CN102174142B - Free radical emulsion polymerization manufacturing method and application of functional nanocapsule slurry - Google Patents
Free radical emulsion polymerization manufacturing method and application of functional nanocapsule slurry Download PDFInfo
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Abstract
The invention discloses a free radical emulsion polymerization manufacturing method and application of functional nanocapsule slurry. The manufacturing method comprises the following steps of: mixing 1 to 100 weight parts of functional material, 5 to 30 weight parts of oil-soluble monomer, 0.5 to 5 weight parts of cross-linking agent and 0.01 to 0.5 weight part of initiator to obtain mixed liquor, and heating the mixed liquor to a temperature higher than the melting point of the functional material; and mixing and emulsifying the mixed liquor and 150 to 400 weight parts of emulsifier aqueous solution which contains 0.1 to 20 weight parts of amphiphilic block copolymer, adding 0.01 to 5 weight parts of co-emulsifier in the emulsifying process, introducing nitrogen to remove oxygen, regulating the temperature of polymerization reaction to be between 60 and 90 DEG C under low-speed stirring, and reacting for 3 to 5 hours to obtain the functional nanocapsule slurry. In the application, the functional nanocapsule slurry is directly used as a solvent for wet spinning to prepare spinning solution for preparing functional fibers.
Description
Technical field
The present invention relates to Na capsule and fiber applications technology of preparing, be specially a kind of free-radical emulsion polymerization manufacture method of functional Na capsule slurries and use these functional Na capsule slurries to prepare the purposes of 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, drape), more need certain specific functionality (antibiotic, antistatic, fire-retardant, antiultraviolet, anti-electromagnetic radiation), namely require comprehensively have comfortableness, the characteristics of functionalization, high-quality, fitnessization.
Functional fiber can adopt several different methods to obtain.The one, functional substance is mixed rear directly blending method with spinning solution.For example, the disclosed a kind of fragrant fiber of Chinese patent CN 100478505C, it is a kind ofly to make perfume compound with natural phant hydrosol, flower water or liquid distilled from honeysuckle flowers or lotus leaves, the spinning solution that flavouring agent and the viscose spinning dope of massfraction 0.2～15% is mixed to get viscose fiber, then wet-spinning sprays the silk technological forming routinely, obtains aromatic viscose fiber.The method has the following disadvantages: 1, the method is directly mixed functional perfume compound routinely wet-spinning spray silk technological forming with spinning solution, obtains aromatic viscose fiber, and perfume compound wherein is easy to distribute totally; What the flavouring agent that 2, uses in the method adopted is the water-soluble aromatic agent, difficult for the manufacture of synthon.The 2nd, with the skin-core structure spinning processes of functional substance 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 transverse section comprises a cortex and has the core of hollow space, boiling point is higher than 150 ℃ spices and adds with the amount of massfraction 0.1 to 10% and be scattered in the thermoplastic polymer that consists of core under a kind of normal pressure, this core composition is take the polyethylene polymkeric substance as good, the cortex composition take polyethylene to the benzene diester polymer as good, a kind of classical group of spices becomes a kind of volatile oil, and it comprises the lemon oil of (1) massfraction 10% to 20%; (2) bergamot oil of massfraction 5% to 15%; (3) oleum lavendulae of massfraction 2% to 8%; (4) lemon-grass oil of massfraction 2% to 8%; (5) Juniperus virginiana oil of massfraction 2% to 8%; And the jasmine absolute of (6) massfraction 0.5% to 1.5%.The method has the following disadvantages: 1, the fiber of the method preparation is skin-core structure, and its core easily overflows, and protects fragrant limited time; 2, the flavouring agent of the method use is essential oil, belongs to oily matter, can not be for the manufacture of viscose fiber; 3, the method complex process, production cost is higher, is unfavorable for applying.The 3rd, microcapsule spin processes and microcapsule cladding process.For example, the 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 consists of at least 8% of granular mass mark, and polymer shell comprises by the formed multipolymer of the monomer mixture of following component: the unsaturated water-soluble monomer of alkene class of (1) massfraction 5～90%; (2) massfraction 5～90% polyfunctionality monomers, and (3) massfraction 0～55% other monomer, wherein the material proportion of the amount of polymer shell and (1), (2) and (3) so that particle partly highly be 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 textiles.In the preferred form of this invention, water-soluble the emulsifying agent with high HLB value first before emulsified monomer solution, perhaps, monomer solution is emulsified in the water that is dissolved with polymerization stabilizer.Polymerization stabilizer can be hydrophilic polymer, for example, contains the polymkeric substance of pendant hydroxyl group, such as polyvinyl alcohol and Natvosol.Utilize the method can access 1～20 micron microcapsule granule.International monopoly WO 01/54809A1 also provides similar method, and uses it in the fiber sprinning.The deficiency that this two patented method exists is: when 1, adopting the emulsifier aqueous solution of high HLB value, although emulsifying power is higher, and the packing decrease in efficiency; When adopting polymerization stabilizer, packing efficient improves, but capsule grain diameter becomes large; 2, the micron order capsule of median size＞1 micron can only be obtained, low-fiber intensity will be greatly fallen if be used for the spinning of 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 massfraction is 84.7～92.85%, and the phase-change material micro-capsule massfraction is 2～25% in the bone dry fiber; The moisture content massfraction is 7～15%; Oil content is 0.15-0.30; This fiber is when having inherited the viscose fiber good characteristic, have significant accumulation of heat, heat release bidirectional temp regulation function, it solidifies heat release enthalpy Δ H 〉=2.5J/g, and melting heat absorption enthalpy Δ H 〉=2.5J/g can be widely used in the fields such as clothes, underwear, bedclothes.The deficiency that the method exists is: the particle diameter of the microcapsule that 1, use about 5 microns, because particle diameter is large, when add-on is higher, the strength degradation of fiber; 2, the slurries that use dry powder microcapsule redispersion method to prepare microcapsule can increase energy consumption and cost, are unfavorable for large-scale production.
Summary of the invention
For the deficiencies in the prior art, technical problem to be solved by this invention is that a kind of free-radical emulsion polymerization Manufacturing approach and use of functional Na capsule slurries is provided.This manufacture method has raw material and is easy to get, and reaction process is easily controlled, and the Na capsule pattern is regular, and encapsulated productive rate is high, the characteristics such as the easy control of the Na capsule slurry solid content that obtains; These slurries need not increase equipment and change technique for the production of functional Na capsule fiber, 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, design a kind of free-radical emulsion polymerization manufacture method of functional Na capsule slurries, this manufacture method adopts following technique: first with the oil-soluble monomer of 1～100 weight part functional substance and 5～30 weight parts, 0.5 the initiator of the linking agent of～5 weight parts and 0.01～0.5 weight part is made mixed solution, and mixed solution is heated to more than the melting temperature of this functional substance, the amphiphilic block polymers emulsifier aqueous solution mixing and emulsifying that again mixed solution and 150～400 weight parts is contained 0.1～20 weight part, the assistant for emulsifying agent that adds 0.01～5 weight part in the emulsion process, letting nitrogen in and deoxidizing, under stirring at low speed, telo merization is warmed up to 60～90 ℃, react after 3～5 hours, namely obtain functional Na capsule slurries.
Described functional substance comprises at least a in the following organic substance: phase change material, flavouring agent, fire retardant, fluorescent agent, photochromic agent or other known functional substance; Described oil-soluble monomer is vinyl free radical monomer, and described vinyl free radical monomer is styrenic, a, a kind of in beta-unsaturated esters class, ketone, amides or nitrile compounds or their derivative; Described linking agent is double vinyl compound, comprises Vinylstyrene, diacrylate butanediol ester or allyl methacrylate(AMA); Described initiator refers to oil-soluble azo-initiator or peroxide initiator; The HLB value of described amphiphilic block polymers is 5-20, comprises phenylethylene-maleic anhydride segmented copolymer or ethene-maleic anhydride segmented copolymer; Described assistant for emulsifying agent refers to that general formula is C
nH
2n+1OH, the straight chained alkyl alcohol matter of n=1～20.
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 again the functional fibre of described functional Na capsule according to known wet spinning process manufacturing.
Compared with prior art, characteristics of the present invention are: the production technique of (1) functional Na capsule is simple, the packing rate is high, the cyst wall sealing is not revealed, and (can be used for making the several functions Na capsule) applied widely; (2) the functional Na capsule slurries of producing 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 wastees; 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 fall low-fiber intensity; (4) the functional nano capsule that is present in fibrous inside can keep its functional permanence.
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 free-radical emulsion polymerization manufacture method (abbreviation manufacture method), it adopts following technique: first with the oil-soluble monomer of 1～100 weight part functional substance and 5～30 weight parts, 0.5 the initiator of the linking agent of～5 weight parts and 0.01～0.5 weight part is made mixed solution, and mixed solution is heated to more than the melting temperature of this functional substance, the amphiphilic block polymers emulsifier aqueous solution mixing and emulsifying that again mixed solution and 150～400 weight parts is contained 0.1～20 weight part, the assistant for emulsifying agent that adds 0.01～5 weight part in the emulsion process, letting nitrogen in and deoxidizing, under stirring at low speed, telo merization is warmed up to 60～90 ℃, react after 3～5 hours, namely obtain functional Na capsule slurries.
Functional substance of the present invention comprises at least a in the following organic substance: phase change material, flavouring agent, fire retardant, fluorescent agent, photochromic agent or other known functional substance.Described organic phase change material comprises at least a in aliphatic hydrocarbon compounds, alkane compound, alcohol compound and the ester compound, and they all have temp regulating function, is 20～80 ℃ such as the transformation temperature of aliphatic hydrocarbon compounds.During two or more described compound, require to mix; Described alkane compound comprises n-tetradecane, n-hexadecane, Octadecane, NSC 77136, NSC 62789, heneicosane or n-docosane etc.; Described alcohol compound comprises lauryl alcohol, hexalin or the trimethyl carbinol etc.; Described ester compound comprises n-butyl stearate etc.; Described phase change material massfraction is 10～60%.Described organic flavouring agent refers to the oiliness flavouring agent, such as lemon oil, Oleum Cinnamomi, spearmint oil, jasmine oil, rose oil, rock rose oil, santal oil, cananga oil, tangerine oil, Touch-me-notAction Plant oil, tea oil, volatile oil extracted from eucalyptus' leaves or twigs, Herba Erodii oil, sage oil, Oils, Elettaria cardamomum, olium anisi, ginger oil, juniper oil, Oleum Menthae Rotundifoliae, hazelnut oil, Fructus piperis nigrum oil, white oil of camphor, lavender and violet compound wet goods; Described fire retardant refers to organic fire-retardant, comprises that chlorine wax-52, chlorine wax-40, chlorinated paraffin-70, decabromodiphynly oxide, tetrabromo-bisphenol, pentabromotoluene, hexabromocyclododecane, tricresyl phosphate phenol, xylenylphosphate or butylbenzene are phosphoric acid ester etc.; Described fluorescent agent refers to the organic fluorescence agent, comprises stilbene compound, coumarin derivatives, pyrazoline derivative, naphthalimide derivative or rhodamine analog derivative etc.; Described photochromic agent refers to the organic photochromic agent, comprises spiro-pyrans, diarylethene or nitrogen benzide etc.
Oil-soluble monomer of the present invention comprises vinyl free radical monomer, and described vinyl free radical monomer is styrenic, a, a kind of in beta-unsaturated esters class, ketone, amides or nitrile compounds or their derivative.Vinylbenzene, vinyl toluene, (methyl) methyl acrylate or β-dimethyl-aminoethylmethacrylate are used in the special special recommendation of the present invention.
The HLB value of amphiphilic block polymers of the present invention is 5-20, comprises phenylethylene-maleic anhydride segmented copolymer or ethene-maleic anhydride segmented copolymer.Described amphiphilic block polymers emulsifying agent, its molecule is comprised of hydrophilic segment and hydrophobic segment, is to be prepared from by the hydrophilic/hydrophobic monomer copolymerization.Hydrophilic segment comprises polyoxyethylene, polymine, polyacrylamide or polymaleic anhydride; Hydrophobic segment comprises polyoxypropylene, polyoxy butylene, polystyrene or polysiloxane; Described segmented copolymer comprises Vinyl Acetate Copolymer-polyoxyethylene, hydrogenated butadiene polymer-poly styrene sulfonate, polystyrene-poly oxygen ethene, polymethylmethacrylate (PMMA)-polyoxyethylene, PMMA-acrylate etc.; Be used for emulsifying agent of the present invention and be preferably phenylethylene-maleic anhydride segmented copolymer or ethene-maleic anhydride segmented copolymer.Different with two kinds of different monomers of hydrophilic segment in the molecule and hydrophobic segment proportion in described multipolymer (phenylethylene-maleic anhydride segmented copolymer or ethene-maleic anhydride segmented copolymer), the HLB value of multipolymer also changes thereupon.Such as, maleic anhydride (MA) causes the variation of HLB value as follows with the ratio of vinylbenzene (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, according to the character of institute's emulsification function material, select the amphiphilic block polymers emulsifying agent of different hydrophilic segment and hydrophobic segment ratio.Each emulsifying agent all has certain HLB value, and each emulsified functional substance has a required HLB value, when the HLB of the emulsifying agent of selecting value accords with required HLB value, just can make more stable emulsifying agent.But, the HLB value that single emulsifying agent has, not necessarily the required HLB value of lucky and emulsified functional substance adapts, so select different hydrophilic segment and the amphiphilic block polymers emulsifying agent of hydrophobic segment ratio namely to select the emulsifying agent of different HLB values.
Assistant for emulsifying agent of the present invention refers to the alkyl alcohols material, better is straight-chain alkyl alcohol, and general formula is C
nH
2n+1OH, n=1～20.This class alkyl alcohol commonly used has methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, nonanol-, nonylcarbinol, positive undecyl alcohol, n-dodecanol, positive tridecanol, tetradecanol, pentadecanol, positive hexadecanol, positive heptadecyl alcohol, positive stearyl alcohol, positive nonadecanol or positive eicosanol etc., the straight-chain alkyl alcohol of recommendation n=8～16 is the straight-chain alkyl alcohol that uses n=8～12 better.
Linking agent of the present invention refers to contain in the molecule double vinyl compound of plural carbon-carbon double bond, comprises at least a in Phthalic acid, diallyl ester, glycol diacrylate, glycerol diglycidyl ether diacrylate, dimethyl diacrylate, Ethylene glycol dimethacrylate, toxilic acid two propylenes, trimethylolpropane trimethacrylate, trimethylolpropane acrylates, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Vinylstyrene, diacrylate butanediol ester or the allyl methacrylate(AMA).Preferred Vinylstyrene, diacrylate butanediol ester or the allyl methacrylate(AMA) of using.
Initiator of the present invention comprises and refers to oil-soluble azo-initiator or peroxide initiator, preferably uses Diisopropyl azodicarboxylate or benzoyl peroxide.
First inventive point of the present invention is, using emulsifying agent is that the HLB value is amphiphilic block polymers, the alkyl alcohol assistant for emulsifying agent of 5-20, obtains by surfactant compound that functional substance requires or optimum HLB value.Emulsification of the present invention can be taked more than one emulsifying manner emulsification in powerful mechanical stirring and emulsifying, high-speed shearing emulsion machine emulsification or the ultrasonic emulsification.In the present invention, with the functional substance emulsion dispersion at aqueous phase, obtain the high density functional substance nanoemulsions of massfraction 20～60% through emulsification, adopt the functional Na capsule slurries of high solids content of free-radical emulsion polymerization known technology quality of production mark 20～70%.As everyone knows, emulsification is that the production polymkeric substance is the indispensable process of functional micro-nano capsule of shell.Functional substance is dispersed in the water that contains the water soluble surfactant active, and functional substance overcomes surface force under the effect of mechanical stirring and tensio-active agent becomes small emulsion droplet.Usually, after tensio-active agent was determined, stir speed (S.S.) was faster, and the particle diameter of the drop that obtains is just less.The hydrophilic ability of the tensio-active agent of high HLB value is strong, easily obtains the drop of small particle size, 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 solvent or the diluent 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 wastees, the efficient raising, and cost, and make the serialization of functional fibre process for making.
In existing spining technology, viscose fiber, vinylon fibre, acrylic fiber all are to obtain by the wet-spinning technology take water as solvent.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 processes.
For example, for the manufacture of the viscose fiber that contains the function nano capsule: spinning solution comprises the viscose fiber stoste in sulfidation or the ripening process, its fiber quality mark is 5～20 weight parts, slurries 10～50 weight parts of above-mentioned functions Na capsule are joined in the rayon spinning stoste, high-speed stirring is by three-stage filtration, then routinely wet spinning process spinning after the volume pump metering, enters 10～60 ℃ of precipitation bath through candle filter and spinning nozzle; Described precipitation bath is comprised of 30～150g/L sulfuric acid, 50～350g/L sodium sulfate and 5～80g/L zinc sulfate, total drawing ratio is 20～30%, spinning speed is 10～100m/min, and technique namely obtains containing the viscose fiber of function nano capsule after the oven dry that oils routinely again.Described viscose fiber manufacturing technology process is: pulp → soda cellulose → Mierocrystalline cellulose sulfonic acid fat → viscose glue and functional nano capsule be mixed → spinning → shaping → drawing-off → cut-out → fine purifiation → drying → shredding → make function nano capsule viscose fiber.
Also for example, for the manufacture of the acrylic fiber that contains the functional nano capsule: with the vinyl cyanide of 80～95 weight parts, the methyl acrylate of 5～12 weight parts, 0.5 the methacrylic disulfonate acid of～1.5 weight parts, add the polymerization in the functional nano capsule slurries that contain Sodium Thiocyanate 99 of 60～120 weight parts of initiator Diisopropyl azodicarboxylate, perhaps direct polymkeric substance with 100 weight parts is dissolved in the aqueous solution of 60～120 weight part functional nano capsule slurries that contain Sodium Thiocyanate 99, obtain spinning solution, again routinely wet spinning process spinning, through precipitation bath, washing, after the stretching, namely obtain containing the acrylic fiber of functional nano capsule.
Again for example, for the manufacture of the vinylon fibre that contains the functional nano capsule: with the functional nano capsule slurries of 100 weight parts as solvent, be mixed with spinning solution by the polyvinyl alcohol of 14～20 weight parts and linking agent formaldehyde or the boric acid of 1～6 weight part, through orifice Cheng Sihou, enter precipitation bath and drawing-off, then through damp and hot drawing-off bath, acid bath, neutralization bath, drying, the dry heat drafting technological process namely 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 for being described in further detail the present invention, does not limit claim of the present invention.
Embodiment 1
(1) free-radical emulsion polymerization is produced photochromic Na capsule slurries:
The aqueous solution (solid content 19.0% weight) with 1.0 kilograms of styrene-maleic anhydride copolymers is dissolved in 20 kg of water first, obtains the emulsifying agent water; Again with 300 Ke Luo oxazines; 3.2 the methyl methacrylate of kilogram; 0.32 the linking agent diacrylate 1 of kilogram; behind 4-butanediol ester and the initiator dibenzoyl peroxide mixed dissolution; join aforesaid aqueous phase as oil phase; rotating speed with 7500 rev/mins; high-shear emulsifying 2 hours (emulsion droplet median size 758nm); the assistant for emulsifying agent n-Heptyl alcohol that slowly adds 55ml between emulsified phase; logical nitrogen deoxygenation is after 30 minutes; change 160 rev/mins blade stirring into; be warming up to 75 ℃; carried out polyreaction 5 hours, cool to room temperature namely obtains photochromic Na capsule slurries.The solid content of these slurries is 23% weight.
(2) manufacturing of photochromic vinylon fibre:
20 kilograms in the photochromic Na capsule slurries of above-mentioned 23% weight solid content are as solvent, the polymerization degree DP1750 ± 50 that adds 3.2 kilograms, the polyvinyl alcohol of alcoholysis degree 99.9%, in polyvinyl alcohol, add again 0.03 kilogram boric acid and 0.002 kilogram oxyethane superpolymer, make spinning solution; Through after spinning jet extrudes, through conventional precipitation bath, neutralization baths, damp and hot drawing-off, washing and drying then, after the dry heat drafting processing, namely obtain photochromic vinylon fibre long filament again.The baked tensile strength of this long filament was 3.2 gram/dawn, and initial modulus was 260 gram/dawn, and degree of stretching is 26.5%.
Embodiment 2
(1) free-radical emulsion polymerization is produced heat-accumulation temperature-adjustment Na capsule slurries:
The aqueous solution (solid content 19.0% weight) with 0.5 kilogram of styrene-maleic anhydride copolymer is dissolved in 20 kg of water first, obtains the emulsifying agent water; Again with behind 4.5 kilograms of n-hexadecanes, 3.5 kilograms vinylbenzene, 0.4 kilogram the linking agent Vinylstyrene and 18.3g initiator Diisopropyl azodicarboxylate mixed dissolution, join aforesaid aqueous phase as oil phase, rotating speed with 9200 rev/mins, high-shear emulsifying 1.5 hours (emulsion droplet median size 650nm), the n-hexyl alcohol that slowly adds 48ml between emulsified phase, remaining with embodiment 1 (1), namely obtain n-hexadecane heat-accumulation temperature-adjustment Na capsule slurries.The solid content of these slurries is 29% weight.
(2) manufacturing of heat-accumulation temperature-adjustment viscose fiber:
10.0 the above-mentioned slurries of kilogram be made into alkali lye after 330 kilograms water mixes, add 38 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 stirring, then enter 40 ℃ of precipitation bath through the volume pump metering by candle filter and spinning nozzle.Described precipitation bath is by 75g/L sulfuric acid, and 260g/L sodium sulfate and 20g/L zinc sulfate form, and total drawing ratio is 150%, and spinning speed is 40m/min, and technique becomes finished fiber after the oven dry that oils routinely again, obtains having the viscose fiber of heat-accumulation temperature-adjustment function.
Embodiment 3
(1) free-radical emulsion polymerization is produced vitamin-E Na capsule slurries:
The aqueous solution (solid content 20.0% weight) with 1.2 kilograms of ethene-copolymer-maleic anhydrides is dissolved in 18.8 kg of water first, obtains the emulsifying agent water; Again with 2.8 kilograms of vitamin E oils, 3.0 kilograms vinylbenzene, 0.4 kilogram linking agent diacrylate 1; behind 4-butanediol ester and the 15.0g initiator benzoyl peroxide mixed dissolution; join aforesaid aqueous phase as oil phase; rotating speed with 9000 rev/mins; high-shear emulsifying 2.0 hours (emulsion droplet median size 920nm); slowly add the positive certain herbaceous plants with big flowers alcohol of 60ml between emulsified phase, remaining with embodiment 1, namely obtain vitamin-E Na capsule slurries.The solid content of these slurries is 23% weight.
(2) manufacturing of vitamin-E viscose fiber:
10.0 the above-mentioned slurries of kilogram be made into alkali lye after 330 kilograms water mixes, remaining with embodiment 2 (2), obtain having the vitamin-E viscose fiber that improves skin function.
Embodiment 4
(1) free-radical emulsion polymerization is produced tool fragrance Na capsule slurries:
The aqueous solution (solid content 19% weight) with 0.8 kilogram of styrene-maleic anhydride copolymer is dissolved in 18.2 kg of water first, obtains the emulsifying agent water; Again with behind 4.2 kilograms of cananga oils, 2.5 kilograms methyl methacrylate, 0.3 kilogram the linking agent allyl methacrylate(AMA) and 23.0g initiator benzoyl peroxide mixed dissolution; join aforesaid aqueous phase as oil phase; rotating speed with 9000 rev/mins; high-shear emulsifying 2.0 hours (emulsion droplet median size 760nm); the n-dodecanol that slowly adds 60ml between emulsified phase; remaining with embodiment 1, namely obtain tool Yilan fragrance of a flower Na capsule slurries.The solid content of these slurries is 26% weight.
(2) 25 kilograms in the Yilan fragrance of a flower Na capsule slurries of above-mentioned 26% solid content are as solvent, the polymerization degree DP1750 ± 50 that adds 3.7 kilograms, the polyvinyl alcohol of alcoholysis degree 99.9%, in polyvinyl alcohol, add again 0.07 kilogram boric acid and 0.01 kilogram oxyethane superpolymer, make spinning solution.Through after spinning jet extrudes, through precipitation bath, neutralization baths, damp and hot drawing-off, washing and drying then, after the dry heat drafting processing, namely obtaining baked tensile strength was 3.8 gram/dawn, 240 gram/dawn of initial modulus, the tool fragrance vinylon fibre long filament of degree of stretching 29% again.
Embodiment 5
Embodiment 5 is as the comparing embodiment of embodiment 4, prepares Na capsule by the method for embodiment 4 (1), do not add n-dodecanol in the emulsion process, obtains the microcapsule slurry of median size 5.2 μ m.Press embodiment 4 (2) with this microcapsule slurry and make vinylon fibre, the spinning jet latch up phenomenon appears in spinning process, normally spinning.
Claims (5)
1. the free-radical emulsion polymerization manufacture method of functional Na capsule slurries, this manufacture method adopts following technique: first with the oil-soluble monomer of 1～100 weight part functional substance and 5～30 weight parts, 0.5 the initiator of the linking agent of～5 weight parts and 0.01～0.5 weight part is made mixed solution, and mixed solution is heated to more than the melting temperature of this functional substance, the amphiphilic block polymers emulsifier aqueous solution mixing and emulsifying that again mixed solution and 150～400 weight parts is contained 0.1～20 weight part, the assistant for emulsifying agent that adds 0.01～5 weight part in the emulsion process, letting nitrogen in and deoxidizing, under stirring at low speed, telo merization temperature to 60～90 ℃, react after 3～5 hours, namely obtain functional Na capsule slurries;
Described functional substance comprises at least a in the following organic substance: phase change material, flavouring agent, fire retardant, fluorescent agent and photochromic agent; Described oil-soluble monomer is vinylbenzene, vinyl toluene, (methyl) methyl acrylate or β-dimethyl-aminoethylmethacrylate; Described linking agent is double vinyl compound; Described initiator refers to oil-soluble azo-initiator or peroxide initiator; The HLB value of described amphiphilic block polymers is 5-20, comprises phenylethylene-maleic anhydride segmented copolymer or ethene-maleic anhydride segmented copolymer; Described assistant for emulsifying agent refers to that general formula is C
nH
2n+1OH, the straight-chain alkyl alcohol of n=1～20.
2. the free-radical emulsion polymerization manufacture method of functional Na capsule slurries according to claim 1 is characterized in that described assistant for emulsifying agent refers to that general formula is C
nH
2n+1OH, the straight-chain alkyl alcohol of n=8～12.
3. the free-radical emulsion polymerization manufacture method of functional Na capsule slurries according to claim 1 is characterized in that described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
4. the free-radical emulsion polymerization manufacture method of functional Na capsule slurries according to claim 1 is characterized in that described linking agent is Vinylstyrene, diacrylate butanediol ester or allyl methacrylate(AMA).
5. the purposes of any one functional Na capsule slurries of claim 1-4, it is characterized in that described functional Na capsule slurries directly are used as the solvent of wet-spinning, prepare spinning solution, comprise again the functional fibre of described functional Na capsule according to known wet spinning process manufacturing.
Priority Applications (1)
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|---|---|---|---|
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| CN103537238B (en) * | 2013-09-26 | 2015-06-10 | 航天海鹰(镇江)特种材料有限公司 | Preparation method of residual emulsifying agent-free flame-retardant phase-change material capsule |
| CN108192240B (en) * | 2017-12-29 | 2020-04-28 | 宜兴市光辉包装材料有限公司 | Photochromic PVC heat-shrinkable label film and preparation method thereof |
| CN109369878A (en) * | 2018-09-20 | 2019-02-22 | 俞小峰 | A kind of low aldehyde high temperature resistant polyurethane material and preparation method thereof |
| US11260360B2 (en) | 2018-10-18 | 2022-03-01 | Encapsys, Llc | Microencapsulation |
| CN110669477B (en) * | 2019-09-29 | 2020-09-25 | 淮阴工学院 | Controllable preparation method of clay-based microcapsule phase change material |
| CN110820068B (en) * | 2019-10-17 | 2021-01-26 | 浙江大学 | Preparation method of phase change fiber |
| CN113913160B (en) * | 2021-11-09 | 2023-08-15 | 青岛尼希米生物科技有限公司 | Double-layer capsule wall energy storage temperature adjustment microcapsule, polyacrylonitrile fiber and preparation method thereof |
| CN118374898B (en) * | 2024-06-24 | 2024-09-24 | 德州学院 | Ginger powder composite viscose fiber, preparation method and application thereof |
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| JP3910877B2 (en) * | 2001-11-22 | 2007-04-25 | パイロットインキ株式会社 | Temperature-sensitive discolorable composite fiber |
| JP5537776B2 (en) * | 2005-03-04 | 2014-07-02 | ビーエーエスエフ ソシエタス・ヨーロピア | Microcapsule powder |
| CN101225296A (en) * | 2008-02-01 | 2008-07-23 | 北京服装学院 | Method for preparing photochromic micro-encapsulation |
| CN101701146B (en) * | 2009-10-22 | 2011-10-26 | 天津工业大学 | Phase-change material microcapsule and preparation method thereof |
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