CN114059185A - Plant source tencel fiber and preparation method thereof - Google Patents

Plant source tencel fiber and preparation method thereof Download PDF

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Publication number
CN114059185A
CN114059185A CN202111299288.3A CN202111299288A CN114059185A CN 114059185 A CN114059185 A CN 114059185A CN 202111299288 A CN202111299288 A CN 202111299288A CN 114059185 A CN114059185 A CN 114059185A
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solution
plant
extract
cellulose
sodium alginate
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CN114059185B (en
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山传雷
姜明亮
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Qingdao Bangte Ecological Textile Technology Co ltd
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Qingdao Bangte Ecological Textile Technology Co ltd
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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
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms

Abstract

The invention provides a plant source tencel fiber and a preparation method thereof, which comprises the steps of preparing a cellulose dissolving solution, preparing a plant extract modifier, mixing and spinning. A small amount of ammonium chloride is added into the cellulose dissolving solution, so that the orientation structure of the fiber is improved, and the mechanical property of the fiber is improved; sodium alginate has more active sites after oxidation, and is easier to adsorb effective components in plant extracts; aldehyde groups in the oxidized sodium alginate are combined with hydroxyl groups in cellulose molecules, so that the plant extract is more firmly combined with tencel fibers, and the functionality is more durable; the active groups of the effective components in the plant extract react with the hydroxyl groups in the cellulose molecules in a covalent bond form, so that the cross-linking effect among fibrils is promoted, the transverse binding force among the fibrils is enhanced, the fibrillation of the fibers is inhibited, the fibrillation grade is 1, the fibers are not easy to ball after being rubbed, and the quality of yarns and fabrics is effectively improved in the spinning process.

Description

Plant source tencel fiber and preparation method thereof
Technical Field
The invention belongs to the technical field of fibers, and particularly relates to a plant-derived tencel fiber and a preparation method thereof.
Background
The tencel fiber is commonly called as 'tencel velvet', takes natural plant fiber as a raw material, has multiple excellent performances of natural fiber and synthetic fiber, has the characteristics of comfort, good hand feeling, easy dyeing and the like of natural fiber cotton, has the environmental protection advantage which is not possessed by the traditional viscose fiber, and is widely applied to the fields of clothes, home textiles, non-woven fabrics and the like.
With different living demands of people, higher requirements are provided for the functions and the performances of the fibers, and the fibers can be endowed with the effects of flame retardance, antibiosis, magnetic therapy, heating and the like by adding the functional auxiliary agent into the spinning solution.
The patent number "CN 202010380895.1" named as "plant functional polyester fiber and its preparation method" provides a plant functional polyester fiber, which is prepared by mixing and extruding plants as functional substances with polyester powder to prepare plant functional master batch, and then mixing and spinning the master batch with polyester chips to obtain the polyester fiber with good functions of antibiosis, skin care, health care, etc.
The patent number CN201610321202.5 entitled "preparation method of environmental protection type antibacterial polyester fiber" provides an antibacterial polyester fiber, and antibacterial extract is added into the fiber, so that the antibacterial effect is good, and the fiber is environment-friendly and safe.
The green tea extract contains rich total tea polyphenol, the Chinese gall extract contains rich tannic acid and gallic acid, the mint extract contains rich menthone, the sarcandra glabra extract contains rich isofraxidin, and the plant extracts are added into the lyocell fiber to endow the lyocell fiber with natural antibacterial and antioxidant functions, but with the addition of the functional extracts, the mechanical property of the lyocell fiber is reduced; meanwhile, the functional effects of the functions are greatly weakened along with washing and wearing, so that the use feeling of people is reduced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the plant source tencel fiber and the preparation method thereof, so that the tencel fiber has natural antibacterial and antioxidant properties and still has good mechanical properties; meanwhile, the tencel fiber has more lasting functionality and prolonged service life.
In order to solve the technical problems, the invention adopts the following technical scheme:
a plant-derived Tencel fiber contains plant extracts including green tea extract, Galla chinensis extract, herba Menthae extract, and herba Pileae Scriptae extract.
A preparation method of plant source tencel fiber comprises the following steps:
1. preparation of cellulose dissolving solution
(1) Swelling of cellulose pulp
Soaking cellulose pulp into deionized water, and ultrasonically stirring for 13-18min to fully swell cellulose and reduce the ash content in the pulp;
the cellulose pulp is one or more of cotton pulp, bamboo pulp or wood pulp, the cellulose content is more than or equal to 98 percent, and the cellulose pulp is purchased from Changzhou Fengrun special fiber company Limited.
(2) Enzymolysis
Dewatering the swelled pulp to 10-15% of water, putting the pulp into a reaction kettle, adding a cellulase solution and a buffer solution, adjusting the pH value to 4.5-5.5, stirring at 45-50 ℃ for 3-4h at a stirring speed of 150-;
the ratio of the cellulase solution to the pulp is 20-25: 1; the cellulase content in the cellulase hydrolysate is 5-8%, and the cellulase hydrolysate is purchased from Shangxi Chengcheng biological technology Co., Ltd;
the buffer solution is 0.1mol/L phosphate buffer solution and 0.05-0.15mol/L sodium citrate buffer solution, and the ratio of the two buffer solutions is 1: 1-1.5; the addition amount of the buffer solution is 20-30% of the cellulose enzymolysis solution.
(3) Dissolution
Carrying out vacuum decompression concentration on the NMMO solution with the concentration of 50% to obtain an NMMO solution with the concentration of 65% -70%, wherein the vacuum degree is-0.08-0.05 MPa, and the decompression temperature is 75-90 ℃;
adding cellulose and the concentrated NMMO solution into a reaction kettle according to the proportion of 1:10-15, and performing ultrasonic dispersion for 5-8min at the ultrasonic frequency of 60-80KHz to fully mix the cellulose and the concentrated NMMO solution and dissolve the cellulose and the NMMO solution more fully; adding a stabilizer, adjusting the vacuum degree to 0.05-0.1MPa, stirring at 70-80 ℃ for 40-60min at the stirring speed of 300-400r/min to obtain a cellulose dissolving solution;
the stabilizer is one or more of disodium ethylene diamine tetraacetate, n-propyl gallate and antioxidant 1010; the addition amount of the stabilizer is 3-5% of the NMMO solution.
(4) Modification of
Adding ammonium chloride into the cellulose dissolving solution, heating to 100-110 ℃, stirring for 30-50min, and reacting for 80-100min to obtain the modified cellulose dissolving solution, wherein the addition amount of the ammonium chloride is 1.5-2% of the cellulose dissolving solution.
2. Preparation of plant extract modifier
(1) Oxidation by oxygen
Placing sodium alginate and deionized water in a reaction kettle according to the proportion of 1:40-50, stirring for 8-12min, adding anhydrous ethanol, ultrasonic dissolving at 40-45 deg.C for 15-20min, and ultrasonic frequency of 100-120KHz to obtain sodium alginate solution; the addition amount of the absolute ethyl alcohol is 20-25% of the deionized water;
placing sodium periodate and deionized water in a reaction kettle according to the proportion of 1:15-20, ultrasonically dissolving for 15-20min at the temperature of 45-50 ℃, and preparing sodium periodate solution by ultrasonic frequency of 100-120 KHz;
the sodium periodate accounts for 50-60% of the sodium alginate;
adding sodium periodate solution into sodium alginate solution while stirring, performing ultrasonic reaction at 30-35 deg.C for 2-3 hr to oxidize secondary hydroxyl in sodium alginate to form aldehyde group with ultrasonic frequency of 80-100 KHz; adding ethylene glycol to stop the reaction after the full reaction, adding absolute ethyl alcohol, stirring for 5-10min, dehydrating by a centrifuge, washing for 3-4 times by the absolute ethyl alcohol, drying at 70-80 ℃, and crushing to 180-mesh 220-mesh powder to obtain oxidized sodium alginate powder;
the addition amount of the ethylene glycol is 65-70% of the addition amount of the sodium periodate;
the addition amount of the absolute ethyl alcohol is 20-30% of the mixed solution of sodium periodate and sodium alginate.
(2) Ultrasonic treatment
Mixing and stirring oxidized sodium alginate and deionized water according to the proportion of 1:20-25 for 20-30min at the temperature of 45-50 ℃ and the stirring speed of 100-;
pulverizing green tea extract, Galla chinensis extract, herba Menthae extract, and herba Pileae Scriptae extract to 100-150 mesh, soaking in 6-8 times of ethanol solution at a ratio of 3-5:2:1:1, stirring at 50-60 deg.C for 15-20min at a stirring rate of 100-200r/min to obtain plant extract solution;
the concentration of the ethanol solution is 85-97%;
the content of total tea polyphenols in the green tea extract is more than 25%, wherein EGCG (epigallocatechin gallate) is more than 2.8%, and EGC (epigallocatechin) is more than 6%; the gallnut extract contains more than 6.2% of tannic acid, more than 8% of gallic acid and more than 0.5% of oleic acid; the mint extract has a menthone content of more than 200 ppm; the content of isofraxidin in the sarcandra glabra extract is more than 300 ppm; the above extracts are all commercially available;
adding the plant extract solution into oxidized sodium alginate solution, performing ultrasonic treatment at 55-65 deg.C and ultrasonic frequency of 50-60KHz for 40-60min to increase the active sites of oxidized sodium alginate and facilitate adsorption of effective components of plant extract, and performing ultrasonic treatment and vacuum concentration to obtain plant extract modifier with concentration of 50-60%;
the mass ratio of the plant extract in the plant extract solution to the oxidized sodium alginate in the oxidized sodium alginate solution is 1: 2-4.
3. Mixing
Adding a plant extract modifier into the modified cellulose dissolving solution obtained in the step 1, adding 0.5mol/L glacial acetic acid to adjust the pH value to 4.5-5.5, carrying out ultrasonic reaction at 50-60 ℃ for 60-80min, and obtaining a spinning stock solution by ultrasonic frequency of 120KHz and 140 KHz; the aldehyde group in the oxidized sodium alginate is combined with the hydroxyl group in the cellulose molecule, so that the plant extract can be combined with the fiber more firmly, and the functionality is more durable;
the addition amount of the plant extract modifier is 6-8% of the modified cellulose dissolving solution.
4. Spinning
And (3) spinning and forming the spinning stock solution by a coagulating bath to obtain the plant source tencel fiber prepared by the invention, wherein the length of an air gap is 6-8cm, the number of holes of a spinneret plate is 100-150, the spinning speed is 65-80m/min, the coagulating bath is an NMMO solution with the concentration of 10-14%, and the temperature is 10-15 ℃.
Due to the adoption of the technical scheme, the invention achieves the technical effects that:
1. the plant source tencel fiber prepared by the invention has the advantages of dry breaking strength of 5.1-5.8cN/dtex, wet breaking strength of 3.25-4.0cN/dtex, wet elongation at break of 18.3-21.5%, and good mechanical property.
2. The plant-derived tencel fiber prepared by the invention has natural antibacterial and antioxidant effects, and better meets the requirements of people on functionality in life, wherein the bacteriostasis rate to escherichia coli is more than 99%, the bacteriostasis rate to klebsiella pneumoniae is more than 99%, the bacteriostasis rate to candida albicans is more than 98% (detected according to the national standard GB/T20944.3-2008), and the bacteriostasis loss rate is lower than 2% after washing for 100 times.
3. The pulp is treated by cellulase to destroy hydrogen bonds in cellulose macromolecular chains, and can be more fully dissolved in NMMO solution subsequently.
4. The NMMO solution is used for preparing tencel fiber, so that the environment is protected, no pollution is caused, the solution can be recycled, and the cost is saved.
5. After the cellulose is added into the NMMO solution, hydrogen bonds among cellulose molecules are broken, cellulose molecular chains are broken, and the cellulose is dissolved to form a uniform solution system.
6. A small amount of ammonium chloride is added into the cellulose dissolving solution, cellulose molecular chains are uniformly broken and have more active hydroxyl groups, at the moment, the ammonium chloride is added, part of ammonia molecules react with the broken hydroxyl groups on the cellulose molecules to form hydrogen bonds, a small amount of weak crosslinking effect is generated, when spinning trickle enters an air gap section, the weak crosslinking structure is easily destroyed under the action of external stress, the orientation structure of the fiber can be improved, and the mechanical property of the tencel fiber is improved; when the amount of the added ammonium chloride is too small, the crosslinking effect among cellulose molecules is increased, the external stress hardly changes the orientation structure of the fiber, so that relatively weak hydrogen bonds among the cellulose molecules are broken, the structure of the molecular chain is damaged, and the mechanical property of the fiber is reduced.
7. If the ammonium chloride is added in the cellulose dissolving process, the cellulose molecular chain is not completely broken, the exposed hydroxyl is less, the selectivity of ammonia molecules is reduced, the orientation degree of the fiber is improved less, and the mechanical property is not obviously improved.
8. Sodium alginate and iodate have selective oxidation hydroxyl reaction, secondary hydroxyl of sodium alginate is oxidized to form multifunctional aldehyde group, and oxidized sodium alginate has more active sites, so that effective components in the plant extract can be better adsorbed; the aldehyde group in the oxidized sodium alginate reacts with the hydroxyl group in the cellulose molecule, so that the plant extract can be more firmly combined with the tencel fiber, the functionality is more durable, the fiber is more compact, and the mechanical property of the tencel fiber is further improved.
9. The plant extract modifier is combined with the tencel fiber, so that the fibrillation degree of the tencel fiber is greatly reduced, the transverse bonding force among fibrils is enhanced, the fiber is smoother, smoother and denser, the fibrillation grade of the fiber is 1 measured by an ultrasonic oscillation method, and the fibrillation grade of common tencel fiber sold in the market is generally 2-3.
10. After the plant extract modifier is added into the modified cellulose dissolving solution, under the condition of weak acidity, active groups of active ingredients in the plant extract react with hydroxyl groups in cellulose molecules in a covalent bond mode, so that cross-linking action is generated among fibrils, the transverse binding force among the fibrils is enhanced, the fibrillation of tencel fibers is inhibited, the practicability of the tencel fibers is enhanced, the tencel fibers are not easy to ball up after being rubbed, and the quality of yarns and fabrics is effectively improved in the textile process.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Embodiment 1 a plant source tencel fiber and a preparation method thereof, comprising the following steps:
1. preparation of cellulose dissolving solution
(1) Swelling of cellulose pulp
Immersing the cotton pulp in deionized water, and ultrasonically stirring for 15min to fully swell the cellulose and reduce the ash content in the pulp.
(2) Enzymolysis
Dehydrating the swollen cotton pulp to water content of 13%, placing into a reaction kettle, adding cellulase solution and buffer solution, adjusting pH to 5, stirring at 50 deg.C for 4h at a stirring speed of 200r/min, inactivating enzyme at high temperature after stirring, filtering, and drying at 80 deg.C for 2.5h to obtain cellulose;
the ratio of the cellulase solution to the pulp is 25: 1; the cellulase content in the cellulase hydrolysate is 6 percent;
the buffer solution is 0.1mol/L phosphate buffer solution and 0.08mol/L sodium citrate buffer solution, and the ratio of the phosphate buffer solution to the sodium citrate buffer solution is 1: 1; the addition amount of the buffer solution is 25 percent of the cellulose enzymolysis solution.
(3) Dissolution
Carrying out vacuum decompression concentration on the NMMO solution with the concentration of 50% to obtain an NMMO solution with the concentration of 70%, wherein the vacuum degree is-0.08 MPa, and the decompression temperature is 85 ℃;
adding cellulose and the concentrated NMMO solution into a reaction kettle according to the proportion of 1:12, and performing ultrasonic dispersion for 8min at the ultrasonic frequency of 70KHz to fully mix the cellulose and the concentrated NMMO solution and dissolve the cellulose and the NMMO solution more fully; adding stabilizer, adjusting vacuum degree to 0.1MPa, stirring at 75 deg.C for 50min at stirring speed of 350r/min to obtain cellulose solution;
the stabilizer is disodium ethylene diamine tetraacetate, and the addition amount of the stabilizer is 4% of the NMMO solution.
(4) Modification of
Adding ammonium chloride into the cellulose dissolved solution, heating to 105 ℃, stirring for 40min, and reacting for 90min to obtain the modified cellulose dissolved solution, wherein the addition amount of the ammonium chloride is 1.85% of the cellulose dissolved solution.
2. Preparation of plant extract modifier
(1) Oxidation by oxygen
Placing sodium alginate and deionized water in a reaction kettle according to a ratio of 1:45, stirring for 10min, adding anhydrous ethanol, ultrasonically dissolving at 45 deg.C for 20min, and ultrasonically dissolving at 110KHz to obtain sodium alginate solution; the addition amount of the absolute ethyl alcohol is 23 percent of that of the deionized water;
placing sodium periodate and deionized water in a reaction kettle according to the proportion of 1:18, ultrasonically dissolving for 20min at 47 ℃, and ultrasonically dissolving at the frequency of 110KHz to prepare sodium periodate solution;
the sodium periodate is 55 percent of the sodium alginate;
adding sodium periodate solution into sodium alginate solution while stirring, performing ultrasonic reaction for 2.5h at 32 ℃, oxidizing secondary hydroxyl in the sodium alginate to form aldehyde group, and performing ultrasonic treatment at 90KHz frequency; adding ethylene glycol to stop the reaction after the full reaction, adding absolute ethyl alcohol, stirring for 10min, dehydrating by a centrifugal machine, washing for 4 times by the absolute ethyl alcohol, drying at 80 ℃, and crushing to 180 meshes to obtain oxidized sodium alginate powder;
the addition amount of the ethylene glycol is 68 percent of the addition amount of the sodium periodate;
the addition amount of the absolute ethyl alcohol is 26 percent of the mixed solution of sodium periodate and sodium alginate.
(2) Ultrasonic treatment
Mixing and stirring oxidized sodium alginate and deionized water according to the proportion of 1:20 for 25min at the temperature of 50 ℃ and the stirring speed of 160r/min to obtain an oxidized sodium alginate solution;
pulverizing green tea extract, Galla chinensis extract, herba Menthae extract, and herba Pileae Scriptae extract to 100 mesh, soaking in 7 times of ethanol solution at a ratio of 4:2:1:1, stirring at 55 deg.C for 20min and stirring rate of 150r/min to obtain plant extract solution; the concentration of the ethanol solution is 90 percent;
adding the plant extract solution into oxidized sodium alginate solution, performing ultrasonic treatment at 60 deg.C and ultrasonic frequency of 55KHz for 50min to increase the active sites of oxidized sodium alginate, so as to more easily adsorb effective components of plant extract, and performing ultrasonic treatment and vacuum concentration to obtain plant extract modifier with concentration of 60%;
the mass ratio of the plant extract in the plant extract solution to the oxidized sodium alginate in the oxidized sodium alginate solution is 1: 3.
3. mixing
Adding a plant extract modifier into the modified cellulose dissolving solution obtained in the step 1, adding 0.5mol/L glacial acetic acid to adjust the pH value to 5, carrying out ultrasonic reaction at 55 ℃ for 70min, and obtaining a spinning stock solution at the ultrasonic frequency of 130 KHz; the aldehyde group in the oxidized sodium alginate is combined with the hydroxyl group in the cellulose molecule, so that the plant extract can be more firmly combined with the tencel fiber, and the functionality is more durable;
the addition amount of the plant extract modifier is 7.5 percent of the modified cellulose dissolving solution.
4. Spinning
And (3) spinning and forming the spinning stock solution by a coagulating bath to obtain the plant source tencel fiber prepared by the invention, wherein the air gap length is 7cm, the spinneret plate holes are 120, the spinning speed is 70m/min, the coagulating bath is an NMMO solution with the concentration of 12%, and the temperature is 13 ℃.
The tencel fiber prepared by the embodiment has the dry breaking strength of 5.8cN/dtex, the wet breaking strength of 4.0cN/dtex, the wet elongation at break of 18.3 percent, good mechanical properties and the fibrillation grade of 1.
The plant-derived tencel fiber prepared in example 1 has good antibacterial performance, and has 99.7% of inhibition rate on escherichia coli, 99.5% of inhibition rate on klebsiella pneumoniae and 98.6% of inhibition rate on candida albicans (detected according to the national standard GB/T20944.3-2008), and the inhibition loss rate is 1.6% after washing for 100 times.
Embodiment 2A plant-derived Tencel fiber and a method for preparing the same
1. Preparation of cellulose dissolving solution
(1) Swelling of cellulose pulp
Soaking bamboo pulp in deionized water, and ultrasonically stirring for 13min to fully swell cellulose and reduce ash content in the pulp.
(2) Enzymolysis
Dehydrating the swollen bamboo pulp to reach the moisture content of 15%, putting the bamboo pulp into a reaction kettle, adding a cellulase solution and a buffer solution, adjusting the pH value to 5.5, stirring the bamboo pulp at the temperature of 45 ℃ for 3.5 hours at the stirring speed of 150r/min, inactivating enzymes at high temperature after stirring, filtering the bamboo pulp, and drying the bamboo pulp at the temperature of 85 ℃ for 2 hours to obtain cellulose;
the ratio of the cellulase solution to the pulp is 20: 1; the cellulase content in the cellulase hydrolysate is 5%;
the buffer solution is 0.1mol/L phosphate buffer solution and 0.15mol/L sodium citrate buffer solution, and the ratio of the phosphate buffer solution to the sodium citrate buffer solution is 1: 1.5; the addition amount of the buffer solution is 30 percent of the cellulose enzymolysis solution.
(3) Dissolution
Carrying out vacuum decompression concentration on the NMMO solution with the concentration of 50% to obtain an NMMO solution with the concentration of 65%, wherein the vacuum degree is 0.01MPa, and the decompression temperature is 90 ℃;
adding cellulose and the concentrated NMMO solution into a reaction kettle according to the proportion of 1:10, and performing ultrasonic dispersion for 5min at the ultrasonic frequency of 80KHz to fully mix the cellulose and the concentrated NMMO solution and dissolve the cellulose and the NMMO solution more fully; adding stabilizer, adjusting vacuum degree to 0.05MPa, stirring at 70 deg.C for 40min at stirring speed of 400r/min to obtain cellulose solution;
the stabilizer is antioxidant 1010, and the addition amount of the stabilizer is 5% of the NMMO solution.
(4) Modification of
Adding ammonium chloride into the cellulose dissolving solution, heating to 100 ℃, stirring for 30min, and reacting for 80min to obtain the modified cellulose dissolving solution, wherein the addition amount of the ammonium chloride is 1.5% of the cellulose dissolving solution.
2. Preparation of plant extract modifier
(1) Oxidation by oxygen
Placing sodium alginate and deionized water in a reaction kettle according to a ratio of 1:40, stirring for 8min, adding anhydrous ethanol, ultrasonic dissolving at 40 deg.C for 20min, and ultrasonic frequency of 100KHz to obtain sodium alginate solution; the addition amount of the absolute ethyl alcohol is 20 percent of that of the deionized water;
placing sodium periodate and deionized water in a reaction kettle according to the proportion of 1:15, ultrasonically dissolving for 15min at 45 ℃, and ultrasonically dissolving at 100KHz to prepare sodium periodate solution;
the sodium periodate is 50% of sodium alginate;
adding sodium periodate solution into sodium alginate solution while stirring, performing ultrasonic reaction for 2h at 30 ℃, oxidizing secondary hydroxyl in the sodium alginate to form aldehyde group, and performing ultrasonic treatment at the ultrasonic frequency of 80 KHz; adding ethylene glycol to stop the reaction after the full reaction, adding absolute ethyl alcohol, stirring for 5min, dehydrating by a centrifugal machine, washing for 3 times by the absolute ethyl alcohol, drying at 70 ℃, and crushing to 220 meshes to obtain oxidized sodium alginate powder;
the addition amount of the ethylene glycol is 65% of the addition amount of the sodium periodate;
the addition amount of the absolute ethyl alcohol is 20 percent of the mixed solution of sodium periodate and sodium alginate.
(2) Ultrasonic treatment
Mixing and stirring oxidized sodium alginate and deionized water according to the proportion of 1:25 for 20min at the temperature of 45 ℃ and the stirring speed of 100r/min to obtain an oxidized sodium alginate solution;
pulverizing green tea extract, Galla chinensis extract, herba Menthae extract, and herba Pileae Scriptae extract to 150 mesh, soaking in 8 times of ethanol solution at a ratio of 3:2:1:1, stirring at 50 deg.C for 15min at a stirring speed of 100r/min to obtain plant extract solution; the concentration of the ethanol solution is 85 percent;
adding the plant extract solution into oxidized sodium alginate solution, performing ultrasonic treatment at 55 deg.C and ultrasonic frequency of 60KHz for 40min, increasing the active sites of oxidized sodium alginate, and making it easier to adsorb effective components of plant extract, and performing ultrasonic treatment and vacuum concentration to 55% to obtain plant extract modifier;
the mass ratio of the plant extract in the plant extract solution to the oxidized sodium alginate in the oxidized sodium alginate solution is 1: 2.
3. mixing
Adding plant extract modifier into modified cellulose solution, adding 0.5mol/L glacial acetic acid to adjust pH to 4.5, performing ultrasonic reaction at 50 deg.C for 60min, and performing ultrasonic frequency of 140KHz to obtain spinning solution; the aldehyde group in the oxidized sodium alginate is combined with the hydroxyl group in the cellulose molecule, so that the plant extract can be combined with the fiber more firmly, and the functionality is more durable;
the addition amount of the plant extract modifier is 6 percent of the modified cellulose dissolving solution.
4. Spinning
And (3) spinning and forming the spinning stock solution by a coagulating bath to obtain the plant source tencel fiber prepared by the invention, wherein the length of an air gap is 6cm, the number of spinneret holes is 150, the spinning speed is 65m/min, the coagulating bath is an NMMO solution with the concentration of 10%, and the temperature is 10 ℃.
The tencel fiber prepared by the embodiment has the dry breaking strength of 5.1cN/dtex, the wet breaking strength of 3.25cN/dtex, the wet elongation at break of 21.5 percent, good mechanical properties and the fibrillation grade of 1.
The plant-derived tencel fiber prepared in example 2 has good antibacterial performance, and has 99.5% of inhibition rate on escherichia coli, 99.3% of inhibition rate on klebsiella pneumoniae and 98.5% of inhibition rate on candida albicans (detected according to the national standard GB/T20944.3-2008), and the inhibition loss rate is 1.7% after washing for 100 times.
Example 3A plant-derived Tencel fiber and a method for preparing the same
1. Preparation of cellulose dissolving solution
(1) Swelling of cellulose pulp
And (3) immersing the wood pulp into deionized water, and ultrasonically stirring for 18min to fully swell the cellulose and reduce the ash content in the pulp.
(2) Enzymolysis
Dewatering the swollen wood pulp to 10% of water, putting the swollen wood pulp into a reaction kettle, adding a cellulase solution and a buffer solution, adjusting the pH to 4.5, stirring the mixture at 50 ℃ for 3 hours at a stirring speed of 250r/min, inactivating enzymes at high temperature after stirring, filtering the mixture, and drying the mixture at 75 ℃ for 3 hours to obtain cellulose;
the ratio of the cellulase solution to the pulp is 25: 1; the cellulase content in the cellulase hydrolysate is 8 percent;
the buffer solution is 0.1mol/L phosphate buffer solution and 0.05mol/L sodium citrate buffer solution, and the ratio of the phosphate buffer solution to the sodium citrate buffer solution is 1: 1; the addition amount of the buffer solution is 20 percent of that of the cellulose enzymolysis solution.
(3) Dissolution
Carrying out vacuum decompression concentration on the NMMO solution with the concentration of 50% to obtain an NMMO solution with the concentration of 70%, wherein the vacuum degree is 0.05MPa, and the decompression temperature is 75 ℃;
adding cellulose and the concentrated NMMO solution into a reaction kettle according to the proportion of 1:15, and performing ultrasonic dispersion for 8min at the ultrasonic frequency of 60KHz to fully mix the cellulose and the concentrated NMMO solution and dissolve the cellulose and the NMMO solution more fully; adding stabilizer, adjusting vacuum degree to 0.1MPa, stirring at 80 deg.C for 60min at stirring speed of 300r/min to obtain cellulose solution;
the stabilizing agent is n-propyl gallate, and the adding amount of the stabilizing agent is 3% of the NMMO solution.
(4) Modification of
Adding ammonium chloride into the cellulose dissolved solution, heating to 110 ℃, stirring for 50min, and reacting for 100min to obtain the modified cellulose dissolved solution, wherein the addition amount of the ammonium chloride is 2% of the cellulose dissolved solution.
2. Preparation of plant extract modifier
(1) Oxidation by oxygen
Placing sodium alginate and deionized water in a reaction kettle according to a ratio of 1:50, stirring for 12min, adding anhydrous ethanol, ultrasonically dissolving at 45 deg.C for 15min, and ultrasonically dissolving at 120KHz to obtain sodium alginate solution; the addition amount of the absolute ethyl alcohol is 25 percent of that of the deionized water;
placing sodium periodate and deionized water in a reaction kettle according to the proportion of 1:20, ultrasonically dissolving for 20min at 50 ℃, and ultrasonically dissolving at the ultrasonic frequency of 120KHz to prepare a sodium periodate solution;
the sodium periodate accounts for 60 percent of the sodium alginate;
adding sodium periodate solution into sodium alginate solution while stirring, performing ultrasonic reaction for 3h at 35 ℃, oxidizing secondary hydroxyl in the sodium alginate to form aldehyde group, and performing ultrasonic treatment at 100 KHz; adding ethylene glycol to stop the reaction after the full reaction, adding absolute ethyl alcohol, stirring for 10min, dehydrating by a centrifugal machine, washing for 4 times by the absolute ethyl alcohol, drying at 80 ℃, and crushing to 200 meshes to obtain oxidized sodium alginate powder;
the addition amount of the ethylene glycol is 70% of the addition amount of the sodium periodate;
the addition amount of the absolute ethyl alcohol is 30 percent of the mixed solution of sodium periodate and sodium alginate.
(2) Ultrasonic treatment
Mixing and stirring oxidized sodium alginate and deionized water according to the proportion of 1:25 for 30min at the temperature of 50 ℃ and the stirring speed of 200r/min to obtain an oxidized sodium alginate solution;
pulverizing green tea extract, Galla chinensis extract, herba Menthae extract, and herba Pileae Scriptae extract to 130 mesh, soaking in 6 times of ethanol solution at a ratio of 5:2:1:1, stirring at 60 deg.C for 20min and stirring at 200r/min to obtain plant extract solution; the concentration of the ethanol solution is 97 percent;
adding the plant extract solution into oxidized sodium alginate solution, performing ultrasonic treatment at 65 deg.C and ultrasonic frequency of 50KHz for 60min, increasing the active sites of oxidized sodium alginate, and making it easier to adsorb effective components of plant extract, and performing ultrasonic treatment and vacuum concentration to 50% to obtain plant extract modifier;
the mass ratio of the plant extract in the plant extract solution to the oxidized sodium alginate in the oxidized sodium alginate solution is 1: 4.
3. mixing
Adding plant extract modifier into modified cellulose solution, adding 0.5mol/L glacial acetic acid to adjust pH to 5.5, performing ultrasonic reaction at 60 deg.C for 80min, and performing ultrasonic frequency of 120KHz to obtain spinning solution; the aldehyde group in the oxidized sodium alginate is combined with the hydroxyl group in the cellulose molecule, so that the plant extract can be combined with the fiber more firmly, and the functionality is more durable;
the addition amount of the plant extract modifier is 8 percent of the modified cellulose dissolving solution.
4. Spinning
And (3) spinning and forming the spinning stock solution by a coagulating bath to obtain the plant source tencel fiber prepared by the invention, wherein the length of an air gap is 8cm, the number of spinneret holes is 100, the spinning speed is 80m/min, the coagulating bath is an NMMO solution with the concentration of 14%, and the temperature is 15 ℃.
The tencel fiber prepared by the embodiment has the dry breaking strength of 5.35cN/dtex, the wet breaking strength of 3.42cN/dtex, the wet elongation at break of 20.8 percent, good mechanical properties and the fibrillation grade of 1.
The plant-derived tencel fiber prepared in example 3 has good antibacterial performance, and has 99.7% of inhibition rate on escherichia coli, 99.4% of inhibition rate on klebsiella pneumoniae and 98.6% of inhibition rate on candida albicans (detected according to the national standard GB/T20944.3-2008), and the inhibition loss rate is 1.6% after washing for 100 times.
Comparative examples 1 to 2
By using representative example 1, the addition amounts of ammonium chloride were changed to 1% and 3% of the cellulose dissolving solution, respectively, and the remaining steps were identical to those of example 1, and the breaking strengths of the plant-derived Tencel fibers prepared as comparative examples 1 to 2 were compared in Table 1.
TABLE 1
Figure BDA0003337662260000111
It can be seen that by changing the amount of ammonium chloride added, the mechanical properties of the fibers are significantly reduced and the fibrillation rating is still 1.
Comparative example 3
By adopting the representative example 1, oxidized sodium alginate in the plant extract modifier is removed, the plant extract is directly added into the modified cellulose dissolving solution, and the rest is consistent with the example 1, as the comparative example 3, the prepared plant source tencel fiber has the dry breaking strength of 4.4cN/dtex, the wet breaking strength of 2.5cN/dtex, the fibrillation grade of 2, the bacteriostasis loss rate of about 20 percent after washing for 100 times, and the antibacterial durability is poor.
It can be seen that, in comparative example 3, after the oxidized sodium alginate in the plant extract modifier is removed, the mechanical property is slightly reduced, the antibacterial durability is greatly reduced, and the oxidized sodium alginate has more active sites, so that the effective components in the plant extract can be better adsorbed; aldehyde groups in the oxidized sodium alginate are firstly combined with hydroxyl groups in cellulose molecules, so that a plant extract attached to the oxidized sodium alginate is fully contacted with the cellulose molecules, active groups of active ingredients in the plant extract react with the hydroxyl groups in the cellulose molecules in a covalent bond mode, the antigen fibrillation effect is better, the antibacterial effect is more durable, and meanwhile, the fibers are more compact, so that the mechanical property of the tencel fibers is further improved; however, when the plant extract is simply applied to cellulose molecules, the plant extract cannot be uniformly distributed and cannot fully contact and react with the cellulose molecules, and the anti-fibrillation effect is slightly poor.
Comparative example 4
Using representative example 1, the plant extract modifier was removed and the remainder was the same as example 1 as comparative example 4; ammonium chloride and the plant extract modifier were removed, and the remainder was the same as in example 1, as comparative example 5.
In comparative example 4, after the plant extract modifier is removed, the fibrillation phenomenon of the fiber is particularly serious, the level 1 is changed into the level 4, and a large number of fibrils appear on the surface of the fiber, which shows that the plant extract plays an especially important role in improving the fibrillation of the fiber; in comparative example 5, ammonium chloride and the plant extract modifier are removed, and fibrillation is carried out to grade 3, because the addition of ammonium chloride enhances the mechanical property of the fibers, but the transverse bonding force among fibrils is reduced and the fibrillation phenomenon is aggravated due to the change of the orientation structure of the fibers; the fibrillation grade of the tencel fiber in the embodiment is only grade 1, and the surface of the fiber is flat, smooth and compact.
Adding a plant extract modifier into a modified cellulose dissolving solution, firstly combining aldehyde groups in oxidized sodium alginate with hydroxyl groups in cellulose molecules under a weak acidic condition, and fully contacting the plant extract attached to the oxidized sodium alginate with the cellulose molecules; the active groups of the effective components in the plant extract and the hydroxyl groups in the cellulose molecules react in a covalent bond mode to promote the cross-linking action among fibrils, enhance the transverse binding force among the fibrils, inhibit the fibrillation of the tencel fibers, enhance the practicability of the tencel fibers, are not easy to ball after being rubbed, and effectively improve the quality of yarns and fabrics in the textile process.
Unless otherwise specified, the proportions are mass proportions, and the percentages are mass percentages; the raw materials are all purchased from the market.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The plant-derived tencel fiber is characterized by containing plant extracts, wherein the plant extracts comprise green tea extracts, gallnut extracts, mint extracts and sarcandra glabra extracts.
2. A preparation method of plant source tencel fiber is characterized in that the preparation method comprises the steps of preparing cellulose dissolving solution, preparing plant extract modifier, mixing and spinning;
the preparation of the cellulose dissolving solution comprises swelling, enzymolysis, dissolution and modification of cellulose pulp.
3. The method for preparing the plant-derived tencel fiber as claimed in claim 2, wherein the modification comprises adding ammonium chloride into the cellulose solution, heating to 100-110 ℃, stirring for 30-50min, and reacting for 80-100min to obtain the modified cellulose solution.
4. The method for preparing a plant-derived Tencel fiber as claimed in claim 3, wherein the ammonium chloride is added in an amount of 1.5-2% of the cellulose dissolving solution.
5. The method of claim 2, wherein the plant extract modifier is prepared by oxidation and sonication.
6. The method for preparing the plant-derived tencel fiber as claimed in claim 5, wherein the oxidation comprises adding sodium periodate solution into sodium alginate solution under stirring, and performing ultrasonic reaction at 30-35 deg.C for 2-3h with ultrasonic frequency of 80-100 KHz; after full reaction, adding ethylene glycol to stop the reaction, adding absolute ethyl alcohol, stirring for 5-10min, dehydrating by a centrifuge, washing for 3-4 times by the absolute ethyl alcohol, drying at 70-80 ℃, and crushing to 180-mesh 220-mesh powder to obtain oxidized sodium alginate powder.
7. The method for preparing the plant-derived tencel fiber according to claim 6, wherein the amount of the ethylene glycol added is 65-70% of the amount of the sodium periodate added;
the addition amount of the absolute ethyl alcohol is 20-30% of the mixed solution of sodium periodate and sodium alginate.
8. The preparation method of the plant-derived tencel fiber as claimed in claim 5, wherein the ultrasonic treatment comprises adding the plant extract solution into oxidized sodium alginate solution, ultrasonic treating at 55-65 deg.C for 40-60min at 50-60KHz, and concentrating under reduced pressure to 50-60% concentration;
the mass ratio of the plant extract in the plant extract solution to the oxidized sodium alginate in the oxidized sodium alginate solution is 1: 2-4;
the preparation method of the plant extract solution comprises the steps of crushing the green tea extract, the gallnut extract, the mint extract and the sarcandra glabra extract to 150 meshes, soaking the crushed green tea extract, the gallnut extract, the mint extract and the sarcandra glabra extract in 6-8 times of ethanol solution according to the proportion of 3-5:2:1:1, and stirring the mixture for 15-20min at 50-60 ℃ and at the stirring speed of 100-200 r/min.
9. The method as claimed in claim 2, wherein the mixing step comprises adding the plant extract modifier into the modified cellulose solution, adding 0.5mol/L glacial acetic acid to adjust the pH value to 4.5-5.5, and performing ultrasonic reaction at 50-60 deg.C for 60-80min at an ultrasonic frequency of 120-140 KHz.
10. The method for preparing a plant-derived Tencel fiber as claimed in claim 9, wherein the amount of the plant extract modifier added is 6-8% of the modified cellulose solution.
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