.
[00107] embodiment 5-is used for the stable suspension of the mPCM of Lyocell fiber
The microcapsules (50% microcapsules are available from Ciba Specialty Chemical Co., Bradford, Britain for the alkane PCM of microencapsulation, 120J/g latent heat) that in the 20ml vial, contain the water-wet of phase-change material in conjunction with 0.90g deionized water and 0.20g.Next, (97%NMMO, available from Aldrich Chemical Co., Milwaukee Wis.), obtains having the solution of 1.1wt%mPCM solid to add 8.00gN-methyl morpholine oxide solvent.Bottle is placed in 125 ℃ the baking oven and periodically mixes, mix equably and the solvent fusion up to its content.This solution can use immediately or can cool off/harden it for storage, and then heating.But this circulation repeated multiple times.
[00108] embodiment 6-is used for the stable suspension of the mPCM of Lyocell fiber
The microcapsules (50% microcapsules are available from Ciba Specialty Chemical Co., Bradford, Britain for the alkane PCM of microencapsulation, 120J/g latent heat) that in the 20ml vial, contain the water-wet of phase-change material in conjunction with 0.90g deionized water and 0.20g.Next, (97%NMMO is available from Aldrich Chemical Co. to add 8.00gN-methyl morpholine oxide solvent, Milwaukee, Wis.) and the 0.90g microcrystalline cellulose (available from Aldrich Chemical Co., Milwaukee, Wis.), obtain having the solution of 10wt% solid.This solid comprises the cellulose of 90/10 weight ratio/the contain microcapsules of phase-change material.Bottle is placed in 125 ℃ the baking oven and periodically mixes, mix equably and fusion up to its content.This solution can use immediately or can cool off/harden it for storage, and then heating.But this circulation repeated multiple times.
[00109] for a person skilled in the art, it is evident that, the invention is not restricted to the details of aforementioned illustrative embodiment, with under the situation that does not break away from essential characteristic of the present invention, the present invention may be embodied in that other are concrete in form, therefore in wishing in all respects embodiment of the present invention and embodiment are considered as setting forth rather than restriction, scope of the present invention relates to claims, rather than above stated specification and thereby all changes that drop in the implication of equal value of claim and the scope intend comprising within it.

Claims (39)

1. produce the first stable suspension of the temperature adjustment fabric that contains polymer, described suspension comprises solvent and contains a plurality of microcapsules of at least a phase-change material, wherein said microcapsules are incorporated in the described fabric that contains polymer and the wherein said first stable suspension is characterised in that:
(i) described solvent can dissolve and be selected from fabric formation component at least a in described polymer and the precursor thereof; With
(ii) described effect suspension stabilization was at least about 20 hours.
2. first suspension of claim 1 is further characterized in that the described microcapsules at least about 95% are kept perfectly at least about 20 hours in described suspension.
3. first suspension of claim 1, wherein said fabric is formed by at least one base polymer fiber.
4. first suspension of claim 1, wherein said polymer is selected from acrylonitrile based polymer, cellulose-based polymer, polyester based polymer, polyamide-based polymers and polyolefin based polymer.
5. first suspension of claim 1, wherein said solvent is the aqueous solution.
6. first suspension of claim 1 further comprises at least a further component that is selected from defoamer, flow control agent, wetting agent, dispersant and the surfactant.
7. first suspension of claim 5, the wherein said aqueous solution comprise at least a further component that is selected among soda (sodiumbase), sodium sulfocyanate, zinc chloride, positive methyl morpholine oxide, ammonia, copper sulphate, nitric acid, acetone, DMF and the NMP.
8. first suspension of claim 1, wherein said microcapsules comprise shell and nuclear, and wherein said shell is formed by at least a component that is selected from acrylic acid and derivative thereof, methacrylic acid and derivative thereof, formaldehyde, isocyanates, urea, carboxylic acid derivates, silica precursor and the gelatin.
9. first suspension of claim 1, wherein said microcapsules comprise that shell and nuclear and wherein said nuclear comprise and are selected from octadecane, have the straight-chain hydrocarbons of 15-25 carbon atom and have phase-change material in the branched-chain hydrocarbons of 15-25 carbon atom.
10. first suspension of claim 1, wherein said microcapsules comprise that the weight ratio scope of shell and nuclear and described shell and nuclear is the about 4:6 of about 0.5:9.5-.
11. first suspension of claim 1, wherein said microcapsules form the about 40wt% of about 5-of described suspension.
12. first suspension of claim 1, the max line size range of wherein said microcapsules is about 20 microns of about 0.1-.
13. first suspension of claim 1, further comprise having functional at least a compound, described functional fire-retardant, biologically active, antimicrobial acivity, anti-smell, UV Absorption, moisture monitoring and water-fast, grease, dirt and/or the spot of being selected from.
14. first suspension of claim 1, it is maintained at about under the interior temperature of environment-120 ℃ scope.
15. first suspension of claim 1, wherein said polymer is an acrylonitrile based polymer, wherein said solvent comprises water and sodium sulfocyanate, and wherein the concentration range of sodium sulfocyanate is the about 60wt% of about 40-of solvent and the about 30wt% of about 5-that wherein said microcapsules form described suspension.
16. first suspension of claim 1, wherein said polymer is a cellulose-based polymer, wherein said solvent comprises water and NaOH, and wherein the concentration sodium hydroxide scope forms about 5-about 30% of described suspension for about 1%-about 5% and wherein said microcapsules.
17. second suspension is formed component and forms in conjunction with being selected from least a fabric in polymer and the precursor thereof by first suspension of claim 1.
18. second suspension of claim 17, wherein said microcapsules are evenly dispersed in the whole described suspension.
19. second suspension of claim 17, wherein said second effect suspension stabilization was at least about 20 hours.
20. contain the commercial product of the fabric of right requirement 1.
21. the method for first suspension of preparation claim 1, this method comprises the steps:
(i) provide the microcapsules that contain phase-change material;
(ii) provide and to dissolve the solvent that at least a fabric that is selected from described polymer and the precursor thereof forms component; With
(iii) mix described solvent and described microcapsules, form described first suspension.
22. the method for claim 21 wherein provides described microcapsules and described solvent is joined in the described microcapsules in described container in container, form described first suspension.
23. the method for claim 21, wherein said solvent is the aqueous solution.
24. the method for claim 21 further comprises and adds the step that is selected from least a further component in defoamer, flow control agent, wetting agent, dispersant and the surfactant.
25. the method for claim 21 wherein provides described microcapsules with the 3rd form of suspension of microcapsules in fluid.
26. the method for claim 25, wherein in container, provide described microcapsules in fluid the 3rd suspension and described solvent joined in the described microcapsules in described container, form described first suspension.
27. the method for claim 25, wherein said fluid is a water-bearing media.
28. the method for claim 25, the range of viscosities of wherein said the 3rd suspension is about 3000 centipoises of about 100-.
29. the method for claim 25 wherein provides described the 3rd suspension under the temperature in about environment-120 ℃ scope.
30. the method for claim 21 wherein provides described solvent under the temperature in about environment-120 ℃ scope.
31. the method for claim 21, wherein said first suspension are maintained at about under the interior temperature of environment-120 ℃ scope.
32. the method for claim 21, wherein said first suspension remain under the low shear-mixed.
33. the method for second suspension of preparation claim 17, this method comprise the steps: to provide at least a fabric that is selected from polymer and the precursor thereof to form component, and in conjunction with described component and described first suspension, form described second suspension.
34. the method for claim 33 further comprises described second suspension of wet spinning or dry-spinning.
35. the method for claim 34 wherein with described suspension spinning, forms fiber.
36. the method for claim 35 wherein in conjunction with described fiber and other fibers, forms fabric.
37. fiber according to the preparation of the method for claim 35.
38. the fiber of claim 35, wherein said microcapsules are evenly dispersed in the whole described fiber.
39. contain the commercial product of the fiber of right requirement 35.
CNA2007800252886A 2006-07-04 2007-06-15 Stable suspensions containing microcapsules and methods for the preparation thereof Pending CN101484630A (en)

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