CN107675278A - A kind of preparation method for the functional fiber element for improving functional materials effective content - Google Patents
A kind of preparation method for the functional fiber element for improving functional materials effective content Download PDFInfo
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- CN107675278A CN107675278A CN201710908241.XA CN201710908241A CN107675278A CN 107675278 A CN107675278 A CN 107675278A CN 201710908241 A CN201710908241 A CN 201710908241A CN 107675278 A CN107675278 A CN 107675278A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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Abstract
The invention provides a kind of preparation method for the functional fiber element that can greatly improve the functional material effective content in fiber, in the fiber material material products that this method obtains, the functional materials account for the 5 60% of relative quality of item ratio, it is even more more, it is generally capable of up to more than 15% or more than 30%.Thus the functional fiber element prepared, its effect, such as fire-retardant, antibacterial, moisturizing, skin care, beauty, heat storage and release, fragrance, catalysis, resistanceization and other effects, because functional materials content is high, can be substantially improved.Method raw material sources of the present invention are extensive, and whole process is environment-friendly, is easy to industrial production, can be applied to the fields such as textile manufacture, medicine, cosmetics, agricultural.
Description
Technical field
The present invention relates to a kind of fiber material preparation method for material, and in particular to one kind improves functional materials effective content
Functional fiber element preparation method, and using this method prepare functional fiber element long material.
Background technology
In each fiber, cellulose fibre is even more important.Different from fossil energy, cellulose is extensive in nature
Existing renewable resource, played then in weaving, light industry, oil, national defence, metallurgy, biology, medicine and other fields very important
Be effect.Compared with other spinning process, the preparation temperature of cellulose fibre is relatively low, and condition is relatively mild, like excellent
Functional materials carrier.Therefore functional material is incorporated into the existing many trials of research of fibrous material.
The method that polyethylene glycol is added to doughnut is described in US4908238, and then will in EP1430168
Phase-change material directly mixes with cellulose.These are directly by functional materials such as fire retardant, retardant, heat accumulating, suppression
Microbial inoculum etc., is directly mixed with spinning solution, then the method by the way that cellulose crystallite or solidification to be obtained to fiber, such
To fiber there is certain temperature-responsive, can absorb heat in good time or heat release, but functional material therein, otherwise nothing
Method is firmly retained in the fibre, causes functional material to leak or fibrous mechanical property can be caused to decline.
Europatent EP0306202, which is disclosed, a kind of to be blended in the microballoon containing phase-change material or plastic crystal material
The technology with reversible thermal energy storage performance fibers is made in polymer；Disclosed in CN103225123A it is a kind of by peppermint oil and
Antiseptic microencapsulation, then microcapsules are mixed with rayon spinning liquid, obtained through wet spinning containing functional materials
Fiber；Described phase-change microcapsule in CN101942706A in yellow process, dissolution process, mixed processes or spinning work
It is added to during sequence in cellulose substances, the method for functional fiber is being obtained by spinning.These methods are all taken feature
After material (peppermint oil, antiseptic or phase-change material) microencapsulation, the method that is mixed with spinning solution, the microballoon system of this technology
Standby process is more complicated, and the diameter of microballoon, heat-resistant stability, solvent resistant stability etc. influence preparation and the performance of fiber, such as
The sizes of microcapsules requires stricter, the problems such as otherwise causing spinneret hole plug；And when the relative of functional materials adds
When entering amount and exceeding mass ratio 5%, because the interfacial area between microcapsules and cellulose is significantly increased, fiber can be largely effected on
The forming process of cellulose fiber and the physical property of product.But the relative amounts of functional materials are less than mass ratio 5%, fiber
Functional result it is bad.
One kind is described in WO2009/062657 functional materials are first formed into emulsion, then by emulsion and cellulose
Solution mixes, and is carried by addition after highly viscous hydrophobic agents make the emulsion stabilization, add nano particle formed it is outstanding
Supernatant liquid, then recrystallize cellulose, the method for obtaining fibre in differentiation.This method effectively increases feature material in fiber
The content of material, but find in actual applications, it may be possible to because functional material is in disperse state, it is between cellulose
Interface can be too high, the loss of (weaving of such as fiber, dyeing and finishing etc.) functional material is extremely serious in further processing,
Also have an impact to the mechanical property of fiber.Certainly, this method can have a lot of reference to the application in the fields such as medicament slow release.
As can be seen here, there is provided a kind of method that can greatly improve the functional material effective content in fiber, be included in fibre
In the preparation process of dimension, the addition of functional material, and merging for fibrous matrix, and during the post-processing of fiber still
The method for keeping higher functional material retention, is that pole is necessary.
The content of the invention
It is an object of the invention to for the problems of the prior art, there is provided a kind of function that can be greatly improved in fiber
Property material effective content functional fiber element preparation method.
Inventors noted that Microencapsulation Method can provide the shell material for effectively protecting functional materials.But prepare respectively
Microcapsules and spinning solution, then the two method mixed is had into great limitation, the compatibility and adaptability of microcapsules, grain
Footpath and shape etc. can all influence the function of fiber product.Therefore this method, otherwise enough functional materials can not be accommodated,
As for peppermint oil no more than 1%, antiseptic is no more than 8% in foregoing CN103225123A；Under fibre property such as mechanical strength
Drop is serious even can not to be adapted to be processed further, and feature persistence is poor, and loss is serious.EP1243326 also give spices or
The class microcapsule preparation method of other functional materials, same takes the step of microencapsulation and fibrosis are carried out respectively,
This causes its great limitation in being prepared on a large scale and uneconomical.The method provided in WO2009/062657, though
The content of functional material can be so improved, but higher functional material can't be kept during the post-processing of fiber
Retention.
Inventors noted that during cellulose solution forms fiber, the emulsion droplet diameter of functional additive is
It is very crucial, such as cured in subsequent technique, collide and may all cause drop to be grown up, and excessive particle diameter is for spinning
Process may result in blockage；But liquid-drop diameter is too small, specific surface area increase, it means that the relative of functional materials contains
Amount can be reduced seriously, essentially result in effective content decline.Therefore, in the preparation process of functional fiber cellulosic material, emulsion
Liquid-drop diameter need to be stably held in a scope.Usually solves this problem using microcapsule method at this stage.And from liquid
The formation of drop and for growing up, oil-water interfaces performance is very crucial, and it is also to be related to functional material in cellulose
It is dispersed in solution, and one of key of junction mechanical strength between functional material and cellulose.Microcapsule method
Liquid-drop diameter can be made stable in certain size, but the interface of microcapsule method has stabilized, and the interface being stabilized has it solid
The defects of having, the present invention set out from another point of view, give one kind and functional material is added in cellulose solution and forms breast
Liquid drop and the method for solidifying oil-water interfaces in subsequent technique.
The preparation of the functional fiber element of the present invention that the functional material effective content in fiber can be greatly improved
Method, comprise the following steps：
1) configuration include mass concentration 5%-12% sodium hydroxide, mass concentration 0.1%-9% zinc oxide dissolving
The solvent of cellulose, then add solution gross mass 2%-15% cellulose, be refrigerated to less than -5 DEG C, then not higher than
45 DEG C of defrostings, the step of obtaining cellulose solution；
2) using the cellulose solution that step 1) obtains as continuous phase, using functional materials as dispersed phase, breast is formed
Liquid；
3) polymer monomer or performed polymer are added in the emulsion system obtained to step 2), triggers polymerization, in emulsion
Polymer is formed at oil-water interfaces；Wherein, the 0.05%- of the quality function material mass of the monomer or performed polymer
29.99%；
4) the cellulose solidification in the system for obtaining step 3), obtains functional materials and is dispersed in cellulosic matrix
Functional fiber element.
With the dissolving method of existing cellulose, particularly industrialized conventional method：Highly basic at high temperature under high pressure is molten
Cellulose dissolution is carried out under liquid, or is compared with NMMO, ionic liquid high-temperature dissolving, the purpose of step 1) is formed as even
The cellulose solution of continuous phase, the continuous phase make it possible that a step adds and solidified functional materials in a subsequent step.
In step 1), the cellulose includes cellulose carbamate, lignocellulosic, reed, cotton, flax, shallow lake
At least one of powder, chitosan or polysaccharide of synthesis or its any combination；It is wherein preferable, cellulose carbamate, wood
Matter cellulose, starch, chitosan or the polysaccharide of the synthesis degree of polymerization are 300-800.
The solution can be the aqueous solution, NMMO (N-methylmorpholine-N oxides) aqueous solution, ionic liquid etc., wherein
N-methylmorpholine-N- oxides can be mixed with water with arbitrary proportion in N-methylmorpholine-N- oxide water solutions.
Wherein, ionic liquid is more recent development, be made up of completely a kind of cation and a kind of anion,
The compound being in a liquid state, referred to as ionic liquid, it is typical such as methylimidazole hexafluorophosphate.
Research finds that the key factor for influenceing stability of emulsion also has the composition of cellulose solution, cellulose dissolution process
Relatively mild, too high or too low temperature and pressure is totally unfavorable.The aqueous solution containing sodium hydroxide, zinc oxide, or
Further comprise that N-methylmorpholine-N- oxides or ionic liquid etc. can be so that cellulose dissolution process be easily controlled.Inventor
It is noted that it will be extremely helpful to contain a certain amount of water in above-mentioned solution.But cause therein need further research and explained
Release.
In step 2), the method that emulsion is formed has many kinds, general single from mixed method, at least 3 kinds of the formation of emulsion
Method：1) positive phase emulsion is added to what stirring in continuous phase was formed generally by by scattered；2) phase inversion, it is typical case
Will continuously be added to the method for forming emulsion in dispersed phase, feature is to obtain smaller, more homogeneous emulsion；3) will
Continuous phase and dispersed phase are added in high shear pump simultaneously, are typical pressurization emulsion processes.Therefore step 2) can use this area
Conventional method is carried out, and obtains emulsion.
The functional materials addition be relative fiber element part by weight for more than 5%, can be more than 15%,
It is even more more, more than 30%, reach 50% or more, 5-60% can at present；It is preferred that 15-60%, more preferably 30-60%.
Drop size in emulsion can influence addition, such as prepare fiber, and it is straight typically to require that liquid-drop diameter is less than single fiber
The half in footpath；Such as require to be less than 3.5 microns, or even require that D90 is less than 2 microns.
The functional materials include fire retardant, retardant, fragrant plant extract, Chinese patent medicine preparation, vitamin A, dimension
Raw plain D, vitamin E, aliphatic hydrocarbon, fatty alcohol, aliphatic acid, fatty acid ester, acid anhydrides, polyalcohol, hydrated salt, paraffin, binary acid,
Fat-soluble protein, vegetable oil, bactericide, insecticide, bacteriostatic agent, pest repellant, catalyst, crosslinking agent, heat stabilizer, light are steady
Determine at least one of agent, liquid crystal, dyestuff, pigment, temperature-sensing color-changing material, photosensitive colour-changing material or its any combination.
The selection of functional materials can select according to the purposes and characteristic requirements of required fiber, and this may be referred to ability
The common knowledge in domain is carried out.
Further, above-mentioned functional materials, in addition to the solution of aforementioned functional material arbitrary proportion or dispersion liquid,
It is adsorbed with the porous material or stratified material, nanotube of above-mentioned functional materials.
In step 3), the polymer includes polyurethane, melamine resin, polyacrylate, styrenic polymer, second
Vinyl polymer, acrylic polymer, polycarbonate, polyester, polyethers, fluorocarbon polymer, epoxy polymer, siliceous polymerization
The mixture of thing, polyamide, polyimides, polyhydric alcohol polymer, copolymer or more arbitrary proportion.
The introducing of polymer monomer or performed polymer, primarily to stablized, be not easy destroyed oil-water interfaces,
Its addition and polymerization time can influence the drop and stability of emulsion.
The introducing of polymer monomer or prepolymer, it will be determined according to factors such as system polarity, compatibility, mechanical strengths.
Its initiation is the common knowledge of this area, and initiator or initiation conditions are determined according to the difference of type of polymer and dosage, is gathered
Monomer adduct or prepolymer will form different molecular weight or the shell of the extent of reaction, with separation function material and matrix, simultaneously
Play a part of connecting again and protect.
The step of polymer monomer or prepolymer add into system, Thermodynamics or kinetic factor may be caused
Change, so as to produce different curing mechanisms, the formation of shell is probably from outside to inside, it is also possible to from inside to outside, and this
The surface nature or particle diameter at interface will be influenceed.These properties will cause the isolation degree of functional material and the external world or contact
Degree, as phase-change material has good hot storage, it is more suitable for non-direct contact；Plant perfume be then more suitable for slowly release and
It is not to completely cut off completely.Importantly, the inventive method can greatly improve the effective content of functional materials, and follow-up
Loss late is extremely low in processing.
Further, the step 2) and step 3) can be carried out simultaneously, i.e., add simultaneously into the cellulose solution system
Enter functional materials and polymer monomer or performed polymer, trigger polymerization, form emulsion system, now the process includes polymer
The step of monomer or performed polymer and functional materials form the dispersed phase of emulsion together, it is included in after emulsion is formed or i.e. by shape
Into when add polymer monomer or the step of performed polymer.
In step 4), it is described it is fiber solidifying use method commonly used in the art, such as：1. coagulating bath method：Highly basic will be dissolved in
Cellulose in the aqueous solution is sprayed into acid, and cellulose separates out, solidification；2. temperature differential method：Using cellulose solution concentration, temperature not
Together, as being first configured to the solution of 20% cellulose concentration and being heated to 60 DEG C, quickly through the low dense of low temperature (such as 20 DEG C)
The cellulose solution of (such as 5%) is spent, substantial amounts of cellulose separates out solidification；3. separating dry space from moist space method, spinning solution flies in the air after spraying
The segment distance of row one, enter back into spinning solution, cellulose solidification.After described cellulose solidification, functional materials are distributed in fiber
At the inside of plain matrix or at least the one of surface, when functional materials are distributed in matrix surface, the part of functional materials is embedding
Enter in matrix.
The cellulosic material finally obtained is that functional material, functional material and cellulose are included in cellulose parent
There is polymeric layer between parent, the polymeric layer can be continuously or discontinuously.
Cellulose solidification, in addition to fibrous material is formed, it can also obtain including film, tablet, block spongy
Thing or sphere.The long filament of threadiness can be used for other fibers using the yarn manufacture of arbitrary proportion, face weave, as filling out
Fill the preparation of thing or thin-film material；The products such as fiber, film, sponge, or its derivative block, cellular thing, sheet is made
Thing, sphere etc., there is important use in preparation of yarn, the manufacture of fabric, filler or thin-film material etc..
, it is necessary to consider the film forming of cellulosic material when the product species of cellulosic material is determined, therefore this hair
Bright method can further include：4 ') the cellulose even spread for obtaining step 3) on the glass sheet, solidification, passes through
With the comparison of control sample, the film forming of cellulosic material is evaluated；Wherein control sample is the fiber for being not added with functional material
Cellulosic material (same selection, formula and process).
Film forming illustrates spinnability to a certain extent, you can obtains the possibility size of fiber.Specifically, film forming
Property test be film forming procedure (as far as possible and spinning moulding condition, such as drying temperature, speed, washing etc. is consistent for process) is carried out with
Blank film (i.e. non-functional material) is compared.Assessed for the easily peelable degree of film on the glass sheet, it is more easy-peel
It is better from explanation film forming.By means such as microscopes, arbitration functions material is in film surface or the distributing homogeneity of section.
The corresponding function of test film simultaneously.If test passes through, illustrating to obtain the possibility of fiber, larger (spinning still has with film forming
Difference, film forming are adequate condition, rather than necessary condition), while the intensity of fiber, washability can pass through the performance of test film
Necessarily fed back；If film forming is bad, may be selected to prepare such as other shapes such as block, sponge, granular substances
Fiber material material products.
Step 4 ') it can be carried out before or while step 4).
In addition, in film forming test, at least two materials can be produced：Film and filtrate, by the analysis to both, greatly
Cause it will be seen that the distribution situation of the functional materials in fiber material material products.
Experiment proves that the above method can obtain the high fiber material material products of functional materials effective content, the work(
Energy property material accounts for the 5-50%, even more more, preferably 15-60%, more preferably 30-60% of relative quality of item ratio.
Compared with the preparation method of existing functional fiber element, method of the invention has the characteristics that：
1) it is different from and is directly added into functional material, such as fire retardant, aromatic extract, vegetable oil, the present invention program is more
The careful strong acid/weak base that may be faced in fiber production and process, high temperature, high pressure etc. of considering is to functional materials
Caused by too high loss, there is provided the shell of defencive function material, be advantageous to the feature of material product more significantly (such as
Fire-retardant, heat absorption/heat release, antibacterial etc.) or more persistently (such as fragrant, antibacterial, insoluble drug release)；
2) method carried out respectively compared to microcapsules and fiberizing, the inventive method can greatly improve feature thing
Content of the matter in cellulosic matrix, the weight content of functional material can reach 5-60% in product, even more more；
3) in functional material, such as fibre in differentiation, functional film or cavernous body manufacturing field, The present invention gives
Beneficial enlightenment, aspect is prepared on a large scale specific, the present invention program has simplified process, reduced operation link, had bright
Aobvious progress and economic value；
4) in the applicability of method, it is not limited in the functional materials addition of high content, it is close simultaneously for property
(such as surface nature is close, hydrophobe property is close, surface charge is mutually equal) but it is limited to fail the work(of exhaustion known to inventor
Energy property material, this method also provide certain enlightenment and reference.
Brief description of the drawings
Fig. 1 is that a kind of DSC of fiber prepared by the embodiment of the present invention 1 characterizes curve.
Fig. 2 is that a kind of DSC of fiber prepared by the embodiment of the present invention 9 characterizes curve.
Embodiment
The present invention is specifically addressed by embodiment below in conjunction with the accompanying drawings, is mass ratio unless otherwise specified
Example.
Embodiment 1
A kind of regenerated cellulose filaments for improving phase-change material effective content are prepared via a method which：
1) by by the cellulose of the degree of polymerization 650, being dissolved in the sodium hydroxide containing mass ratio 6.15%, 8% zinc oxide
The aqueous solution in, be refrigerated to less than -5 DEG C, then not higher than 45 DEG C (25 DEG C) defrosting, obtain cellulose solution；
2) using step 1 gained cellulose solution as continuous phase, using fusing point as 28 DEG C of paraffin (10 parts) and calcium stearate
(2 parts), methyl diphenylene diisocyanate (0.6 part), toluene di-isocyanate(TDI) (1.5 parts) are used as dispersed phase, and form breast
Liquid；High-speed shearing machine 12000r/min forms emulsion；
3) induce above-mentioned system prepolymer and polymer is formed at emulsion droplet oil-water interfaces；Made with 0.02 part of ethylenediamine
For initiator, system is allowed uniformly to mix 1 minute.Initiator is very active, and very short time will complete to react.
4) above-mentioned system is passed through into spinneret, solidifies cellulose, obtain one kind that paraffin is dispersed in cellulosic matrix
Cellulose fibre with temperature adjustment function.
Analyzed (INSTRUMENT MODEL TA Q20, test curve are as shown in Figure 1) through differential scanning calorimetery, it is obtained in this example
A kind of cellulose fibre with temperature adjustment function, the wherein content of paraffin about 38.99%.
In table 1 below comparative sample be with WO2009/062657 methods describeds prepare functional fiber (commercial goods,
Clima, 6.67dtex), baked and banked up with earth respectively, alkali contracting, bleaching, dyeing after feature contrast, equally with differential scanning calorimetric
Method contrasts the loss function rate of the present embodiment sample and comparative sample.
It is fine obtained by commercially available contrast fiber (commercial goods, Clima, 6.67dtex) and the present embodiment it was found from test data
Dimension can all obtain the functional fiber of high effective content, but by baking and banking up with earth, alkali contracting, bleaching, comparative sample occurs after dyeing
Serious functional materials loss, by contrast, the present embodiment fiber loss is very little.
Table 1
Embodiment 2
A kind of regenerated cellulose filaments for improving protein effective content are prepared via a method which：
1) by by the cellulose of the degree of polymerization 550, being dissolved in the sodium hydroxide containing mass ratio 9% (7%-10%),
The water and the butyl imidazole villaumite of ionic liquid 1- methyl -3 of 0.25% (0.1%-5%) zinc oxide) (wherein, water is
20%, ionic liquid is surplus) mixed solvent solution in, be refrigerated to less than -7 DEG C, then 40 DEG C defrosting, obtain fiber
Plain solution；
2) using step 1 gained cellulose solution as continuous phase, with the silk-fibroin of cellulose mass ratio 35% and 2%
Cellulose (the ratio 1 of the PEG of dispersant Span80 and molecular weight about 1300 grafting：3) dispersed phase is used as, with phase inversion
Continuous phase is added dropwise into dispersed phase with 0.5ml/min speed and forms emulsion；
3) after emulsion is formed, the toluene di-isocyanate(TDI) of cellulose mass ratio 8.5% is added thereto；
4) above-mentioned system is induced using the triethylene tetramine of cellulose mass ratio 0.09% as initiator, prepolymer is in breast
Polymer is formed at liquid drop oil-water interfaces；System is allowed uniformly to mix 1 minute.
5) above-mentioned system is passed through into spinneret, solidifies cellulose, obtain silk-fibroin is dispersed in cellulosic matrix one
Cellulosic filaments of the kind rich in protein.
Protein quality ratio in fiber can be adjusted between 20-40% as needed.
The cellulosic filaments are by cut-out, a kind of cellulose fluff rich in silk-fibroin of getting back.
It is above-mentioned to be rich in protein fibre, yarn, all kinds of woven, knitting fabrics, or facial mask etc. can be further processed into.
In existing cellulose dissolution system, the dissolving of protein, particularly animal protein is a problem, more than 5%
Addition is relatively difficult.
Embodiment 3
A kind of regenerated cellulose filaments for improving temperature-sensing color-changing material effective content are prepared via a method which：
1) by by bamboo cellulose, being dissolved in the sodium hydroxide containing mass ratio 7%, the N- methyl of 4.5% zinc oxide
In quinoline-N- oxide water solutions, less than -5 DEG C are refrigerated to, then in not higher than 40 DEG C defrostings, obtains cellulose solution；
2) using step 1 gained cellulose solution as continuous phase, using cellulose mass ratio 10-25% critical-temperature as
50 DEG C and 70 DEG C of three sections of heat discoloration pigment, 15-25% phase change paraffin and 5% dispersant phenylethylene-maleic anhydride tree
Fat forms emulsion as dispersed phase；
3) in emulsion formation, it is added dropwise thereto with the nano kaoline particle of cellulose mass ratio 2% and 10%
The melamine resin aqueous solution；
4) induce above-mentioned system prepolymer and polymer is formed at emulsion droplet oil-water interfaces, being adjusted to faintly acid, (pH is about
5), after being mixed, to stand 1 hour, then be adjusted to neutrality；
5) above-mentioned system is passed through into spinneret, solidifies cellulose, obtain the multistage temperature-sensitive change that content is up to 10-25%
Color fibre element long filament.
Fiber obtained by this example can show different colors at different temperatures, for it is false proof, warn, decorate, cold and hot protection
Deng the manufacturing of product.
Compared to commercially available chameleon fibre, such as the illusion-colour silk of egression chemical fibre, it uses discoloration microcapsules to add viscose rayon
The addition of method, wherein off-color material is only 2%-5%.
Embodiment 4
A kind of regenerated cellulose filaments for improving fire retardant effective content are prepared via a method which：
1) by by cotton pulp-wood pulp, being dissolved in the sodium hydroxide containing mass ratio 12%, 5% zinc oxide, 0.1% urea
The aqueous solution in, be refrigerated to less than -5 DEG C, then not higher than 45 DEG C defrosting, obtain cellulose solution；
2) using step 1 gained cellulose solution as continuous phase, with the organophosphorous fire retardant of cellulose mass ratio 50% and
1% nano silicon oxide, 12% toluene di-isocyanate(TDI) form emulsion as dispersed phase；
3) using 0.02 part of ethylenediamine as initiator, above-mentioned system prepolymer shape at emulsion droplet oil-water interfaces is induced
Into polymer.Initiator is very active, and very short time will complete to react, and general processing is to allow system uniformly to mix a period of time,
Such as 1 minute.
4) above-mentioned system is passed through into spinneret, solidifies cellulose, obtain a kind of cellulose fiber of excellent fireproof performance
Dimension.Wherein flame retardant agent content even more more (highests 60% at present), can effectively improve fire resistance, or even improve up to 50%
Fire-protection rating.
This example obtained flame-retardant fiber is tested with fiber strength tester, its strength modulus is listed in the table below in 2.By
Data are understood in table, and the fire retardant addition of this example fire resistance fibre is than commercially available fire resistance fibre Visil (Finland of explanation producer fibers
Manufacturer Sateri) it is high, and strength modulus is higher than its, it is with the obvious advantage.
The fibre strength modulus of table 2
Embodiment 5
A kind of regenerated cellulose filaments for improving plant essence effective content are prepared via a method which：
1) by by the cellulose of the degree of polymerization 650, being dissolved in the sodium hydroxide containing mass ratio 7%, 4% zinc oxide,
In the aqueous solution of 0.1% urea, less than -5 DEG C are refrigerated to, then in not higher than 45 DEG C defrostings, obtains cellulose solution；
2) by vacuum suction, lavender type plant essence is adsorbed onto in porous nano silica (spices：Dioxy
SiClx=1：1), silica average grain diameter 120nm, with the silica of the 50% of cellulose quality above-mentioned absorption essence
With 7.5% toluene di-isocyanate(TDI) as dispersed phase；Using step 1 gained cellulose solution as continuous phase, with 5% it is scattered
Agent phenylethylene-maleic anhydride resin, and form emulsion；
3) induce above-mentioned system prepolymer and polymer is formed at emulsion droplet oil-water interfaces；Made with 0.02 part of ethylenediamine
For initiator.
4) above-mentioned system is passed through into spinneret, solidifies cellulose, obtain a kind of cellulose fiber of fragrant excellent performance
Dimension.Wherein fragrance level is even more more up to 25%, can effectively improve fragrant performance, extend fragrant storage period.
Compared with this example, conventional method is to use microcapsule coated plant essence, adds and spinning is carried out in spinning solution, its
Microcapsules addition is only 5% (even lower), and effectively essence content need to be multiplied by with microcapsule coated rate.
Embodiment 6
A kind of regenerated cellulose filaments of raising culicifuge and phase-change material effective content are prepared via a method which：
1) by by the cellulose of the degree of polymerization 550, being dissolved in the sodium hydroxide containing mass ratio 9%, 0.35% zinc oxide
Water and the butyl imidazole villaumite of ionic liquid 1- methyl -3 mixed solvent solution in, less than -7 DEG C are refrigerated to, then at 40 DEG C
Thaw, obtain cellulose solution；
2) using step 1 gained cellulose solution as continuous phase, with the octadecane of cellulose mass ratio 35% and 10%
Culicifuge, 2% benzene-horse resin under high shear 10000r/min speed and form emulsion as dispersed phase；
3) after emulsion is formed, the butyl methacrylate and 1% methyl-prop of cellulose mass ratio 5% are added thereto
Olefin(e) acid allyl ester；
4) induce above-mentioned system prepolymer and polymer is formed at emulsion droplet oil-water interfaces；With cellulose mass ratio
0.02% potassium peroxydisulfate is incubated 2 hours as initiator at 50 DEG C.
5) above-mentioned system is passed through into spinneret, solidifies cellulose, obtained octadecane and culicifuge is dispersed in cellulose base
A kind of cellulosic filaments of functional mass containing bi-component in body.
The cellulosic filaments are by cut-out, a kind of cellulose fluff rich in bi-component functional mass of getting back.
The above-mentioned fiber rich in bi-component functional mass, can be further processed into yarn, all kinds of woven, knitting fabrics, or
Filler, as outdoor goods or home textile articles for use etc..
Prior art is temporarily reported without phase-changing and temperature-regulating and mosquito repellent two-component.
Embodiment 7
A kind of regenerated cellulose filaments for improving liquid crystal material effective content are prepared via a method which：
1) by by bamboo cellulose, being dissolved in the sodium hydroxide containing mass ratio 7%, the N- methyl of 4.5% zinc oxide
In quinoline-N- oxide water solutions, less than -5 DEG C are refrigerated to, then in not higher than 40 DEG C defrostings, obtains cellulose solution；
2) using step 1 gained cellulose solution as continuous phase, using the critical-temperature of cellulose mass ratio 25% as 50 DEG C
Liquid crystal (cholesteryl nonanoate) and 5% dispersant phenylethylene-maleic anhydride resin form emulsion as dispersed phase；
3) in emulsion formation, it is added dropwise thereto with the graphene particles of cellulose mass ratio 0.5% and 8% benzene
Ethene, 1% divinylbenzene；
4) induce above-mentioned system prepolymer and polymer is formed at emulsion droplet oil-water interfaces, add light trigger, it is ultraviolet
Light irradiation 30 minutes；
5) above-mentioned system is passed through into spinneret, solidifies cellulose, obtain the multistage liquid crystal fibre that content is up to 10-25%
Tie up plain long filament.
Fiber obtained by this example, in addition to containing liquid crystal, the grapheme material of enhancing heat conduction is also distributed with, liquid crystal can be made to ring
Border change is sensitiveer.This example product can be used in commodity, signboard, trade mark, logo, warning sign etc., for it is false proof, warn, fill
The manufacturing of the products such as decorations, cold and hot protection.
Embodiment 8
A kind of regenerated cellulose film for improving mosquito repellent agent content is prepared via a method which：
1) by by the cellulose of the degree of polymerization 550, being dissolved in the sodium hydroxide containing mass ratio 9%, 0.35% zinc oxide
Water and the butyl imidazole villaumite of ionic liquid 1- methyl -3 mixed solvent solution in, less than -7 DEG C are refrigerated to, then at 40 DEG C
Thaw, obtain cellulose solution；
2) using step 1 gained cellulose solution as continuous phase, with the culicifuge of cellulose mass ratio 35%, 2%
Benzene-horse resin under high shear 10000r/min speed and forms emulsion as dispersed phase；
3) after emulsion is formed, the butyl methacrylate and 1% methyl-prop of cellulose mass ratio 5% are added thereto
Olefin(e) acid allyl ester；Induce above-mentioned system prepolymer and polymer is formed at emulsion droplet oil-water interfaces；With cellulose mass ratio
0.02% potassium peroxydisulfate is incubated 2 hours as initiator at 50 DEG C
4 ') take above-mentioned system even spread on the glass sheet, solidify cellulose, obtain culicifuge and be dispersed in cellulose
A kind of cellulose membrane of raising mosquito repellent agent content in matrix.
To the peeling degree (more easy to fall off better) of gained film on the glass sheet, (culicifuge is particularly into film uniformity
Distribution) analysis test is carried out, such as carry out electron microscope observation film surface and section；(GB/T 30126-2013 are spun mosquito repellent
The detection and evaluation of the mosquito-proof performance of fabric) tested.
Test result is shown, is easily peeled off, and the film after the drying, i.e., voluntarily separates with substrate, is peeled off naturally, peeling
Film is complete, rupture or defect not in stripping process, and film forming is uniform, and film is White-opalescent, and surface is smooth, nothing
Obvious bubble.Technique film forming used is good in this explanation this example, has very high spinnability.Tested through mosquito repellent, scattering ratio is
74.3%.
Film obtained by this example can be used for mosquito repellent, transmission etc. be prevented, suitable for clothes, bedding, outdoor
Product, automotive trim, medical supplies, health treatment etc..
Embodiment 9
A kind of regenerated cellulose film for improving phase-change material content is prepared via a method which：
1) by by the cellulose of the degree of polymerization 550, being dissolved in the sodium hydroxide containing mass ratio 9%, 0.35% zinc oxide
Water and the butyl imidazole villaumite of ionic liquid 1- methyl -3 mixed solvent solution in, less than -7 DEG C are refrigerated to, then at 40 DEG C
Thaw, obtain cellulose solution；
2) using step 1 gained cellulose solution as continuous phase, with the butyl stearate of cellulose mass ratio 55%, 2%
Benzene-horse copolymer resin as dispersed phase, under high shear 8000r/min speed and form emulsion；
3) after emulsion is formed, the lauryl methacrylate and 1% methyl of cellulose mass ratio 5% are added thereto
Allyl acrylate；Induce above-mentioned system prepolymer and polymer is formed at emulsion droplet oil-water interfaces；With cellulose mass ratio
0.02% potassium peroxydisulfate is incubated 2 hours as initiator at 50 DEG C.
4 ') take above-mentioned system even spread on the glass sheet, solidify cellulose, obtain butyl stearate and be dispersed in fibre
Tie up a kind of cellulose membrane of raising phase-change material content in plain matrix.
To the peeling degree (more easy to fall off better) of gained film on the glass sheet, (culicifuge is particularly into film uniformity
Distribution) analysis test is carried out, such as carry out polarized light microscope observing, or electron microscope observation film surface and section.
Test result is shown, is easily peeled off, and the film after the drying, i.e., voluntarily separates with substrate, is peeled off naturally, peeling
Film is complete, rupture or defect not in stripping process, and film forming is uniform, and film is that milky is opaque, and surface is smooth,
Without obvious bubble.Illustrate that technique film forming used is good in this example, there is very high spinnability.Use differential scanning calorimeter
The test of (model METTLER DSC822e) is as shown in Fig. 2 illustrating about 22 degree of the transformation temperature of the film has enthalpy 71.49J/g.
Film obtained by this example can be used for temperature adjustment, such as radiates, is incubated, is heat-insulated, suitable for clothes, bedding, open air
Articles for use, automotive trim, electronic product, construction material, medical supplies, biological self reproducing raising etc..
Embodiment described above, only the preferred embodiment of the present invention is described, not to the present invention's
Scope is defined.Because embodiment can not be exhaustive, on the premise of design spirit of the present invention is not departed from, this area unskilled labor
The various modifications and improvement that journey technical staff makes to technical scheme, all should only by simply changing shape person
It is considered as in the protection domain of claims of the present invention determination.
Claims (10)
1. a kind of preparation method for the functional fiber element that can greatly improve the functional material effective content in fiber, including with
Lower step：
1) configuration include mass concentration 5%-12% sodium hydroxide, mass concentration 0.1%-9% zinc oxide dissolving fiber
The solvent of element, solution gross mass 2%-15% cellulose is then added, is refrigerated to less than -5 DEG C, then in not higher than 45 DEG C solutions
Freeze, the step of obtaining cellulose solution；
2) using the cellulose solution that step 1) obtains as continuous phase, using functional materials as dispersed phase, emulsion is formed；
3) polymer monomer or performed polymer are added in the emulsion system obtained to step 2), triggers polymerization, the profit in emulsion
Interface forms polymer；Wherein, the quality of the polymer monomer or performed polymer is the 0.05%- of functional materials quality
29.99%；
4) the cellulose solidification in the system for obtaining step 3), obtains the function that functional materials are dispersed in cellulosic matrix
Property cellulose.
2. preparation method as claimed in claim 1, it is characterised in that：In step 1), the cellulose includes cellulose amino
At least one of formic acid esters, lignocellulosic, reed, cotton, flax, starch, chitosan or polysaccharide of synthesis or its is any
Combination；Preferably, cellulose carbamate, lignocellulosic, starch, chitosan or the polysaccharide of synthesis selective polymerization degree are
300-800。
3. preparation method as claimed in claim 1, it is characterised in that：In step 1), the solution is the aqueous solution, N- methyl
One or more mixtures in quinoline-N oxide water solutions, ionic liquid.
4. preparation method as claimed in claim 1, it is characterised in that：In step 2), the functional materials add quality phase
It is 5-60%, preferably 15-60%, more preferably 30-60% to cellulose mass ratio.
5. preparation method as claimed in claim 1, it is characterised in that：In step 2), the functional materials include fire retardant,
Retardant, fragrant plant extract, Chinese patent medicine preparation, vitamin A, vitamin D, vitamin E, aliphatic hydrocarbon, fatty alcohol, fat
Acid, fatty acid ester, acid anhydrides, polyalcohol, hydrated salt, paraffin, binary acid, fat-soluble protein, vegetable oil, bactericide, insecticide,
Bacteriostatic agent, pest repellant, catalyst, crosslinking agent, heat stabilizer, light stabilizer, liquid crystal, dyestuff, pigment, temperature-sensing color-changing material, light
At least one of sensitive allochromatic material or its any combination.
6. preparation method as claimed in claim 5, it is characterised in that：The functional materials, in addition to aforementioned functional thing
The solution or dispersion liquid of matter arbitrary proportion, the porous material for being adsorbed with above-mentioned functional materials or stratified material, nanotube.
7. preparation method as claimed in claim 1, it is characterised in that：In step 3), the polymer includes polyurethane, melamine
It is resin, polyacrylate, styrenic polymer, polyvinyls, acrylic polymer, polycarbonate, polyester, poly-
Ether, fluorocarbon polymer, epoxy polymer, silicon-containing polymer, polyamide, polyimides, polyhydric alcohol polymer, copolymer or more
The mixture of arbitrary proportion.
8. preparation method as claimed in claim 1, it is characterised in that：Further, the step 2) and step 3) can be simultaneously
Carry out.
9. preparation method as claimed in claim 1, it is characterised in that：Methods described also includes：4 ') fibre for obtaining step 3)
Tie up plain even spread on the glass sheet, solidify, by the comparison with control sample, evaluate the film forming of cellulosic material；Wherein
Control sample is the cellulosic material for being not added with functional material.
10. functional fiber cellulosic material prepared by a kind of preparation method using as described in claim 1-9 any one, it is special
Sign is, functional material is included in the fiber, also has polymeric layer between functional material and cellulose parent, described poly-
Compound layer for continuously or discontinuously, the functional material effective content relative fiber element part by weight wherein in fiber be more than
5%, preferably 15-60%, more preferably 30-60%.
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| PCT/CN2017/112519 WO2019061768A1 (en) | 2017-09-29 | 2017-11-23 | Method for preparing functional cellulose capable of increasing effective content of functional materials |
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| WO2019061768A1 (en) | 2019-04-04 |
| CN107675278B (en) | 2020-03-31 |
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