CN106283268B - A kind of preparation method of cellulose/calcium alginate blended fiber - Google Patents

A kind of preparation method of cellulose/calcium alginate blended fiber Download PDF

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Publication number
CN106283268B
CN106283268B CN201610848098.5A CN201610848098A CN106283268B CN 106283268 B CN106283268 B CN 106283268B CN 201610848098 A CN201610848098 A CN 201610848098A CN 106283268 B CN106283268 B CN 106283268B
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cellulose
calcium alginate
blended fiber
spinning
calcium
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CN106283268A (en
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姚勇波
颜志勇
易洪雷
胡英
陈超
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ZHEJIANG SHENNAN PLASTIC Co.,Ltd.
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Jiaxing University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02Cellulose; Modified cellulose
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00Treatment of filament-forming or like material
    • D01D1/02Preparation of spinning solutions
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/04Dry spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/06Wet spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • D01D5/088Cooling filaments, threads or the like, leaving the spinnerettes
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/12Applications used for fibers

Abstract

The present invention relates to a kind of cellulose/calcium alginate blended fiber preparation methods, more particularly to a kind of Wound dressing cellulose/calcium alginate blended fiber preparation method.Key step includes: that cellulose is uniformly mixed by (1) with N-methylmorpholine-N- oxide (NMMO) aqueous solution, is mixed after complete swelling with sodium alginate soln, while calcium chloride is added, cellulose/calcium alginate blend solution is made.(2) cellulose/calcium alginate spinning solution is made using thin film evaporation mode.(3) ultrasonication is accompanied by using dry-jet wet-spinning and prepares cellulose/calcium alginate blended fiber.This blended fiber is for manufacturing wound dressing, feature is that the calcium alginate of blended fiber is evenly distributed, particle size is less than 100nm, filament number is 1.3~3.5dtex, 2.0~3.5cN/dtex of dry break strength, wet break strength is 1.5~3.0cN/dtex, and saturation moisture absorption regain is 20~30%, and water retention is 70~80%.

Description

A kind of preparation method of cellulose/calcium alginate blended fiber
Technical field
The invention belongs to blended fiber technical fields, are related to a kind of preparation method of cellulose/calcium alginate blended fiber, More particularly to a kind of Wound dressing cellulose/calcium alginate blended fiber preparation method.
Background technique
Calcium alginate fibre can absorb a large amount of wound fluids using the natural sea calcium alginate with gel characteristic as raw material And surface of a wound moist environment is kept, it is used as novel Wound dressing.But calcium alginate fibre hygrometric state mechanical strength is poor, the surface of a wound is wet Fibre structure destroys under environment, affects the scope of application and ease of use of calcium alginate dressing.Cellulose is nature storage Maximum natural polymer is measured, the cellulose fibres such as cotton, viscose rayon are widely used traditional dressing materials.However cellulose Fiber dressing air-moisture-permeable, is unfavorable for the holding of wound moist environment, causes surface of a wound incrustation and dressing bonding.Set fiber element is fine Dimension hygrometric state condition under structural intergrity and alginic acid fibre moisture-absorbing moisture-keeping function fibrous material by be dressing desirable feedstock.
The exploitation of cellulose/calcium alginate blended fiber is the feasible method for realizing above-mentioned requirements.Current published money In material, sodium alginate soln is blended related patents with cellulose xanthate ester, alkali cellulose, with the process route of viscose rayon Prepare cellulose/calcium alginate blended fiber (patent No.: 200610044596 cellulose/alginate composite fibers and its system Preparation Method;The patent No.: 201010501609 a kind of preparation methods of alginate/cellulose composite fibre).Such method preparation Cellulose/calcium alginate blended fiber, performance of keeping humidity be better than viscose rayon, hygrometric state mechanical strength be better than calcium alginate fibre. But (common binder fiber dry break strength is 1.6~2.7cN/dtex, wet since the breaking strength of viscose rayon itself is limited State breaking strength be its 50% or so), the mechanical strength of blended fiber it is still relatively low (wet break strength be less than 1.2cN/ dtex).Pollution hidden trouble existing for cellulose viscose manufacturing technique is also the obstacle of its sustainable development.
Lyocell fiber is with N-methylmorpholine-N- oxide (NMMO)/H2O solution is direct solvent, dry-jet wet-spinning system The dry break strength of standby regenerated celulose fibre, Lyocell fiber is 3.0~5.0cN/dtex, and wet break strength is It 70~80%.On this basis, it is molten to be mixed into cellulose by Lyocell fiber main manufacturer Lenzing company for seaweed particle Liquid is prepared for cellulose/seaweed composite fibre.Since seaweed contains, there are many skin compatible materials such as alginate, protein, compound fibres Dimension is favored in the field of taking by user.But such composite fibre be not directed to Wound dressing Demand Design production, seaweed at Divide complexity, is not particularly suited for the surface of a wound.Also there is the patent (patent No.: 200910016898 bacterial cellulose/sodium alginate composite fibers And preparation method thereof) direct solvent of the proposition using ionic liquid as cellulose, sodium alginate micro-nano powder is mixed into fiber Element/ionic liquid solution, dry-jet wet-spinning prepare cellulose/sodium alginate blended fiber.It is asked existing for above two preparation method Topic is that is, seaweed and sodium alginate powder difficulty and highly viscous cellulose solution are evenly dispersed, seaweed or sodium alginate powder It is easy to reunite, influences the stability of fiber forming process and properties of product.
Summary of the invention
The object of the present invention is to provide a kind of cellulose/calcium alginate blended fiber preparation methods.Of the invention is obvious It is characterized in for cellulose being uniformly mixed with the NMMO aqueous solution that water content is 40~60wt% and makes cellulose complete swelling;It will be molten Swollen object is mixed with sodium alginate soln, and calcium chloride is added in mixed process, cellulose/calcium alginate blend is made;Using Thin film evaporation mode makes the moisture of mixed liquor be reduced to 15wt% hereinafter, cellulose/calcium alginate spinning solution is made;Using dry spray Wet spinning accompanies by ultrasonication and prepares cellulose/calcium alginate blended fiber.
A kind of cellulose/calcium alginate blended fiber preparation method of the invention includes the following steps:
(1) cellulose pulp is uniformly mixed with NMMO aqueous solution and makes cellulose complete swelling;Meanwhile preparing alginic acid Sodium solution;
(2) swelling object is mixed with sodium alginate soln, and in mixed process, calcium chloride is added;
(3) moisture of mixed liquor obtained by step is made to be reduced to 15wt% hereinafter, cellulose/calcium alginate spinning solution is made;
(4) through dry-jet wet-spinning, cellulose/calcium alginate blended fiber is made.
As a preferred technical scheme:
A kind of preparation method of cellulose/calcium alginate blended fiber as described above, in the dry-jet wet-spinning, fiber Element/calcium alginate spinning solution accompanies by ultrasonication when squeezing out from spinneret orifice.
A kind of preparation method of cellulose/calcium alginate blended fiber as described above, the ultrasonication is using ultrasound Generator, supersonic frequency are 20~35kHz, and power is 20~300W.
A kind of preparation method of cellulose/calcium alginate blended fiber as described above, fiber in the cellulose pulp The degree of polymerization of element is 400~1000, and the water content of cellulose pulp is 4~6wt%;The water content of the NMMO aqueous solution is 40 ~60wt%;The temperature of the swelling is 60~80 DEG C.
A kind of preparation method of cellulose/calcium alginate blended fiber as described above, the sodium alginate soln it is dense Degree is 0.5~5wt%;The amount of the sodium alginate is 0.1~15wt% of cellulose in the cellulose pulp;The chlorination The molar ratio of sodium ion is 1:2 in calcium and the sodium alginate soln;The calcium chloride can be added in the form of powder or aqueous solution Enter, for the particle size of calcium chloride powder less than 1 μm, the concentration of calcium chloride solution is 2~5wt%.
A kind of preparation method of cellulose/calcium alginate blended fiber as described above, the moisture are reduced to film steaming Originating party formula specifically uses thin film evaporator, technological parameter are as follows: solution temperature is 85~120 DEG C, and vacuum degree is -8.0 × 10-4~- 9.0×10-4Pa。
A kind of preparation method of cellulose/calcium alginate blended fiber as described above, the cellulose/calcium alginate are spun In silk liquid, the total amount of cellulose and calcium alginate accounts for 6~15wt% of spinning solution.
A kind of preparation method of cellulose/calcium alginate blended fiber as described above, the dry-jet wet-spinning keep spinning thin Temperature is reduced to 5~10 DEG C in outflow spinneret orifice 50mm;Specially using ring coldblast, the wind-warm syndrome of the ring coldblast is -5~ 5 DEG C, blowing flow is 200~400L/min, and humidity is 10~60%.
A kind of preparation method of cellulose/calcium alginate blended fiber as described above, the technique ginseng of the dry-jet wet-spinning Number are as follows: the extrusion temperature of spinning solution is 85~120 DEG C, and air layer length is 10~100mm, and air layer temperature is -5~5 DEG C;It is solidifying Gu bath group becomes NMMO and water, NMMO content is 1~10wt%, and coagulation bath temperature range is 5~25 DEG C;Drying temperature be 70~ 150℃。
A kind of preparation method of cellulose/calcium alginate blended fiber as described above, the cellulose/calcium alginate are total The calcium alginate of combined filament is evenly distributed, and particle size is less than 100nm, and filament number is 1.3~3.5dtex, and dry state fracture is strong 2.0~3.5cN/dtex is spent, wet break strength is 1.5~3.0cN/dtex, and saturation moisture absorption regain is 20~30%, water conservation Rate is 70~80%.
Calcium chloride is added in cellulose swelling object and sodium alginate soln mix stages in the present invention, and the principle is as follows, is blended The Blending Processes of object are the dynamic processes of " dispersion " and " aggregation ", and screw extruder, which provides Strong shear active force, can make point Dephasing rupture, phase size reduce.Calcium chloride is added in the process, the sodium alginate under Strong shear power can be made to act on is cured as Calcium alginate nano particle effectively improves the dispersing uniformity of cellulose and calcium alginate, is prepared for particle size and is less than The calcium alginate particle of 100nm.
Spinning solution spinneret orifice extrusion of the invention accompanies by ultrasound functions, and the principle is as follows, cellulose/calcium alginate spinning solution In calcium alginate nano particle specific surface area and surface can be big, be easy to reunite.In view of the above-mentioned problems, spinning solution spinneret of the present invention Hole squeezes out and accompanies by ultrasonic wave, destroys calcium alginate nano particle by the powerful shearing force that ultrasonic wave " ultrasonic cavitation " phenomenon generates Reunion.
Beneficial effect
Compared with the prior art, cellulose of the invention/two phase dispersing uniformity of calcium alginate blended fiber is good, dispersed phase Phase size is small, therefore the mechanical strength of fiber is high, moisture-absorbing moisture-keeping performance is good.
The present invention is not necessarily to change the composition of Lyocell fiber coagulating bath, conducive to the recycling of NMMO solvent.Existing Lyocell The production that can be used for fiber of the present invention is simply transformed just in fiberline.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Embodiment 1
A kind of preparation method of cellulose/calcium alginate blended fiber, under the conditions of 60 DEG C, by the fibre of water content 4wt% It ties up plain pulp and cellulose complete swelling, fiber in cellulose pulp is uniformly mixed and made with the NMMO aqueous solution of water content 40wt% The degree of polymerization of element is 400;The sodium alginate soln for being swollen object with concentration is 0.5wt% is mixed, and is added in mixed process Cellulose/calcium alginate blend solution is made in the calcium chloride powder body that particle size is 0.8um, and the amount of sodium alginate is cellulose slurry The molar ratio of sodium ion is 1:2 in the 1wt% of cellulose in the dregs of rice, calcium chloride and sodium alginate soln;It is 85 DEG C in solution temperature, Vacuum degree is -8.0 × 10-4Under conditions of Pa, cellulose/calcium alginate blend solution moisture is reduced using thin film evaporator Cellulose/calcium alginate spinning solution is made to 15wt%, and the total amount of cellulose and calcium alginate accounts for the 6wt% of spinning solution.
Cellulose/calcium alginate spinning solution is prepared by cellulose/calcium alginate blended fiber, spinning using dry-jet wet-spinning Liquid accompanies by ultrasonication when squeezing out from spinneret orifice, ultrasonication uses ultrasonic generator, supersonic frequency 20kHz, and power is 20W;The extrusion temperature of spinning solution is 85 DEG C;Air layer length is 10mm, and air layer temperature is -5 DEG C;Make to spin using ring coldblast Temperature is reduced to 5 DEG C when silk thread goes out spinneret orifice 25mm, and the wind-warm syndrome of ring coldblast is -5 DEG C, and blowing flow is 200L/min, wet Degree is 10%;Spinning solution thread passes through air layer, and into the coagulating bath being made of NMMO and water, solidification forming is fiber, NMMO Content be 1wt%, coagulation bath temperature range be 5 DEG C;Fiber is dry under the conditions of 70 DEG C after drawing-off, washing.Test table Bright, cellulose/calcium alginate blended fiber calcium alginate of preparation is evenly distributed, particle size 100nm, and filament number is 1.3dtex, dry break strength 2.0cN/dtex, wet break strength 1.5cN/dtex, saturation moisture absorption regain are 20%, Water retention is 70%.
Embodiment 2
A kind of preparation method of cellulose/calcium alginate blended fiber, under the conditions of 65 DEG C, by water content 4.5wt%'s Cellulose pulp is uniformly mixed with the NMMO aqueous solution of water content 45wt% and makes cellulose complete swelling, fibre in cellulose pulp The degree of polymerization of dimension element is 550;The sodium alginate soln for being swollen object with concentration is 1.5wt% is mixed, and is added in mixed process Enter the calcium chloride powder body that particle size is 1um and cellulose/calcium alginate blend solution is made, the amount of sodium alginate is cellulose slurry The molar ratio of sodium ion is 1:2 in the 3.8wt% of cellulose in the dregs of rice, calcium chloride and sodium alginate soln;It is 94 in solution temperature DEG C, vacuum degree is -8.2 × 10-4Under conditions of Pa, using thin film evaporator by cellulose/calcium alginate blend solution moisture It is reduced to 14wt% to be made cellulose/calcium alginate spinning solution, the total amount of cellulose and calcium alginate accounts for spinning solution 8.3wt%.
Cellulose/calcium alginate spinning solution is prepared by cellulose/calcium alginate blended fiber, spinning using dry-jet wet-spinning Liquid accompanies by ultrasonication when squeezing out from spinneret orifice, ultrasonication uses ultrasonic generator, supersonic frequency 24kHz, and power is 90W;The extrusion temperature of spinning solution is 94 DEG C;Air layer length is 33mm, and air layer temperature is -2.5 DEG C;Made using ring coldblast Dynamic analysis of spinning goes out temperature at spinneret orifice 28mm and is reduced to 6.3 DEG C, and the wind-warm syndrome of ring coldblast is -2.5 DEG C, and blowing flow is 250L/ Min, humidity 23%;Spinning solution thread passes through air layer, and into the coagulating bath being made of NMMO and water, solidification forming is fibre Dimension, the content of NMMO are 3.3wt%, and coagulation bath temperature range is 10 DEG C;Fiber is done under the conditions of 90 DEG C after drawing-off, washing It is dry.Test shows that cellulose/calcium alginate blended fiber calcium alginate of preparation is evenly distributed, particle size 90nm, single Silk size is 1.8dtex, dry break strength 2.4cN/dtex, wet break strength 1.9cN/dtex, saturation moisture absorption resurgence Rate is 22%, water retention 72%.
Embodiment 3
A kind of preparation method of cellulose/calcium alginate blended fiber, under the conditions of 70 DEG C, by the fibre of water content 5wt% It ties up plain pulp and cellulose complete swelling, fiber in cellulose pulp is uniformly mixed and made with the NMMO aqueous solution of water content 50wt% The degree of polymerization of element is 700;The sodium alginate soln for being swollen object with concentration is 2.25wt% is mixed, and is added in mixed process Cellulose/calcium alginate blend solution is made in the calcium chloride solution that concentration is 2wt%, and the amount of sodium alginate is in cellulose pulp The molar ratio of sodium ion is 1:2 in the 7.5wt% of cellulose, calcium chloride and sodium alginate soln;It is 103 DEG C in solution temperature, Vacuum degree is -8.5 × 10-4Under conditions of Pa, cellulose/calcium alginate blend solution moisture is reduced using thin film evaporator Cellulose/calcium alginate spinning solution is made to 13wt%, and the total amount of cellulose and calcium alginate accounts for the 10.5wt% of spinning solution.
Cellulose/calcium alginate spinning solution is prepared by cellulose/calcium alginate blended fiber, spinning using dry-jet wet-spinning Liquid accompanies by ultrasonication when squeezing out from spinneret orifice, ultrasonication uses ultrasonic generator, supersonic frequency 28kHz, and power is 160W;The extrusion temperature of spinning solution is 103 DEG C;Air layer length is 55mm, and air layer temperature is 0 DEG C;Made using ring coldblast Dynamic analysis of spinning goes out temperature at spinneret orifice 35mm and is reduced to 7.5 DEG C, and the wind-warm syndrome of ring coldblast is 0 DEG C, and blowing flow is 300L/min, Humidity is 35%;Spinning solution thread passes through air layer, and into the coagulating bath being made of NMMO and water, solidification forming is fiber, The content of NMMO is 5.5wt%, and coagulation bath temperature range is 15 DEG C;Fiber is dry under the conditions of 110 DEG C after drawing-off, washing. Test shows that cellulose/calcium alginate blended fiber calcium alginate of preparation is evenly distributed, particle size 85nm, monofilament Fiber number is 2.4dtex, dry break strength 2.8cN/dtex, wet break strength 2.3cN/dtex, is saturated moisture absorption regain It is 25%, water retention 75%.
Embodiment 4
A kind of preparation method of cellulose/calcium alginate blended fiber, under the conditions of 75 DEG C, by water content 5.5wt%'s Cellulose pulp is uniformly mixed with the NMMO aqueous solution of water content 55wt% and makes cellulose complete swelling, fibre in cellulose pulp The degree of polymerization of dimension element is 850;The sodium alginate soln for being swollen object with concentration is 3.5wt% is mixed, and is added in mixed process Enter the calcium chloride solution that concentration is 3wt% and cellulose/calcium alginate blend solution is made, the amount of sodium alginate is cellulose pulp The molar ratio of sodium ion is 1:2 in the 11wt% of middle cellulose, calcium chloride and sodium alginate soln;It is 112 DEG C in solution temperature, Vacuum degree is -8.8 × 10-4Under conditions of Pa, cellulose/calcium alginate blend solution moisture is reduced using thin film evaporator Cellulose/calcium alginate spinning solution is made to 13wt%, and the total amount of cellulose and calcium alginate accounts for the 12.8wt% of spinning solution.
Cellulose/calcium alginate spinning solution is prepared by cellulose/calcium alginate blended fiber, spinning using dry-jet wet-spinning Liquid accompanies by ultrasonication when squeezing out from spinneret orifice, ultrasonication uses ultrasonic generator, supersonic frequency 32kHz, and power is 230W;The extrusion temperature of spinning solution is 112 DEG C;Air layer length is 77mm, and air layer temperature is 2.5 DEG C;Using ring coldblast So that dynamic analysis of spinning is gone out temperature at spinneret orifice 42mm and be reduced to 8.8 DEG C, the wind-warm syndrome of ring coldblast is 2.5 DEG C, and blowing flow is 350L/ Min, humidity 47%;Spinning solution thread passes through air layer, and into the coagulating bath being made of NMMO and water, solidification forming is fibre Dimension, the content of NMMO are 7.8wt%, and coagulation bath temperature range is 20 DEG C;Fiber is done under the conditions of 130 DEG C after drawing-off, washing It is dry.Test shows that cellulose/calcium alginate blended fiber calcium alginate of preparation is evenly distributed, particle size 80nm, single Silk size is 3.0dtex, dry break strength 3.2cN/dtex, wet break strength 2.7cN/dtex, saturation moisture absorption resurgence Rate is 28%, water retention 78%.
Embodiment 5
A kind of preparation method of cellulose/calcium alginate blended fiber, under the conditions of 80 DEG C, by the fibre of water content 6wt% It ties up plain pulp and cellulose complete swelling, fiber in cellulose pulp is uniformly mixed and made with the NMMO aqueous solution of water content 60wt% The degree of polymerization of element is 1000;Object and concentration will be swollen to mix for the sodium alginate soln of 5wt%, and be added in mixed process dense Cellulose/calcium alginate blend solution is made in the calcium chloride solution that degree is 5wt%, and the amount of sodium alginate is fine in cellulose pulp The 15wt% of element is tieed up, the molar ratio of sodium ion is 1:2 in calcium chloride and sodium alginate soln;It is 120 DEG C in solution temperature, vacuum Degree is -9.0 × 10-4Under conditions of Pa, cellulose/calcium alginate blend solution moisture is reduced to using thin film evaporator 13wt% is made cellulose/calcium alginate spinning solution, and the total amount of cellulose and calcium alginate accounts for the 15wt% of spinning solution.
Cellulose/calcium alginate spinning solution is prepared by cellulose/calcium alginate blended fiber, spinning using dry-jet wet-spinning Liquid accompanies by ultrasonication when squeezing out from spinneret orifice, ultrasonication uses ultrasonic generator, supersonic frequency 35kHz, and power is 300W;The extrusion temperature of spinning solution is 120 DEG C;Air layer length is 100mm, and air layer temperature is 5 DEG C;Made using ring coldblast Dynamic analysis of spinning goes out temperature at spinneret orifice 41mm and is reduced to 10 DEG C, and the wind-warm syndrome of ring coldblast is 5 DEG C, and blowing flow is 400L/min, Humidity is 60%;Spinning solution thread passes through air layer, and into the coagulating bath being made of NMMO and water, solidification forming is fiber, The content of NMMO is 10wt%, and coagulation bath temperature range is 15 DEG C;Fiber is dry under the conditions of 150 DEG C after drawing-off, washing. Test shows that cellulose/calcium alginate blended fiber calcium alginate of preparation is evenly distributed, particle size 90nm, monofilament Fiber number is 3.5dtex, dry break strength 3.5cN/dtex, wet break strength 3.0cN/dtex, is saturated moisture absorption regain It is 30%, water retention 80%.

Claims (10)

1. a kind of cellulose/calcium alginate blended fiber preparation method, it is characterized in that the following steps are included:
(1) cellulose pulp is uniformly mixed with NMMO aqueous solution and makes cellulose complete swelling;Meanwhile it is molten to prepare sodium alginate Liquid;
(2) swelling object is mixed with sodium alginate soln, and in mixed process, calcium chloride is added;
(3) moisture of mixed liquor obtained by step is made to be reduced to 15wt% hereinafter, cellulose/calcium alginate spinning solution is made;
(4) through dry-jet wet-spinning, cellulose/calcium alginate blended fiber is made.
2. a kind of preparation method of cellulose/calcium alginate blended fiber according to claim 1, which is characterized in that institute It states in dry-jet wet-spinning, the cellulose/calcium alginate spinning solution accompanies by ultrasonication when squeezing out from spinneret orifice.
3. a kind of preparation method of cellulose/calcium alginate blended fiber according to claim 2, which is characterized in that institute Ultrasonication is stated using ultrasonic generator, supersonic frequency is 20~35kHz, and power is 20~300W.
4. a kind of preparation method of cellulose/calcium alginate blended fiber according to claim 1, which is characterized in that institute The degree of polymerization for stating cellulose in cellulose pulp is 400~1000, and the water content of the cellulose pulp is 4~6wt%;It is described The water content of NMMO aqueous solution is 40~60wt%;The temperature of the swelling is 60~80 DEG C.
5. a kind of preparation method of cellulose/calcium alginate blended fiber according to claim 1, which is characterized in that institute The concentration for stating sodium alginate soln is 0.5~5wt%;The amount of sodium alginate be the cellulose pulp in cellulose 0.1~ 15wt%;The molar ratio of sodium ion is 1:2 in calcium chloride and the sodium alginate soln.
6. a kind of preparation method of cellulose/calcium alginate blended fiber according to claim 1, which is characterized in that institute It states moisture and is reduced to thin film evaporation mode, specifically use thin film evaporator, technological parameter are as follows: solution temperature is 85~120 DEG C, very Reciprocal of duty cycle is -8.0 × 10-4~-9.0 × 10-4Pa。
7. a kind of preparation method of cellulose/calcium alginate blended fiber according to claim 1, which is characterized in that institute It states in cellulose/calcium alginate spinning solution, the total amount of cellulose and calcium alginate accounts for 6~15wt% of spinning solution.
8. a kind of preparation method of cellulose/calcium alginate blended fiber according to claim 1, which is characterized in that institute Dry-jet wet-spinning is stated, so that dynamic analysis of spinning is gone out temperature in spinneret orifice 50mm and is reduced to 5~10 DEG C;Ring coldblast is specially used, it is described The wind-warm syndrome of ring coldblast is -5~5 DEG C, and blowing flow is 200~400L/min, and humidity is 10~60%.
9. a kind of preparation method of cellulose/calcium alginate blended fiber according to claim 1, which is characterized in that institute State the technological parameter of dry-jet wet-spinning are as follows: the extrusion temperature of spinning solution is 85~120 DEG C, and air layer length is 10~100mm, air Layer temperature is -5~5 DEG C;Coagulation bath composition be NMMO and water, NMMO content be 1~10wt%, coagulation bath temperature range be 5~ 25℃;Drying temperature is 70~150 DEG C.
10. a kind of preparation method of cellulose/calcium alginate blended fiber according to claim 1, which is characterized in that institute Cellulose/calcium alginate blended fiber calcium alginate is stated to be evenly distributed, particle size be less than 100nm, filament number be 1.3~ 3.5dtex, 2.0~3.5cN/dtex of dry break strength, wet break strength are 1.5~3.0cN/dtex, and saturation moisture absorption is returned Damp rate is 20~30%, and water retention is 70~80%.
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