CN102172502A - Method for preparing functional nano capsule size by interfacial polymerization and application of functional nano capsule size - Google Patents
Method for preparing functional nano capsule size by interfacial polymerization and application of functional nano capsule size Download PDFInfo
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Abstract
The invention discloses a method for preparing functional nano capsule size by interfacial polymerization and an application of the functional nano capsule size. The preparation method comprises the following processes: firstly preparing 1-100 parts by weight of functional substance and 5-30 parts by weight of oil soluble monomer or prepolymer into mixed solution, heating the mixed solution to the temperature higher than that of the melting point of the functional substance, mixing and emulsifying the mixed solution and 150-400 parts weight of emulsifier aqueous solution containing 0.1-20 parts by weight of amphiphilic block polymers, and adding 0.01-5 parts by weight of auxiliary emulsifier in the emulsifying process to obtain oil-in-water nano emulsion of mixture; and then slowly adding 5-30 parts by weight of water soluble polymer reaction monomer into the emulsion, adjusting the temperature of polymerization to be 50-80 DEG C, and reacting for 0.5-2 hours, thus the functional nano capsule size is obtained. The application comprises that the size is directly used as solvent in wet spinning while spinning solution of functional fiber is prepared.
Description
Technical field
The present invention relates to Na capsule and fiber applications technology of preparing, be specially a kind of interfacial polymerization manufacture method of functional Na capsule slurries and use the purposes of this functional Na capsule slurry preparation fiber.
Background technology
21 century is the New Times that high-tech develops rapidly, and the International Textile market competition has also entered a brand-new period.People are also more and more higher to taking the dress material demand, developed into and not only required physiological comfort (frivolous, warming, nice and cool) but also will possess psychosensorial comfortable (visual color light modulation pool, sense of touch feel, flexibility, bulkiness, drapability), more need certain specific functionality (antibiotic, antistatic, fire-retardant, antiultraviolet, anti-electromagnetic radiation), promptly require comprehensively have comfortableness, the characteristics of functionalization, high-quality, fitnessization.
Functional fiber can adopt several different methods to obtain.The one, functional materials is mixed directly blending method of back with spinning solution.For example, the disclosed a kind of fragrant fiber of Chinese patent CN 100478505C, it is a kind ofly to make aromatic with natural plants hydrosol, flower water or liquid distilled from honeysuckle flowers or lotus leaves, the flavouring agent of mass fraction 0.2～15% is mixed the spinning solution that obtains viscose rayon with viscose spinning dope, wet spinning sprays the silk technological forming routinely then, obtains aromatic viscose fiber.This method has the following disadvantages: 1, this method is directly mixed functional aromatic wet spinning spray silk technological forming routinely with spinning solution, obtains aromatic viscose fiber, and aromatic wherein is easy to distribute totally; What the flavouring agent that 2, uses in this method adopted is the water-soluble aromatic agent, and difficulty is used to make synthetic fibers.The 2nd, with the skin-core structure spinning process of functional materials as core.For example, the disclosed a kind of fragrant fiber of Chinese patent CN 1007362B, it is a kind of aromatic skin core combination fiber, its cross section comprises a cortex and has the core of hollow space, boiling point is higher than 150 ℃ spices and adds with the amount of mass fraction 0.1 to 10% and be scattered in the thermoplastic polymer that constitutes core under a kind of normal pressure, this core composition is good with the polyethylene polymer, the cortex composition is good with polyethylene to the benzene diester polymer, a kind of classical group of spices becomes a kind of essential oil, and it comprises the lemon oil of (1) mass fraction 10% to 20%; (2) bergamot oil of mass fraction 5% to 15%; (3) lavender oil of mass fraction 2% to 8%; (4) lemon-grass oil of mass fraction 2% to 8%; (5) Cedar wood oil of mass fraction 2% to 8%; And the absolute of jasmine of (6) mass fraction 0.5% to 1.5%.This method has the following disadvantages: 1, the fiber of this method preparation is a skin-core structure, and its core overflows easily, protects fragrant limited time; 2, the flavouring agent of this method use is an essential oil, belongs to oily matter, can not be used to make viscose rayon; 3, this method complex process, production cost is higher, is unfavorable for applying.The 3rd, microcapsules spin processes and microcapsules cladding process.For example, disclosed a kind of granular composition of Chinese patent CN 1946475A and manufacture method thereof, it is included in the core in the polymer shell, wherein core comprises hydrophobic substance, wherein the amount of polymer shell constitutes at least 8% of granular mass mark, and polymer shell comprises by the formed copolymer of the monomer mixture of following component: the unsaturated water-soluble monomer of alkene class of (1) mass fraction 5～90%; (2) mass fraction 5～90% polyfunctionality monomers and (3) mass fraction 0～55% other monomer, what wherein the material proportion of the amount of polymer shell and (1), (2) and (3) made particle partly highly is at least 350 ℃.This invention comprises method and the particle purposes in goods such as fabric and coating composition of making particle, is particularly useful for the application in the coating composition of textile.In the preferred form of this invention, water-soluble emulsifying agent earlier before emulsified monomer solution with high HLB value, perhaps, monomer solution is emulsified in the water that is dissolved with polymerization stabilizer.Polymerization stabilizer can be a hydrophilic polymer, for example, contains the polymer of pendant hydroxyl group, as polyvinyl alcohol and hydroxyethylcellulose.Utilize this method can access 1～20 micron microcapsule granule.International monopoly WO 01/54809A1 also provides similar method, and uses it in the fibre spinning.The deficiency that this two patented method exists is: when 1, adopting the emulsifier aqueous solution of high HLB value, though emulsifying power is higher, and the packing decrease in efficiency; When adopting polymerization stabilizer, packing efficient improves, but capsule grain diameter becomes big; 2, can only obtain the micron order capsule of average grain diameter＞1 micron, if be used for the intensity that the spinning of fiber will greatly reduce fiber; When 3, being used for fiber and applying, coat very easily comes off, and makes fiber lose that it is functional.In addition, Chinese patent CN 101328625A also provides a kind of intellectual and temperature-adjusting viscose and preparation method thereof.It is to add phase-change material micro-capsule to make in the common viscose fiber production process, and wherein fiber weight percentage consists of: the bone dry fiber mass fraction is 84.7～92.85%, and the phase-change material micro-capsule mass fraction is 2～25% in the bone dry fiber; The moisture content mass fraction is 7～15%; Oil content is 0.15-0.30; This fiber is when having inherited the viscose rayon good characteristic, have significant accumulation of heat, heat release bidirectional temp regulation function, it solidifies heat release enthalpy Δ H 〉=2.5J/g, and fusion heat absorption enthalpy Δ H 〉=2.5J/g can be widely used in fields such as clothes, underwear, bedding.The deficiency that this method exists is: 1, the particle diameter of the microcapsules of Shi Yonging is about 5 microns, and because of particle diameter is big, when addition was higher, the intensity of fiber descended; 2, use the dry powder microcapsules again the process for dispersing slurries that prepare microcapsules can increase energy consumption and cost, be unfavorable for large-scale production.
Summary of the invention
At the deficiencies in the prior art, technical problem to be solved by this invention is that a kind of interfacial polymerization Manufacturing approach and use of functional Na capsule slurries is provided.This manufacture method has raw material and is easy to get, and course of reaction is controlled easily, and the Na capsule pattern is regular, encapsulated productive rate height, characteristics such as the easy control of the Na capsule slurry solid content that obtains; These slurries are used to produce functional Na capsule fiber and need not increase equipment and change technology, and described functional Na capsule is included in difficult drop-off in the product fiber, and fibre strength is not subjected to the adding of Nano capsule and obviously descends the degradation characteristics.
The technical scheme that the present invention solves described manufacture method technical problem is, designs a kind of interfacial polymerization manufacture method of functional Na capsule slurries, and this manufacture method adopts following technology:
Earlier the oil-soluble monomer or the oil-soluble performed polymer of 1～100 weight portion functional materials and 5-30 weight portion are made mixed liquor, and mixed liquor is heated to more than the melting temperature of this functional materials, the amphiphilic block polymers emulsifier aqueous solution mixing and emulsifying that again mixed liquor and 150～400 weight portions is contained 0.1～20 weight portion, the assistant for emulsifying agent that adds 0.01～5 weight portion in the emulsion process obtains the oil-in-water nanometer emulsion of mixture; Water-soluble polymer reaction monomers with 5～30 weight portions slowly joins in the described emulsion then, and the telo merization temperature is 50～80 ℃, reacts after 0.5～2 hour, promptly obtains functional Na capsule slurries.
Described functional materials comprises at least a in the following organic substance: phase-change material, flavouring agent, fire retardant, fluorescer, photochromic agent or other known functional materials;
Described oil-soluble monomer is meant the condensation polymerization monomer of 2 above functional groups, comprises as acyl chlorides, sulfonic acid chloride, isocyanates, bischloroformate, epoxy resin or organosiloxane performed polymer;
Described oil-soluble performed polymer is meant the oligomer of a kind of degree of polymerization DP=2～8 that obtained by isocyanates and polyol reaction; The preparation method of described oil-soluble performed polymer is: the isocyanates with 100 weight portions is heated to 50～90 ℃ earlier, drips the polyalcohol of 10～100 weight portions again, and stirring reaction is 10～60 minutes then, promptly obtains the oil-soluble performed polymer;
The HLB value of described amphiphilic block polymers is 5-20, comprises phenylethylene-maleic anhydride block copolymer or ethene-maleic anhydride block copolymer;
Described assistant for emulsifying agent is meant that general formula is C
nH
2n+1OH, the straight-chain alkyl alcohol of n=1～20;
Described water-soluble polymer reaction monomers is meant the condensation polymerization monomer of water miscible 2 above functional groups, comprises ethylene glycol, polyethylene glycol, pentanediol, hexylene glycol, glycerine, pentaerythrite, ethylenediamine, diethyl triamine, triethyl group tetramine, benzenediol or phloroglucin.
The technical scheme that the present invention solves described purposes technical problem is, design a kind of purposes of functional Na capsule slurries, this purposes is the solvent that the functional Na capsule slurries that manufacture method of the present invention is made directly is used as wet spinning, prepare spinning solution, comprise the functional fibre of described functional Na capsule again according to known wet spinning process manufacturing.
Compared with prior art, characteristics of the present invention are: the production technology of (1) functional Na capsule is simple, packing rate height, cyst wall sealing are not revealed, and (can be used for making multiple functional Na capsule) applied widely; (2) the functional Na capsule slurries of Sheng Chaning are directly used in the aqueous solution wet spinning technology, have saved because of problems such as equipment increase that capsule fortreating AIDS disperses to bring again, energy losses; That (3) makes contains functional Na capsule because of the little parcel spinning that is fit to very much fiber of particle diameter, can significantly not reduce the intensity of fiber; (4) the functional nano capsule that is present in fibrous inside can keep its functional permanence.
The specific embodiment
Further specify the present invention below in conjunction with embodiment:
The manufacture method of the functional Na capsule slurries of the present invention's design is interfacial polymerization manufacture method (an abbreviation manufacture method), it adopts following technology: earlier the oil-soluble monomer or the oil-soluble performed polymer of 1～100 weight portion functional materials and 5-30 weight portion are made mixed liquor, and mixed liquor is heated to more than the melting temperature of this functional materials, the amphiphilic block polymers emulsifier aqueous solution mixing and emulsifying that again mixed liquor and 150～400 weight portions is contained 0.1～20 weight portion, the assistant for emulsifying agent that adds 0.01～5 weight portion in the emulsion process obtains the oil-in-water nanometer emulsion of mixture; Water-soluble polymer reaction monomers with 5～30 weight portions slowly joins in the described emulsion then, and the telo merization temperature is 50～80 ℃, reacts after 0.5～2 hour, promptly obtains functional Na capsule slurries.
Functional materials of the present invention comprises at least a in the following organic substance: phase-change material, flavouring agent, fire retardant, fluorescer, photochromic agent or other known functional materials.Described organic phase change material comprises at least a in aliphatic hydrocarbon compounds, alkane compound, alcohol compound and the ester type compound, and they all have temp regulating function, is 20～80 ℃ as the phase transition temperature of aliphatic hydrocarbon compounds.During two or more described compound, require to mix; Described alkane compound comprises n-tetradecane, hexadecane, n-octadecane, NSC 77136, n-eicosane, Heneicosane or n-docosane etc.; Described alcohol compound comprises lauryl alcohol, cyclohexanol or the tert-butyl alcohol etc.; Described ester type compound comprises BS etc.; Described phase-change material mass fraction is 10～60%.Described organic flavouring agent is meant the oiliness flavouring agent, as lemon oil, cinnamon oil, peppermint oil, jasmine oil, attar of rose, rock attar of rose, sandalwood oil, Java Cananga Oil, tangerine oil, sensitive plant oil, tea oil, volatile oil extracted from eucalyptus' leaves or twigs, geranium oil, sage oil, cardamom oil, fennel oil, ginger oil, juniper oil, spearmint oil, hazelnut oil, black pepper oil, camphorated oil, lavender and violet compound wet goods; Described fire retardant is meant organic fire-retardant, comprises that chlorine wax-52, chlorine wax-40, chlorinated paraffin-70, deca-BDE, tetrabromobisphenol A, pentabromotoluene, HBCD, tricresyl phosphate phenol, xylenylphosphate or butylbenzene are phosphate etc.; Described fluorescer is meant the organic fluorescence agent, comprises stilbene compound, coumarin derivative, pyrazoline derivative, naphthalimide derivative or rhodamine analog derivative etc.; Described photochromic agent is meant the organic photochromic agent, comprises spiro-pyrans, diarylethene or azobenzene etc.
Oil-soluble monomer of the present invention is meant the condensation polymerization monomer of 2 above functional groups, comprises as acyl chlorides, sulfonic acid chloride, isocyanates, bischloroformate, epoxy resin or organosiloxane performed polymer; Described oil-soluble performed polymer is meant a kind of oligomer (degree of polymerization DP=2～8) product that is obtained by isocyanates and polyol reaction.The preparation method of described oil-soluble performed polymer is: the isocyanates with 100 weight portions is heated to 50～90 ℃ earlier, drips the polyalcohol of 10～100 weight portions again, and stirring reaction is 10～60 minutes then, promptly obtains the oil-soluble performed polymer; Wherein, described isocyanates comprises toluene di-isocyanate(TDI) or methyl diphenylene diisocyanate; Described polyalcohol comprises ethylene glycol, polyethylene glycol, pentanediol, hexylene glycol, glycerine or pentaerythrite.
The HLB value of amphiphilic block polymers of the present invention is 5-20, comprises phenylethylene-maleic anhydride block copolymer or ethene-maleic anhydride block copolymer.Described amphiphilic block polymers emulsifying agent, its molecule is made up of hydrophilic segment and hydrophobic segment, is to be prepared from by the hydrophilic/hydrophobic monomer copolymerization.Hydrophilic segment comprises polyoxyethylene, polymine, polyacrylamide or HPMA; Hydrophobic segment comprises polyoxypropylene, polyoxy butylene, polystyrene or polysiloxanes; Described block copolymer comprises polyvinyl acetate-polyoxyethylene, hydrogenated butadiene polymer-poly styrene sulfonate, polystyrene-poly oxygen ethene, polymethyl methacrylate (PMMA)-polyoxyethylene, PMMA-acrylates etc.; Be used for emulsifying agent of the present invention and be preferably phenylethylene-maleic anhydride block copolymer or ethene-maleic anhydride block copolymer.Different with two kinds of different monomers of hydrophilic segment in the molecule and hydrophobic segment proportion in described copolymer (phenylethylene-maleic anhydride block copolymer or ethene-maleic anhydride block copolymer), the HLB value of copolymer also changes thereupon.Such as, maleic anhydride (MA) causes the variation of HLB value as follows with the ratio of styrene (S):
MA∶S＝0.3∶1 HLB＝5.75；
MA∶S＝0.5∶1 HLB＝7.5；
MA∶S＝1∶1 HLB＝11.25；
MA∶S＝2∶1 HLB＝15.38；
MA∶S＝3∶1 HLB＝17.60；
During use, select the amphiphilic block polymers emulsifying agent of different hydrophilic segment and hydrophobic segment ratio according to institute's emulsification function Substance Properties.Each emulsifying agent all has certain HLB value, and each emulsified functional materials all has a required HLB value, when the HLB of the emulsifying agent of selecting for use value accords with required HLB value, just can make more stable emulsifying agent.But, the HLB value that single emulsifying agent had, the not necessarily lucky and emulsified required HLB value of functional materials adapts, so select the different hydrophilic segment and the amphiphilic block polymers emulsifying agent of hydrophobic segment ratio promptly to select the emulsifying agent of different HLB values.
Assistant for emulsifying agent of the present invention is meant the alkyl alcohols material, better is straight-chain alkyl alcohol, and general formula is C
nH
2n+1OH, n=1～20.This class alkylol commonly used has methyl alcohol, ethanol, normal propyl alcohol, n-butanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol, n-nonyl alcohol, Decanol, positive undecyl alcohol, n-dodecanol, positive tridecanol, positive tetradecyl alchohol, positive pentadecanol, positive hexadecanol, positive heptadecanol, positive 18 alcohol, positive nonadecanol or positive eicosanol etc., recommend to use the straight-chain alkyl alcohol of n=8～16, be more preferably the straight-chain alkyl alcohol that uses n=8～12.
Water-soluble polymer reaction monomers of the present invention is meant the condensation polymerization monomer of water miscible 2 above functional groups, comprises ethylene glycol, polyethylene glycol, pentanediol, hexylene glycol, glycerine, pentaerythrite, ethylenediamine, diethyl triamine, triethyl group tetramine, benzenediol or phloroglucin.
First inventive point of the present invention is, using emulsifying agent is amphiphilic block polymers, the alkylol assistant for emulsifying agent of HLB value as 5-20, obtains by surfactant compound that functional materials requires or optimum HLB value.Emulsification of the present invention can be taked more than one emulsifying manner emulsification in powerful mechanical agitation emulsification, the emulsification of high speed shear mulser or the ultrasonic emulsification.In the present invention, functional materials emulsification is dispersed in aqueous phase, obtain the high concentration functional materials nanoemulsions of mass fraction 20～60% through emulsification, adopt the functional Na capsule slurries of high solids content of interfacial polymerization known technology quality of production mark 20～70%.As everyone knows, emulsification is that the production polymer is the indispensable process of functional micro-nano capsule of shell.Functional materials is dispersed in the water that contains the water soluble surfactant active, and functional materials overcomes surface force under the effect of mechanical agitation and surfactant becomes small emulsion droplet.Usually, after surfactant was determined, stir speed (S.S.) was fast more, and the particle diameter of the drop that obtains is just more little.The hydrophilic ability of the surfactant of high HLB value is strong, obtains the drop of small particle diameter easily, but encapsulated efficient (Franke Tai Yakesi on the low side, Ka Saleinalandefasi top grade, mini-emulsion polymerization prepare polymer nanocomposite capsule, Lang Gemiuer, 2001,17,908-918; Franca Tiarks, Katharina Landfester, and Markus Antonietti, Preparation of Polymeric Nanocapsules by Miniemulsion Polymerization, Langmuir, 2001,17,908-918), be unfavorable for suitability for industrialized production.
The functional Na capsule slurries of manufacture method manufacturing of the present invention can be used as commodity selling.Second inventive point of the present invention is, the functional Na capsule slurries of manufacture method manufacturing of the present invention directly are used as the solvent or the dilution of wet spinning, prepare spinning solution, and comprise the functional fibre of functionalization Na capsule according to known wet spinning process manufacturing.The design of this fiber fabrication process has been saved because of problems such as equipment increases that capsule fortreating AIDS disperses to bring again, energy losses, and efficient improves, the cost reduction, and make the serialization of functional fibre process for making.
In existing spining technology, viscose rayon, vinylon fibre, acrylic fiber all are by being that the wet spinning technology of solvent obtains with water.Utilize the slurries of the functional Na capsule that the method for the invention obtains all can directly be used to the solvent of these spinning process.
For example, be used for making the viscose rayon that contains the function nano capsule: spinning solution comprises the viscose rayon stoste of sulfidation or maturation, its fiber quality mark is 5～20 weight portions, slurries 10～50 weight portions of above-mentioned functions Na capsule are joined in the rayon spinning stoste, high-speed stirred is after three-stage filtration, wet spinning process spinning routinely then after the measuring pump metering, enters 10～60 ℃ of coagulating baths through candle filter and spinning head; Described coagulating bath is made up of 30～150g/L sulfuric acid, 50～350g/L sodium sulphate and 5～80g/L zinc sulfate, total drawing ratio is 20～30%, spinning speed is 10～100m/min, and technology promptly obtains containing the viscose rayon of function nano capsule after the oven dry that oils routinely again.Described viscose fiber manufacturing technology process is: pulp → alkali cellulose → cellulose sulfonic acid fat → viscose glue and functional nano capsule be mixed → spinning → shaping → drawing-off → cut-out → fine purifiation → drying → shredding → make the gluing fiber of function nano capsule.
Also for example, be used to make the acrylic fiber that contains the functional nano capsule: with the acrylonitrile of 80～95 weight portions, 5～12 parts by weight of acrylic methyl esters, 0.5 the metering system disulfonate acid of～1.5 weight portions, add the polymerization in the functional nano capsule slurries that contain sodium sulfocyanate of 60～120 weight portions of initator azodiisobutyronitrile, perhaps direct polymer with 100 weight portions is dissolved in the aqueous solution of 60～120 weight portion functional nano capsule slurries that contain sodium sulfocyanate, obtain spinning solution, wet spinning process spinning routinely again, through coagulating bath, washing, after the stretching, promptly obtain containing the acrylic fiber of functional nano capsule.
Again for example, be used to make the vinylon fibre that contains the functional nano capsule: with the functional nano capsule slurries of 100 weight portions as solvent, be mixed with spinning solution by the polyvinyl alcohol of 14～20 weight portions and 1～6 parts by weight of cross-linking agent formaldehyde or boric acid, through spinneret orifice Cheng Sihou, enter coagulating bath and drawing-off, then through damp and hot drawing-off bath, acid bath, neutralization bath, drying, the dry heat drafting technical process promptly obtains containing the vinylon fibre of functional nano capsule.
The present invention does not address part and is applicable to prior art.
Below provide specific embodiments of the invention, specific embodiment only is used to be described in further detail the present invention, does not limit claim of the present invention.
Embodiment 1
(1) the phase-change material Na capsule slurries of polyureas cyst wall are produced in interfacial polymerization:
Earlier with the Toluene-2,4-diisocyanate of 10 kilograms of phase-change material n-tetradecanes and 2.5 kilograms, the 4-diisocyanate monomer mixes, and be heated to 40 ℃, mixed liquor is injected reactor, the solution that is mixed that ethene-copolymer-maleic anhydride aqueous solution (solid content 20%) of 1.2 kilograms is dissolved in 18.8 kilograms of distilled water that fills that is heated to 40 ℃ is in advance arranged in the reactor, open the high speed shear mulser, emulsification under 7000～8000 rev/mins speed, the positive tetradecyl alchohol that slowly adds 85mL in the emulsion process, 2.5 after hour, obtain the emulsion that average grain diameter is 820nm, under agitation drip the ethylenediamine solution of 2.0 kilogram of 50% weight again, dripped the back insulation reaction 1.5 hours, and promptly obtained polyureas cyst wall phase-change material Na capsule slurries, its solid content is 39%.
(2) contain the manufacturing of the phase-change material Nano capsule polyvinyl long filament of polyureas cyst wall:
Above-mentioned 39% solid content contains 50 kilograms in the heat accumulating phase change material Na capsule slurries of polyureas cyst wall as solvent, degree of polymerization DP=1750 ± 50 that add 7.5 kilograms, the polyvinyl alcohol of alcoholysis degree 99.9%, in polyvinyl alcohol, add 0.15 kilogram boric acid and 0.01 kilogram oxirane high polymer again, make spinning solution; Through after spinneret extrudes, through coagulating bath, neutralization baths, damp and hot drawing-off, washing and drying then, after the dry heat drafting processing, promptly obtain heat-accumulation temperature-adjustment vinylon fibre long filament again.The baked tensile strength of this fiber was 3.6 gram/dawn, and initial modulus was 230 gram/dawn, and elongation is 28%.
Embodiment 2
(1) the essence Na capsule slurries of polyurethane cyst wall are produced in interfacial polymerization:
The preparation of oil-soluble performed polymer: add 2.5 kilograms Toluene-2,4-diisocyanate in the 10L reactor, the 4-diisocyanate monomer, temperature is heated to 80 ℃, slowly add 0.5 kilogram 1,4-ethylene glycol, insulation reaction 30 minutes obtains light yellow thick oil-soluble performed polymer; The preparation of essence Na capsule slurries: earlier 10 kilograms of jasmine oils and above-mentioned oil-soluble performed polymer are mixed, mixed liquor is injected reactor, there is 0.8 kilogram the styrene-maleic anhydride copolymer aqueous solution (solid content 20%) to be dissolved in the solution that is mixed of 18.2 kilograms of distilled water in the reactor, open the high speed shear mulser, emulsification under 9000 rev/mins speed, the n-dodecanol that slowly adds 85mL in the emulsion process, after 2 hours, obtain the emulsion that average grain diameter is 870nm, under agitation drip 2.0 kilogram 1 again, 4-ethylene glycol dripped the back insulation reaction 1 hour, promptly obtain the fragrant Na capsule slurries of polyurethane cyst wall jasmine, its solid content is 39%.
(2) contain the manufacturing of the tool fragrance Nano capsule acrylic fiber of polyurethane cyst wall:
2.5 kilograms sodium sulfocyanates are dissolved in 1.0 kilograms the fragrant Na capsule slurries of above-mentioned jasmine, and add 62.5 kilograms acrylonitrile, 9.4 the methyl acrylate of kilogram, 0.12 kilogram methylpropene sodium sulfonate and initator azodiisobutyronitrile polymerisation obtain spinning solution; Wet spinning technology spinning routinely, solidification forming, washing subsequently two times of 75 ℃ of following preheat stretch, again in 150 ℃ of of short duration decatizes of superheated steam, stretch in 85 ℃ of water-baths after 2～5 times afterwards, promptly obtain tool fragrance function acrylic fiber.
Embodiment 3
(1) fluorescence Na capsule slurries are produced in interfacial polymerization:
Earlier 2.0 kilograms of disperse yellows 11 are scattered in 3.5 kilograms the acyl chlorides, mixed liquor is injected reactor, fill the solution that is mixed that polyoxyethylene-copolymer-maleic anhydride aqueous solution (solid content 10%) of 1.5 kilograms is dissolved in 18.5 kilograms of distilled water in the reactor, open the high speed shear mulser, emulsification under 8000 rev/mins speed, the n-nonyl alcohol that slowly adds 120mL in the emulsion process, 2.5 after hour, obtain the emulsion that average grain diameter is 750nm, under agitation drip 2.0 kilogram 1 again, 4-ethylene glycol dripped the back insulation reaction 0.5 hour, promptly obtained fluorescence Na capsule slurries.
(2) manufacturing of fluorescence viscose rayon:
5.0 the above-mentioned slurries of kilogram be made into alkali lye after 170 kilograms water mixes, add 20 kilograms of cellulose sulfonate dissolvings and obtain rayon spinning stoste (the fiber quality mark is 10%), leave standstill vacuum row bubble after the high-speed stirred, measure after candle filter and spinning head enter 40 ℃ of coagulating baths through measuring pump then; Described coagulating bath is by 75g/L sulfuric acid, and 260g/L sodium sulphate and 20g/L zinc sulfate are formed, and total drawing ratio is 150%, and spinning speed is 40m/min, and technology obtains having the viscose rayon of anti-flaming function after oiling, drying routinely again.
Embodiment 4
Embodiment 4 is as embodiment 2 comparing embodiments, prepares capsule by the method for embodiment 2 (1), do not add n-dodecanol in the emulsion process, obtains the microcapsule slurry of average grain diameter 8.2 μ m.Press embodiment 2 (2) with this microcapsule slurry and make acrylic fiber, the spinneret clogging appears in spinning process, normally spinning.
Claims (3)
1. the interfacial polymerization manufacture method of functional Na capsule slurries, this manufacture method adopts following technology:
Earlier the oil-soluble monomer or the oil-soluble performed polymer of 1～100 weight portion functional materials and 5-30 weight portion are made mixed liquor, and mixed liquor is heated to more than the melting temperature of this functional materials, the amphiphilic block polymers emulsifier aqueous solution mixing and emulsifying that again mixed liquor and 150～400 weight portions is contained 0.1～20 weight portion, the assistant for emulsifying agent that adds 0.01～5 weight portion in the emulsion process obtains the oil-in-water nanometer emulsion of mixture; Water-soluble polymer reaction monomers with 5～30 weight portions slowly joins in the described emulsion then, and the telo merization temperature is 50～80 ℃, reacts after 0.5～2 hour, promptly obtains functional Na capsule slurries;
Described functional materials comprises at least a in the following organic substance: phase-change material, flavouring agent, fire retardant, fluorescer, photochromic agent or other known functional materials;
Described oil-soluble monomer is meant the condensation polymerization monomer of 2 above functional groups, comprises as acyl chlorides, sulfonic acid chloride, isocyanates, bischloroformate, epoxy resin or organosiloxane performed polymer;
Described oil-soluble performed polymer is meant the oligomer of a kind of degree of polymerization DP=2～8 that obtained by isocyanates and polyol reaction; The preparation method of described oil-soluble performed polymer is: the isocyanates with 100 weight portions is heated to 50～90 ℃ earlier, drips the polyalcohol of 10～100 weight portions again, and stirring reaction is 10～60 minutes then, promptly obtains the oil-soluble performed polymer;
The HLB value of described amphiphilic block polymers is 5-20, comprises phenylethylene-maleic anhydride block copolymer or ethene-maleic anhydride block copolymer;
Described assistant for emulsifying agent is meant that general formula is C
nH
2n+1OH, the straight-chain alkyl alcohol of n=1～20;
Described water-soluble polymer reaction monomers is meant the condensation polymerization monomer of water miscible 2 above functional groups, comprises ethylene glycol, polyethylene glycol, pentanediol, hexylene glycol, glycerine, pentaerythrite, ethylenediamine, diethyl triamine, triethyl group tetramine, benzenediol or phloroglucin.
2. the interfacial polymerization manufacture method of functional Na capsule slurries according to claim 1 is characterized in that described assistant for emulsifying agent is meant that general formula is C
nH
2n+1OH, the straight-chain alkyl alcohol of n=8～12.
3. the purposes of claim 1 or 2 described functional Na capsule slurries, this purposes is the solvent that described functional Na capsule slurries directly is used as wet spinning, prepare spinning solution, comprise the functional fibre of described functional Na capsule again according to known wet spinning process manufacturing.
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| CN109576808A (en) * | 2018-11-29 | 2019-04-05 | 山传雷 | A kind of inorganic fire-retarded intelligent temperature adjusting fiber cellulose fiber and preparation method thereof |
| CN109689952A (en) * | 2016-07-29 | 2019-04-26 | 服饰与高级纺织英国有限公司 | Silicone oil is eliminated from Spandex polymer spinning solution |
| CN115287044A (en) * | 2021-05-04 | 2022-11-04 | 纳米及先进材料研发院有限公司 | Rupture-resistant and easy-to-disperse nano-capsule phase change material and synthesis method thereof |
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| CN107022800A (en) * | 2017-03-24 | 2017-08-08 | 山传雷 | A kind of high heat storage amount phase-changing and temperature-regulating viscose rayon and preparation method thereof |
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| CN109137113A (en) * | 2017-03-24 | 2019-01-04 | 山传雷 | A kind of phase-changing and temperature-regulating viscose rayon of good hygroscopicity and preparation method thereof |
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| CN109137113B (en) * | 2017-03-24 | 2021-06-01 | 青岛邦特生态纺织科技有限公司 | Phase-change thermoregulation viscose fiber with good hygroscopicity and preparation method thereof |
| CN109576808A (en) * | 2018-11-29 | 2019-04-05 | 山传雷 | A kind of inorganic fire-retarded intelligent temperature adjusting fiber cellulose fiber and preparation method thereof |
| CN109576808B (en) * | 2018-11-29 | 2021-08-24 | 青岛邦特生态纺织科技有限公司 | Inorganic flame-retardant intelligent temperature-adjusting cellulose fiber and preparation method thereof |
| CN115287044A (en) * | 2021-05-04 | 2022-11-04 | 纳米及先进材料研发院有限公司 | Rupture-resistant and easy-to-disperse nano-capsule phase change material and synthesis method thereof |
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