CN106521697A - Carboxyethyl chitosan and polyvinyl alcohol composite fiber and preparation method and application thereof - Google Patents
Carboxyethyl chitosan and polyvinyl alcohol composite fiber and preparation method and application thereof Download PDFInfo
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- CN106521697A CN106521697A CN201611011159.9A CN201611011159A CN106521697A CN 106521697 A CN106521697 A CN 106521697A CN 201611011159 A CN201611011159 A CN 201611011159A CN 106521697 A CN106521697 A CN 106521697A
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/123—Polyaldehydes; Polyketones
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Multicomponent Fibers (AREA)
Abstract
The invention relates to carboxyethyl chitosan and polyvinyl alcohol composite fiber and preparation method and application thereof; the composite fiber comprises a skin layer and a core layer, wherein the core layer is polyvinyl alcohol; the skin layer comprises the following components in parts by mass: 30-75 parts of carboxyethyl chitosan fiber, 10-20 parts of alginic acid fiber, and 1-5 parts of aloe fiber. The prepared composite fiber has excellent physical and mechanical property by use of the skin-core type structure and adding the aloe fiber and compounding the alginic acid fiber into the carboxyethyl chitosan fiber.
Description
Technical field
The present invention relates to textile technology field, more particularly to a kind of carboxyethyl chitosan and polyvinyl alcohol composite fiber and its
Preparation method and application.
Background technology
Chitin is the Renewable resource that reserves are only second to cellulose on the earth, its deacetylated derivant chitosan, due to
With characteristics such as good biocompatibility, biodegradability, hemostasis, promotion wound healings so as in absorbable surgery handss
Have a wide range of applications in the various tissue engineering bracket materials such as art stitching thread, wound dressing, drug carrier material, artificial skin
Prospect.
During chitosan is dissolved in organic acid or mineral acid, in thick gel shape, the work such as Jing spinning, solidification, washing, drying
Sequence can be obtained chitosan fiber, for preparing wound dressing.Japanese Patent Publication SHO (JP60,059,123,1985),
China Patent Publication No. is CN1129748A, and publication date is August in 1996 28, entitled " deacetyl chitin fiber
And its manufacture method and application ", China Patent Publication No. be CN1149093A, publication date is on May 7th, 1997, denomination of invention
It is CN101250759A for " chitin fiber and preparation method thereof ", China Patent Publication No., publication date is August 27 in 2008
Day, entitled " medical chitosan fibre and preparation method thereof " etc. discloses the manufacture method of chitosan fiber in succession.So
And, the chitosan fiber that these methods are prepared has the defects such as antibiotic property is weak, absorbency is poor in clinical medicine application,
When being particularly applied to the treatment of the chronic healing wound surface such as the more empyrosis wound surface of easy infection, transudate, decubital ulcer, effect is not very
It is preferable.
Prior art adopts chitin or chitosan solution spun into fiber, for caning absorb suturess and artificial skin
Deng medical application, or for " transdermal effect activating cell, enhance metabolism and enhancing immunity, antibacterial toxin expelling, fat-reducing drop
" drug application principle " health care underwear of fat, slow down aging " etc..But, after pure chitin or chitosan fiber shortage weaving, process institute
The physical and mechanical propertiess of needs, cost are very high, expensive, and its widely available application is restricted.
Prior art spins antibacterial viscose fiber using chitosan minuteness particle is added in rayon spinning stock solution, but
Due to addition very little (1-2%W/W), due various biological functions are not had.
JP0347,263 [9147,2633] discloses a kind of chitosan and manufactures artificial hair with polyvinyl alcohol blending spinning
The polyvinyl alcohol of alcoholysis degree 98-99% is dissolved in the aqueous solution that water is obtained 15% for method, the method, will be low-molecular weight crust amine molten
10% carapace amine aqueous solution is obtained in 10% aqueous acetic acid, by two kinds of solution with poly-vinyl alcohol solution/carapace amine aqueous solution=80/30
Ratio is blended to obtain co-blended spinning stock solution, and Jing spinneret orifices extrusion, Natrii Sulfas coagulating bath solidification, drawing-off obtain blending type chitosan and polyethylene
Alcohol composite fibre, then the fiber of the prepared artificial hair purposes of Jing formalizings technique.But blending type carapace obtained by this method
Amine is 2g/d or so with the intensity of vinal, is added after weaving can not be still met when the weaving purposes thinner for fiber number
Requirement of the work to fibrous physics mechanical performance.
Prior art spinning vinylon (being commonly called as vinylon or polyvinyl), is to adopt polyvinyl alcohol water solution
For spinning solution, Jing wet-formed (Natrii Sulfas or sodium hydrate aqueous solution coagulating bath) or duse process (moisture evaporation in hot-air
Solidification), drawing-off obtain vinal, then Jing formalizings technique is obtained vinylon polyvinyl.Polyvinyl
Major defect is that dyeability is poor, and the amount of stained with is not high and color and luster is not bright-coloured.Further drawback is elastic poor, the easy wrinkle of uni-material fabric,
Therefore be mainly used in and cotton or wool blend.Its major advantage is intensity height, good hygroscopicity.The performance and outward appearance of polyvinyl long filament with it is natural
Silkworm silk is closely similar, but is difficult to as senior dress material because of its not easy dyeing and poor flexibility, and purposes is restricted.But the opposing party
Face, polyvinyl alcohol are a kind of synthesis macromolecules that can not rely on petroleum resources, can (plant is being stagnated from natural gas or biogas
Rot in water and produce) in methane Jing cracking generation acetylene, acetylene and acetic acid reaction obtain vinyl acetate, and vinyl acetate is aggregated
Polyvinyl acetate is obtained, polyvinyl acetate alcohol under methanol and sodium hydroxide effect solves polyvinyl alcohol.And, polyvinyl alcohol belongs to
, there is internal oxidition in Biodegradable high-molecular under microbial action, generate hydrogen peroxide and ketone first during degraded, then ketone enters
One step occur hydrolysis, finally by microbial metabolism be CO2And H2O (also there is document report, under some strain effects, polyvinyl alcohol
What internal oxidition effect generation occurred is alcohol rather than ketone).Therefore, polyvinyl alcohol is that one kind meets sustainable development and environmental protection
The synthesis macromolecule of requirement.
The content of the invention
For above-mentioned existing problems, it is an object of the invention to provide a kind of raw material can natural regeneration, product natural can drop
The composite fibre of solution, the composite fibre have skin-core structure, with excellent physical and mechanical propertiess and dyeability, while having
The individual style of biological fiber and various biological healths and medical functions, production cost.
It is, up to this purpose, to present invention employs technical scheme below:
In a first aspect, the invention provides a kind of carboxyethyl chitosan and polyvinyl alcohol composite fiber, the composite fibre
Including cortex and sandwich layer;
The sandwich layer is polyvinyl alcohol;
The cortex contains following component by mass parts:Carboxyethyl chitosan fiber 30-75 part;Alginic acid fibre 10-20
Part;Aloe fibre 1-5 parts.
Present invention employs with the Carboxyethyl chitosan fiber containing alginic acid fibre and aloe fibre collectively as cortex,
Using polyvinyl alcohol as sandwich layer, carboxyethyl chitosan and polyvinyl alcohol composite fiber are constituted, which has can the composite fibre that obtained
There are excellent physical and mechanical propertiess, the intensity of its fiber is 4.6-5.2g/d, and extension at break is 23-25%.
According to the present invention, the alginic acid fibre and aloe fibre adopt commercially available prod, here not to do special limit
It is fixed.
According to the present invention, in the cortex, the content of Carboxyethyl chitosan fiber is 30-75 parts, such as 30 parts, 31 parts,
32 parts, 33 parts, 34 parts, 35 parts, 40 parts, 42 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts or 75 parts;Alginic acid fibre
Content be 10-20 parts, such as 10 parts, 12 parts, 14 parts, 15 parts, 18 parts or 20 parts;The content of aloe fibre is 1-5 parts, for example
1 part, 2 parts, 3 parts, 4 parts or 5 parts.
According to the present invention, the 4%-30% of the content of the polyvinyl alcohol for composite fibre gross mass, such as 4%, 5%,
7%th, 10%, 12%, 14%, 15%, 17%, 20%, 22%, 25%, 28% or 30%;Accordingly, each group in the cortex
Point total content for composite fibre gross mass 70%-96%, such as 70%, 72%, 75%, 78%, 80%, 82%, 85%,
90%th, 92%, 95% or 96%;In the polyvinyl alcohol and cortex, the content sum of each component is 100%.
According to the present invention, the deacetylation of the Carboxyethyl chitosan fiber is 70%-90%, such as 70%, 72%,
75%th, 78%, 80%, 82%, 85% or 90%, preferably 75%-85%, more preferably 78%.
According to the present invention, the degree of polymerization of the polyvinyl alcohol is 1800-3800, such as 1800,1900,2000,2200,
2300th, 2500,2800,3000,3500,3600 or 3800;Alcoholysis degree is 90%-99%, such as 90%, 91%, 92%,
94%th, 95%, 97% or 99%.
According to the present invention, fiber number fracture strength 4.6-5.2g/d of the composite fibre, such as 4.6g/d, 4.8g/d,
4.9g/d, 5.0g/d, 5.1g/d or 5.2g/d;Extension at break is 23-25%.
The preparation method of second aspect, described carboxyethyl chitosan and polyvinyl alcohol composite fiber, methods described include:
It is with polyvinyl alcohol spin dope as sandwich layer, fine with the Carboxyethyl chitosan fiber containing aloe fibre and alginic acid
The co-blended spinning stock solution of dimension is cortex, is extruded from core-skin type composite spinneret pack, Jing spinning techniques, then Jing drawing-offs and washing process
Obtain carboxyethyl chitosan and polyvinyl alcohol composite fiber.
According to the present invention, methods described may particularly include following steps:
(1) it is 1800-3800 by the degree of polymerization, alcoholysis degree is dissolved in water for the polyvinyl alcohol of 90%-99% at 95-98 DEG C
Or in the dilute acetic acid aqueous solution of below 3wt%, poly-vinyl alcohol solution being obtained, Jing deaerations obtain polyvinyl alcohol spin dope;
(2) by deacetylation for 70%-90% the carboxyethyl chitosan containing aloe fibre and alginic acid at room temperature
It is dissolved in 1%-10wt% dilute acetic acid aqueous solutions, obtains the mixed solution of carboxyethyl chitosan and alginic acid, Jing deaerations must be spun
Silk stock solution;The spinning solution is delivered to quiet by the thermoregulator that booster pump Jing temperature controls are 95-98 DEG C after extruding from dissolution kettle
State blender, is uniformly mixed with the polyethylene spinning solution of direct pump to static mixer, obtains final product co-blended spinning stock solution;
(3) gained co-blended spinning stock solution Jing prefilter is entered into cortex entrance dosing pump, another road polyvinyl alcohol spinning
To sandwich layer entrance dosing pump, cortex entrance metering revolution speed/sandwich layer entrance metering revolution speed is 1/ to stock solution Jing prefilter pump
0.50-1/1.5, fiber of the composite dope thread that percutaneous core pattern composite spinneret is extruded Jing after spinning technique is at 180-210 DEG C
Under it is xeothermic stretching 2-5.5 times, obtain the carboxyethyl chitosan and polyvinyl alcohol composite fiber.
According to the present invention, the carboxyethyl chitosan that step (3) is obtained is with polyvinyl alcohol composite fiber from the compound spray of core-skin type
Spinning technique after silk component extrusion, is shaped using wet method, wet-dry change or dry-spinning process, and here does not do particular determination.
Wherein, it is described wet-formed to be:Coagulating bath is directly entered from the composite dope thread of composite spinneret extrusion, is coagulated
Gu agent is using saturation Na of polyvinyl spinning2SO4Aqueous solution or NaOH aqueous solutions;Described wet-dry change is configured to:Composite dope thread
Coagulating bath is entered Jing after the air-gap of one section of 1-10cm;Described duse process is:The heat of composite dope thread Jing 100-170 DEG C
Air path makes solvent volatilization and is solidified.
According to the present invention, the carboxyethyl chitosan further carries out acetalization with polyvinyl alcohol composite fiber.
Preferably, the acetalization adopts formaldehyde or glutaraldehyde.
Preferably, the acetalization is:Core-skin type chitosan and polyvinyl alcohol composite fiber are placed in containing formaldehyde or
In the hydroformylation bath of glutaraldehyde, take out after 0.5-2 hours are reacted at -70 DEG C of room temperature, washing, the dry contracting must with skin-core structure
Hydroformylation composite fibre.
In the present invention, the viscosity of the Carboxyethyl chitosan fiber is 150-900cps, and its preparation method can be using such as
Lower step is carried out:
A. chitosan fiber is dispersed in alcohol, chitosan fiber is 1 with the mass volume ratio of alcohol:10~50, then by third
Olefin(e) acid is added in the mixed liquor of chitosan fiber and alcohol, and acrylic acid is 1 with the mol ratio of the amino of chitosan fiber:0.1~
20, stir under room temperature, 4~48h is reacted in water bath with thermostatic control under the conditions of 40~90 DEG C;
B. the mixing liquid that the reacted chitosan fiber of Jing steps a is formed with alcohol, acrylic acid is separated, obtains carboxyethyl
Chitosan fiber first product;
C. the Carboxyethyl chitosan fiber first product for Jing steps b being obtained is dispersed in 80% (v/v) aqueous solutions of organic solvent,
Deca 30% (w/v) inorganic strong alkali aqueous solution, by between aqueous solutions of organic solvent pH regulator to 6~8, soaks 30 minutes, then will
Carboxyethyl chitosan fiber first product is separated with aqueous solutions of organic solvent, inorganic strong alkali aqueous solution liquid, obtains carboxyethyl carapace
Product in the middle of amine fiber;
D. product in the middle of the Carboxyethyl chitosan fiber isolated to Jing steps c with 80% (v/v) aqueous solutions of organic solvent again
Washing 2 times, after dehydration, is dried under the conditions of 40 DEG C, obtains Carboxyethyl chitosan fiber.
In above-mentioned preparation method, the alcohol is methanol or ethanol or propanol or butanol or the one kind in isopropanol;It is described to have
Machine solvent is methanol or ethanol or the one kind in acetone;The inorganic strong alkali is sodium hydroxide or the one kind in potassium hydroxide.
Preparation method of the present invention using above-mentioned Carboxyethyl chitosan fiber, which has an advantage in that:
The present invention is adopted on chitosan fiber strand, by amino on chitosan strand and carbon in acrylic molecules
The Michael addition reaction of carbon double bond, in amino N, positioning introduces carboxyethyl group.On carboxyethyl group, carboxylic acid provides proton,
Protonated amino is caused, so as to increase the polycation characteristic of chitosan fiber, chitosan fiber antibiotic property is improved;By control
The amino of chitosan fiber and the mol ratio and reaction condition of carbon-carbon double bond in acrylic molecules, realize chitosan fiber
In amino N, positioning replaces, and realizes the substitution value of carboxyethyl group in the range of 0.01~0.8, so that reacted fibre
While dimension possesses antibiotic property, substantial amounts of liquid can be also absorbed, remain to keep fiber grown form after absorbing liquid, in addition, also
Greatly strengthen the mechanical performance of chitosan fiber.
Present invention preferably employs method as defined above carries out the preparation of Carboxyethyl chitosan fiber, but this is not limited only to,
It is preferred version using the preparation method, those skilled in the art may also be employed other known method and carry out carboxyethyl carapace
The preparation of amine fiber, which can realize fiber number fracture strength 4.6-5.2g/d of the composite fibre, and extension at break is 23-25%
Technique effect.
The third aspect, present invention also offers carboxyethyl chitosan is existed with polyvinyl alcohol composite fiber as described in relation to the first aspect
Application in medical dressing and functional textile.
Using the present invention prepare composite fibre there are excellent physical and mechanical propertiess, in addition, its can also by cut-out,
Shredding, combing, make non-woven fabrics into net, acupuncture, it is also possible to by being mixed and made into non-woven fabrics with other functional fibres, it is sterilized after
Dressing is formed, for transudate more infectibility wound surface such as burn and scald, decubital ulcer etc., suppression wound surface bacterial growth is played, is inhaled
Wound fluid is received, and the effect of Moist healing environment wound healing is provided.Meanwhile, dressing can be reduced more using the dressing
Number of times is changed, during removal, will not also cause the secondary mechanical of wound surface to damage, reduce the pain of patient.Prepared curable product is right
The clinically antibacterial of the wound surface such as burn and scald, decubital ulcer or ulcer, imbibition has obvious action, and steady quality, low cost, uses
It is convenient, meet Clinical practice requirement.
Compared with prior art, the present invention at least has the advantages that:
Present invention employs with the Carboxyethyl chitosan fiber containing alginic acid fibre and aloe fibre collectively as cortex,
Using polyvinyl alcohol as sandwich layer, carboxyethyl chitosan and polyvinyl alcohol composite fiber are constituted, which has can the composite fibre that obtained
There are excellent physical and mechanical propertiess, the intensity of its fiber is 4.6-5.2g/d, and extension at break is 23-25%.
Specific embodiment
The specific embodiment of the present invention is the following is, described embodiment is, for describing the present invention, rather than to limit this
It is bright.Unless stated otherwise, the equal percetage by weight of solution concentration in embodiment.
Embodiment 1
A kind of carboxyethyl chitosan and polyvinyl alcohol composite fiber, the cortex contain following component by mass parts:Carboxylic second
40 parts of base chitosan fiber;10 parts of alginic acid fibre;1 part of aloe fibre;The sandwich layer (polyvinyl alcohol) accounts for the total matter of composite fibre
The 10% of amount, the cortex each component summation accounts for the 90% of composite fibre gross mass.
Polyvinyl alcohol (degree of polymerization 1950, alcoholysis degree 99%) is dissolved in 2wt% dilute acetic acid aqueous solutions at 98 DEG C, is obtained
To concentration for 15wt% poly-vinyl alcohol solution, Jing deaerations obtain polyvinyl alcohol spin dope.
The carboxyethyl chitosan containing aloe fibre that deacetylation is 90% and alginic acid are dissolved at room temperature
In 10wt% dilute acetic acid aqueous solutions, the mixed solution of carboxyethyl chitosan and alginic acid is obtained, and Jing deaerations obtain spinning solution;The spinning
Silk stock solution is delivered to static mixer by the thermoregulator that booster pump Jing temperature controls are 98 DEG C after extruding from dissolution kettle, and direct
The polyethylene spinning solution of pump to static mixer uniformly mixes, and obtains final product co-blended spinning stock solution.
Wherein, the preparation method of the carboxyethyl chitosan is:
Weigh 5g chitosan fibers to be dispersed in 50mL methanol, add acrylic acid 22.38g, vibration under room temperature stirs,
48h is being reacted in water bath with thermostatic control under the conditions of 90 DEG C, reacted chitosan fiber is separated with reaction mixture, and will be isolated
Chitosan fiber be scattered in 80% (v/v) methanol aqueous solution, Deca 30% (w/v) sodium hydrate aqueous solution, by methanol, hydrogen
Aqueous solution of sodium oxide pH of mixed is transferred to 7.3, soaks 30 minutes, then the chitosan fiber after immersion is isolated from mixed liquor
Come, washed 2 times, after dehydration with 80% (v/v) methanol aqueous solution, be dried under the conditions of 40 DEG C, viscosity is obtained for 150cps, carboxylic second
Base substitution value is 0.8 Carboxyethyl chitosan fiber.
Gained co-blended spinning stock solution Jing prefilter is entered into cortex entrance dosing pump, another road polyvinyl alcohol spin dope
To sandwich layer entrance dosing pump, cortex entrance metering revolution speed/sandwich layer entrance metering revolution speed is 1/0.50, Jing to Jing prefilters pump
5.5 times of the xeothermic stretching at 180 DEG C of fiber of the composite dope thread of core-skin type composite spinneret extrusion Jing after spinning technique, obtains
To the carboxyethyl chitosan and polyvinyl alcohol composite fiber.
By spinning of the carboxyethyl chitosan for obtaining with polyvinyl alcohol composite fiber from after core-skin type composite spinneret pack extrusion
Silk shaping, is shaped using dry-spinning process, and concrete forming technology is:The hot-air path of 170 DEG C of composite dope thread Jing makes
Solvent volatilizees and is solidified.
Carboxyethyl chitosan and polyvinyl alcohol composite fiber are further carried out into acetalization, concrete technology is:By skin
Core pattern chitosan is placed in the bath of the hydroformylation containing formaldehyde or glutaraldehyde with polyvinyl alcohol composite fiber, is reacted 2 hours at -70 DEG C of room temperature
After take out, washing, it is dry obtain have skin-core structure acetalation composite fibre.
Jing tests, the carboxyethyl chitosan and polyvinyl alcohol composite fiber, its intensity are 5.2g/d, extension at break
25%.
Embodiment 2
A kind of carboxyethyl chitosan and polyvinyl alcohol composite fiber, the cortex contain following component by mass parts:Carboxylic second
35 parts of base chitosan fiber;15 parts of alginic acid fibre;3 parts of aloe fibre;The sandwich layer (polyvinyl alcohol) accounts for the total matter of composite fibre
The 20% of amount, the cortex each component summation accounts for the 80% of composite fibre gross mass.
Polyvinyl alcohol (degree of polymerization 2050, alcoholysis degree 98%) is dissolved in 2wt% dilute acetic acid aqueous solutions at 96 DEG C, is obtained
To concentration for 15wt% poly-vinyl alcohol solution, Jing deaerations obtain polyvinyl alcohol spin dope.
The carboxyethyl chitosan containing aloe fibre that deacetylation is 91% and alginic acid are dissolved at room temperature
In 10wt% dilute acetic acid aqueous solutions, the mixed solution of carboxyethyl chitosan and alginic acid is obtained, and Jing deaerations obtain spinning solution;The spinning
Silk stock solution is delivered to static mixer by the thermoregulator that booster pump Jing temperature controls are 96 DEG C after extruding from dissolution kettle, and direct
The polyethylene spinning solution of pump to static mixer uniformly mixes, and obtains final product co-blended spinning stock solution.
Wherein, the preparation method of the carboxyethyl chitosan is:
Weigh 5g chitosan fibers to be dispersed in 250mL ethanol, add acrylic acid 0.11g, vibration under room temperature stirs,
4h is being reacted in water bath with thermostatic control under the conditions of 40 DEG C, reacted chitosan fiber is separated with reaction mixture, and will be isolated
Chitosan fiber be scattered in 80% (v/v) ethanol water, Deca 30% (w/v) potassium hydroxide aqueous solution, by ethanol, hydrogen
Potassium oxide aqueous solution liquid pH is transferred to 8.0, soaks 30 minutes, then the chitosan fiber after immersion is isolated from mixed liquor
Come, washed 2 times, after dehydration with 80% (v/v) ethanol water, be dried under the conditions of 40 DEG C, viscosity is obtained for 900cps, carboxylic second
Base substitution value is 0.01 Carboxyethyl chitosan fiber.
Gained co-blended spinning stock solution Jing prefilter is entered into cortex entrance dosing pump, another road polyvinyl alcohol spin dope
To sandwich layer entrance dosing pump, cortex entrance metering revolution speed/sandwich layer entrance metering revolution speed is 1/0.50, Jing to Jing prefilters pump
5.5 times of the xeothermic stretching at 190 DEG C of fiber of the composite dope thread of core-skin type composite spinneret extrusion Jing after spinning technique, obtains
To the carboxyethyl chitosan and polyvinyl alcohol composite fiber.
By spinning of the carboxyethyl chitosan for obtaining with polyvinyl alcohol composite fiber from after core-skin type composite spinneret pack extrusion
Silk shaping, is shaped using dry-spinning process, and concrete forming technology is:The hot-air path of 175 DEG C of composite dope thread Jing makes
Solvent volatilizees and is solidified.
Carboxyethyl chitosan and polyvinyl alcohol composite fiber are further carried out into acetalization, concrete technology is:By skin
Core pattern chitosan is placed in the bath of the hydroformylation containing formaldehyde or glutaraldehyde with polyvinyl alcohol composite fiber, is reacted 2 hours at -70 DEG C of room temperature
After take out, washing, it is dry obtain have skin-core structure acetalation composite fibre.
Jing tests, the carboxyethyl chitosan and polyvinyl alcohol composite fiber, its intensity are 5.0g/d, extension at break
24%.
Embodiment 3
A kind of carboxyethyl chitosan and polyvinyl alcohol composite fiber, the cortex contain following component by mass parts:Carboxylic second
70 parts of base chitosan fiber;10 parts of alginic acid fibre;5 parts of aloe fibre;The sandwich layer (polyvinyl alcohol) accounts for the total matter of composite fibre
The 31% of amount, the cortex each component summation accounts for the 69% of composite fibre gross mass.
Polyvinyl alcohol (degree of polymerization 3050, alcoholysis degree 98%) is dissolved in 2wt% dilute acetic acid aqueous solutions at 96 DEG C, is obtained
To concentration for 15wt% poly-vinyl alcohol solution, Jing deaerations obtain polyvinyl alcohol spin dope.
The carboxyethyl chitosan containing aloe fibre that deacetylation is 91% and alginic acid are dissolved at room temperature
In 10wt% dilute acetic acid aqueous solutions, the mixed solution of carboxyethyl chitosan and alginic acid is obtained, and Jing deaerations obtain spinning solution;The spinning
Silk stock solution is delivered to static mixer by the thermoregulator that booster pump Jing temperature controls are 96 DEG C after extruding from dissolution kettle, and direct
The polyethylene spinning solution of pump to static mixer uniformly mixes, and obtains final product co-blended spinning stock solution.
Wherein, the preparation method of the carboxyethyl chitosan is:
Weigh 5g chitosan fibers to be dispersed in 200mL isopropanols, add acrylic acid 10.25g, vibration stirring is equal under room temperature
It is even, 24h is being reacted in water bath with thermostatic control under the conditions of 60 DEG C, reacted chitosan fiber is being separated with reaction mixture, and will divide
The chitosan fiber for separating out is scattered in 80% (v/v) aqueous acetone solution, Deca 30% (w/v) potassium hydroxide aqueous solution, by third
Ketone, potassium hydroxide aqueous solution pH of mixed are transferred to 6.0, soak 30 minutes, then by the chitosan fiber after immersion from mixed liquor
Separate, washed 2 times, after dehydration with 80% (v/v) aqueous acetone solution, be dried under the conditions of 40 DEG C, obtaining viscosity is
600cps, the Carboxyethyl chitosan fiber that carboxyethyl substitution value is 0.28.
Gained co-blended spinning stock solution Jing prefilter is entered into cortex entrance dosing pump, another road polyvinyl alcohol spin dope
To sandwich layer entrance dosing pump, cortex entrance metering revolution speed/sandwich layer entrance metering revolution speed is 1/0.50, Jing to Jing prefilters pump
5.5 times of the xeothermic stretching at 190 DEG C of fiber of the composite dope thread of core-skin type composite spinneret extrusion Jing after spinning technique, obtains
To the carboxyethyl chitosan and polyvinyl alcohol composite fiber.
By spinning of the carboxyethyl chitosan for obtaining with polyvinyl alcohol composite fiber from after core-skin type composite spinneret pack extrusion
Silk shaping, is shaped using dry-spinning process, and concrete forming technology is:The hot-air path of 175 DEG C of composite dope thread Jing makes
Solvent volatilizees and is solidified.
Carboxyethyl chitosan and polyvinyl alcohol composite fiber are further carried out into acetalization, concrete technology is:By skin
Core pattern chitosan is placed in the bath of the hydroformylation containing formaldehyde or glutaraldehyde with polyvinyl alcohol composite fiber, is reacted 2 hours at -70 DEG C of room temperature
After take out, washing, it is dry obtain have skin-core structure acetalation composite fibre.
Jing tests, the carboxyethyl chitosan and polyvinyl alcohol composite fiber, its intensity are 4.6g/d, extension at break
23%.
Comparative example 1
Compared with Example 1, in addition to without aloe fibre, other are same as Example 1.
Jing tests, the carboxyethyl chitosan and polyvinyl alcohol composite fiber, its intensity are 4.1g/d, extension at break
18%.
Comparative example 2
Compared with Example 1, in addition to without alginic acid fibre, other are same as Example 1.
Jing tests, the carboxyethyl chitosan and polyvinyl alcohol composite fiber, its intensity are 4.3g/d, extension at break
20%.
Comparative example 3
Compared with Example 1, except being substituted in addition to carboxyethyl chitosan using chitosan, other are same as Example 1.
Jing tests, the carboxyethyl chitosan and polyvinyl alcohol composite fiber, its intensity are 4.0g/d, extension at break
20%.
In sum, present invention employs common with the Carboxyethyl chitosan fiber containing alginic acid fibre and aloe fibre
As cortex, using polyvinyl alcohol as sandwich layer, carboxyethyl chitosan and polyvinyl alcohol composite fiber are constituted, which can make what is obtained to answer
Condensating fiber has excellent physical and mechanical propertiess, and the intensity of its fiber is 4.6-5.2g/d, and extension at break is 23-25%, can be wide
It is general to be applied in medical dressing and functional textile.
Above-described is only the preferred embodiment of the present invention, the invention is not restricted to above example.It is appreciated that this
Art personnel directly derive without departing from the spirit and concept in the present invention or associate other improve and become
Change, be considered as being included within protection scope of the present invention.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But above-mentioned detailed process equipment and technological process are the invention is not limited in, that is, does not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, the selection of concrete mode to the equivalence replacement and auxiliary element of each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (8)
1. a kind of carboxyethyl chitosan and polyvinyl alcohol composite fiber, it is characterised in that the composite fibre includes cortex and core
Layer, the sandwich layer are polyvinyl alcohol;
The cortex contains following component by mass parts:Carboxyethyl chitosan fiber 30-75 part;Alginic acid fibre 10-20 parts;Reed
Luxuriant growth fiber 1-5 parts.
2. composite fibre as claimed in claim 1, it is characterised in that the content of the polyvinyl alcohol is composite fibre gross mass
4%-30%.
3. composite fibre as claimed in claim 1 or 2, it is characterised in that the deacetylation of the Carboxyethyl chitosan fiber
For 70%-90%;
The degree of polymerization of the polyvinyl alcohol is 1800-3800, and alcoholysis degree is 90%-99%;
Fiber number fracture strength 4.6-5.2g/d of the composite fibre, extension at break is 23-25%.
4. the preparation method of the carboxyethyl chitosan as described in one of claim 1-3 and polyvinyl alcohol composite fiber, its feature
It is that methods described includes:
With polyvinyl alcohol spin dope as sandwich layer, with the Carboxyethyl chitosan fiber containing aloe fibre and alginic acid fibre
Co-blended spinning stock solution is cortex, is extruded from core-skin type composite spinneret pack, Jing spinning techniques, then Jing drawing-offs and washing process are obtained
Carboxyethyl chitosan and polyvinyl alcohol composite fiber.
5. method as claimed in claim 4, it is characterised in that methods described includes:
(1) by the degree of polymerization be 1800-3800, alcoholysis degree for 90%-99% polyvinyl alcohol be dissolved at 95-98 DEG C water or
In the dilute acetic acid aqueous solution of below 3wt%, poly-vinyl alcohol solution is obtained, Jing deaerations obtain polyvinyl alcohol spin dope;
(2) the carboxyethyl chitosan containing aloe fibre and alginic acid by deacetylation for 70%-90% dissolves at room temperature
In 1%-10wt% dilute acetic acid aqueous solutions, the mixed solution of carboxyethyl chitosan and alginic acid is obtained, and it is former that Jing deaerations obtain spinning
Liquid;The spinning solution is delivered to static mixed by the thermoregulator that booster pump Jing temperature controls are 95-98 DEG C after extruding from dissolution kettle
Clutch, is uniformly mixed with the polyethylene spinning solution of direct pump to static mixer, obtains final product co-blended spinning stock solution;
(3) gained co-blended spinning stock solution Jing prefilter is entered into cortex entrance dosing pump, another road polyvinyl alcohol spin dope
To sandwich layer entrance dosing pump, cortex entrance metering revolution speed/sandwich layer entrance metering revolution speed is 1/0.50-1/ to Jing prefilters pump
1.5, fiber 180-210 DEG C at xeothermic drawing of the composite dope thread that percutaneous core pattern composite spinneret is extruded Jing after spinning technique
2-5.5 times is stretched, the carboxyethyl chitosan and polyvinyl alcohol composite fiber is obtained.
6. the method as described in claim 4 or 5, it is characterised in that carboxyethyl chitosan and polyvinyl alcohol that step (3) is obtained
Composite fibre from core-skin type composite spinneret pack extrusion after spinning technique, using wet method, wet-dry change or dry-spinning process into
Shape;
It is described wet-formed to be:Coagulating bath is directly entered from the composite dope thread of composite spinneret extrusion, coagulator is adopted
Saturation Na of polyvinyl spinning2SO4Aqueous solution or NaOH aqueous solutions;
Described wet-dry change is configured to:Composite dope thread enters coagulating bath Jing after the air-gap of one section of 1-10cm;
Described duse process is:The hot-air path of composite dope thread Jing 100-170 DEG C makes solvent volatilization and is solidified.
7. the method as described in one of claim 4-6, it is characterised in that the carboxyethyl chitosan and the compound fibre of polyvinyl alcohol
Dimension further carries out acetalization;
Preferably, the acetalization adopts formaldehyde or glutaraldehyde;
Preferably, the acetalization is:Core-skin type chitosan and polyvinyl alcohol composite fiber are placed in containing formaldehyde or penta 2
In the hydroformylation bath of aldehyde, take out after 0.5-2 hours are reacted at -70 DEG C of room temperature, washing, the dry acetalation must with skin-core structure
Composite fibre.
8. the carboxyethyl chitosan as described in one of claim 1-3 and polyvinyl alcohol composite fiber are in medical dressing and feature
Application in textile.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112779644A (en) * | 2020-12-24 | 2021-05-11 | 陕西元丰纺织技术研究有限公司 | Temperature-adjusting antibacterial mosquito-proof yarn and fabric and preparation method thereof |
CN113151925A (en) * | 2021-04-07 | 2021-07-23 | 罗莱生活科技股份有限公司 | Polyquaternary ammonium salt/aloe antibacterial fiber, preparation method thereof and application thereof in antibacterial towels |
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CN102552966A (en) * | 2012-01-31 | 2012-07-11 | 青岛明药堂医药科技开发有限公司 | Alginate antibacterial dressing and its preparation method |
CN103255615A (en) * | 2013-05-27 | 2013-08-21 | 武汉纺织大学 | Carboxyethyl chitosan fiber and preparation method thereof |
CN103736134A (en) * | 2013-12-30 | 2014-04-23 | 深圳先进技术研究院 | Medical sponge dressing and preparation method thereof |
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CN1429937A (en) * | 2002-01-04 | 2003-07-16 | 中国纺织科学研究院 | Chitin amine/polyviny vinyl alcohol composite fiber and its manufacturing method |
CN102552966A (en) * | 2012-01-31 | 2012-07-11 | 青岛明药堂医药科技开发有限公司 | Alginate antibacterial dressing and its preparation method |
CN103255615A (en) * | 2013-05-27 | 2013-08-21 | 武汉纺织大学 | Carboxyethyl chitosan fiber and preparation method thereof |
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