CN111005090A - Preparation method of chitosan/gallnut tannin composite fiber - Google Patents
Preparation method of chitosan/gallnut tannin composite fiber Download PDFInfo
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- CN111005090A CN111005090A CN201910151291.7A CN201910151291A CN111005090A CN 111005090 A CN111005090 A CN 111005090A CN 201910151291 A CN201910151291 A CN 201910151291A CN 111005090 A CN111005090 A CN 111005090A
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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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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- 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
- D01D5/06—Wet spinning methods
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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
- 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
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Abstract
The invention discloses a preparation method of chitosan/gallnut tannin composite fibers, and belongs to the field of bio-based functional fibers. The composite fiber is prepared by blending gallnut tannin and chitosan, has good mechanical property and thermal stability, and has strong antibacterial effect on staphylococcus aureus. The invention adopts natural polyphenol gallnut tannin and chitosan to blend and prepare chitosan/gallnut tannin composite fiber, and gallnut tannin becomes a cross-linking agent to improve the mechanical property of chitosan fiber and endow the chitosan fiber with functionality.
Description
Technical Field
The invention relates to a preparation method of chitosan/gallnut tannin composite fiber, belonging to the field of bio-based functional fiber.
Background
China is a large country for producing chemical fibers, and excessive dependence of the chemical fibers on petroleum-based chemicals causes large consumption of non-renewable resources such as petroleum and the like, thereby causing problems of resource exhaustion, environmental pollution and the like. The current worldwide petroleum resource can be mined for about 40 years, and the national exploitation period is not more than 30 years. To meet market demands, corresponding alternative resources must be sought. Chitosan is a natural polymer compound and is abundant in shells of shrimps and crabs. The chitosan has good biocompatibility, biodegradability and nontoxicity, and also has good antibacterial performance, and can inhibit the growth of some pathogenic microorganisms (such as escherichia coli and staphylococcus aureus). The biodegradability of the chitosan fiber also helps to prevent the pollution of the waste products to the environment and improve the micro-ecological properties of the soil.
At present, the common preparation method of chitosan fiber is wet spinning.
Chitosan fibers have the greatest drawback of having inferior mechanical properties compared to the commonly used textile fibers, which greatly limits their applications; in addition, the chitosan fiber product with single component has great processing and using difficulty. In addition, the conventional chitosan fiber needs to contact 18 hours to reach the bacteriostatic peak value, and modern medicine requires that the bacteriostatic effect is achieved within 2 hours, so that the time for the chitosan fiber to reach the bacteriostatic peak value is required to be shortened or the chitosan fiber has the bactericidal effect.
In order to improve the mechanical properties and functions of chitosan fibers, Yang Qing et al adopt glyoxal as a crosslinking agent to perform crosslinking treatment on the chitosan fibers so as to improve the fiber strength; under the action of an initiator Ammonium Persulfate (APS), Acrylic Acid (AA) is adopted to graft and modify Chitosan (CS) to prepare a CS-g-AA graft copolymer, the CS-g-AA graft copolymer is spun into fibers through wet spinning, and glutaraldehyde is used to crosslink the fibers to obtain modified CS fibers with better mechanical property; the antibacterial performance of chitosan fibers is improved by using cationic surfactant for finishing by Yankee and the like; the Hexueplum and the like adopt nano SiO2The modification method is used for improving the thermal stability of the chitosan fiber; zhang Ping adopts the method of blending spinning of chitosan and polyvinyl alcohol to improve the spinnability and the knittability of chitosan fiber. However, in these methods, glutaraldehyde crosslinking agent is toxic, and polyvinyl alcohol is difficult to be degradedHowever, it is not environmental friendly.
Disclosure of Invention
With the growing interest in fabric health care, there is growing interest in developing the functionality of natural substances. Natural polyphenol as a plant dye has a long history in China. The natural polyphenol is used for dyeing, so that the defect of toxic substance emission of synthetic dyes can be overcome, and a plurality of natural polyphenols come from Chinese herbal medicines and have various health-care functions, such as antioxidation, antibiosis, antiphlogosis and the like. During the functionalized dyeing process, the natural polyphenols are absorbed, so that the functions are given to the dyeing material. In recent years, plant polyphenols such as tea polyphenols, grape seed extracts and the like and chitosan are blended to prepare composite films so as to improve the mechanical properties and endow certain functionalities. However, film formation and spinning have different requirements for dope, and spinning has a higher requirement for dope. The spinning dope needs to have very good rheological properties, and in addition, the spinning process conditions and the selection of the coagulating bath in the spinning process have great influence on the fiber properties. The membrane is not required to be the original liquid, and the original liquid only needs to have certain fluidity. There is also no document reporting or teaching that these polyphenols can be blended with chitosan and used to prepare chitosan composite fibers using a wet spinning process.
In order to solve the problems, the chitosan/gallnut tannin composite fiber is prepared by taking gallnut tannin as a functional component and adding the gallnut tannin into a chitosan spinning solution. The addition amount of the gallnut tannin is 5 to 15 percent of the mass percent of the chitosan, and wet spinning is carried out. The composite fiber contains the gallnut tannin, has the effects of oxidation resistance, antibiosis, inflammation diminishing and the like, and effectively improves the mechanical strength of the pure chitosan fiber.
The first purpose of the invention is to provide a chitosan composite fiber, which is a chitosan/gallnut tannin composite fiber prepared by blending gallnut tannin and chitosan; wherein the addition amount of the gallnut tannin is 5-15% of the mass of the chitosan.
In one embodiment, the gallnut tannin is added in an amount of 7.5% to 15% (mass percentage of gallnut tannin relative to chitosan).
In one embodiment, the amount of the gallnut tannin added is: 5%, 7.5%, 10%, 12.5%, 15%; the weight percentage of the gallnut tannin relative to the chitosan is respectively.
In one embodiment, the preparation of the composite fiber comprises: fully mixing gallnut tannin with a chitosan solution to prepare a spinning solution; and (3) carrying out wet spinning on the spinning solution, and washing, freezing and drying to obtain the chitosan/gallnut tannin composite fiber.
In one embodiment, the preparation of the spinning dope is specifically: dissolving chitosan in acetic acid solution to obtain chitosan acetic acid solution, and mechanically stirring; the mass concentration of the chitosan in the solution is 3-5%; adding the gallnut tannin into a chitosan acetic acid solution in an amount of 5-15% of the mass of the chitosan, stirring to fully dissolve the gallnut tannin, and uniformly mixing the gallnut tannin with the chitosan; and (3) carrying out ultrasonic treatment on the mixed solution of chitosan and gallnut tannin to remove air bubbles in the solution, thus obtaining the spinning solution.
In one embodiment, the wet spinning is specifically: injecting the spinning solution into a reaction tank of a wet spinning machine, extruding and spinning the spinning solution by a metering pump under the pressure of 0.1-0.3MPa, wherein the spinning temperature is from room temperature to 60 ℃, the number of spinneret holes is 50-200, the aperture is 60-120 mu m, the coagulation bath draft ratio is 0.75-1.05, and the washing draft ratio is 1.1-2.0; the fiber was washed to neutral.
In one embodiment, the coagulation bath: preparing NaOH aqueous solution with the mass concentration of 2-5%, and adding ethanol, wherein the dosage of the ethanol is 25-50% of that of the NaOH aqueous solution.
In one embodiment, the composite fiber obtained by wet spinning is soaked in glycerol aqueous solution for treatment for a period of time, taken out and frozen for 1-2h, and then placed in a freeze dryer for drying to obtain the chitosan/gallnut tannin composite fiber.
In one embodiment, the preparation of the chitosan composite fiber comprises the following specific steps:
the method comprises the following steps: preparing spinning solution
(1) Dissolving chitosan in 2% acetic acid solution at room temperature-40 deg.C for 6-8 hr under mechanical stirring, wherein the mass concentration of chitosan in the solution is 3% -5%;
(2) adding gallnut tannin into chitosan acetic acid solution in an amount of 5% -15% of the mass of chitosan, and mechanically stirring for 20-36h at room temperature-40 ℃ to fully dissolve the gallnut tannin and uniformly mix the gallnut tannin with the chitosan;
(3) performing ultrasonic treatment on the mixed solution of chitosan and gallnut tannin for 15-20min under the condition of ultrasonic wave with the frequency of 20KHz to remove bubbles in the solution to obtain spinning solution; the defoaming treatment is carried out by ultrasonic, so that bubbles contained in the liquid are removed, and the phenomenon that the mechanical property of the nascent fiber is influenced by the fracture of the nascent fiber caused by the existence of the bubbles in the spinning process is prevented.
Step two: preparation of coagulating bath
Preparing a NaOH aqueous solution with the mass concentration of 2% -5%, and adding ethanol, wherein the dosage of the ethanol is 25% -50% of that of the NaOH aqueous solution; and the coagulating bath is used for forming the fibers, and the solvent in the spinning solution is diffused out when the spinning solution passes through the coagulating bath to obtain the nascent precursor.
Step three: chitosan/gallnut tannin composite spinning
Injecting the spinning solution prepared in the first step into a liquid storage tank of a wet spinning machine, extruding and spinning the spinning solution by a metering pump under the pressure of 0.1-0.3MPa, wherein the spinning temperature is room temperature-60 ℃, the number of spinneret holes is 50-200 holes, the aperture is 60-120 mu m, the coagulation bath draft ratio is 0.75-1.05, and the washing draft ratio is 1.1-2.0; washing the fiber to be neutral;
step four: dry fiber
Soaking the washed composite fiber in 1% glycerol water solution for 3-4h, taking out, freezing at-80 deg.C in ultra-low temperature refrigerator for 1-2h, and drying in a freeze drier at-54 deg.C and vacuum degree of 18Pa to obtain chitosan/Galla chinensis tannin composite fiber. Through the freeze-drying step, the fibers prepared by wet spinning are not easy to stick together due to the influence of the water loss speed in the drying process.
In one embodiment, the chitosan is a spinning grade chitosan with a viscosity of 800-.
In one embodiment, the gallotannins are gallnut extracts having a tannin content of 93-98%, and are commercially available, such as gallotannins available from red city, Wufeng Biotech, Inc.
The second object of the present invention is to provide a textile comprising a product prepared using the chitosan/gallotannin composite fiber of the present invention.
In one embodiment, the textile is: any one of yarn, blanket, woven fabric, knitted fabric, thermal insulating wadding, filler, non-woven fabric, medical and sanitary product, special work clothes and the like.
The third purpose of the invention is to provide the application of the chitosan/Chinese gall tannin composite fiber.
In one embodiment, the application is in the fields of clothing and medical health.
In one embodiment, the application is used for preparing health-care clothes and clothes with fluorescence effect, such as: antibacterial underpants, antibacterial bra, health T-shirt, infant clothes, etc.
In one embodiment, the application is used for preparing medical sutures and medical dressings, preparing artificial skin and being used in the aspect of drug slow release.
Has the advantages that:
the chitosan/gallnut tannin composite fiber has good mechanical property and thermal stability, has extremely strong antibacterial action on staphylococcus aureus, has the bacterium reduction rate of 70-99.8 percent, and has strong green and red fluorescence. Based on the fluorescence characteristics of the chitosan/gallnut tannin composite fiber, the chitosan/gallnut tannin composite fiber can be used in the field of clothing, so that the fabric has a fluorescence effect; or used in the field of medical health, and the residual amount of the gallnut tannin can be deduced through the intensity of fluorescence.
In order to improve the mechanical property of the chitosan fiber and endow the chitosan fiber with more functionality, the invention adopts the blending of natural polyphenol gallnut tannin and chitosan to prepare the chitosan/gallnut tannin composite fiber. In a large number of experimental processes, the inventor finds that gallnut tannin can generate physical crosslinking with chitosan molecules, including hydrogen bond action and surface-to-surface affinity action of hydrophobic groups, and the gallnut tannin plays the role of a crosslinking agent, improves the mechanical property of chitosan fibers and endows the chitosan fibers with functionality. Wherein, the following acting forces between the chitosan macromolecules and the gallnut tannin molecules are beneficial to improving the performance of the composite fiber:
(1) a large amount of phenolic hydroxyl groups on the gallnut tannin can form a large amount of hydrogen bonds with the macromolecular amino groups of the chitosan, and the hydrogen bond action is beneficial to improving the mechanical property of the chitosan composite fiber.
(2) Gallnut tannin has a plurality of hydrophobic group benzene rings, and surface affinity effect is generated between the gallnut tannin and hydrophobic group hydrocarbon chains on chitosan, so that the hydrophilicity of chitosan fiber is reduced, and the water-resistant stability of the chitosan fiber is improved.
The chitosan/gallnut tannin composite fiber with the additive amount of 10 percent has the moisture regain of 14.3 percent, the water retention rate of 201.4 percent, the wet breaking strength of 0.6834cN/dtex and the elongation at break of 7.13 percent; the moisture regain of the pure chitosan fiber is 15.1 percent, the water retention rate is 228.6 percent, the wet breaking strength is 0.457cN/dtex, and the elongation at break is 5.2 percent; it is apparent that the chitosan/gallotannin composite fiber of the present invention has improved water resistance stability.
Drawings
FIG. 1: the influence of different addition amounts of the gallnut tannin on the breaking strength of the chitosan/gallnut tannin composite fiber;
FIG. 2: comparing the fluorescence effects of the chitosan/gallnut tannin composite fiber and the pure chitosan fiber; in the figure, the lower layer fiber is pure chitosan fiber; from left to right, the excitation light sources are blue light, green light and ultraviolet light respectively;
FIG. 3: FT-IR chart of chitosan fiber and chitosan/gallnut tannin composite fiber with different additive amount of gallnut tannin;
FIG. 4: TG profile of gallnut tannin, chitosan fiber and chitosan/gallnut tannin composite fiber;
FIG. 5: DTG profiles for gallnut tannins, chitosan fibers and chitosan/gallnut tannins composite fibers.
The specific implementation mode is as follows:
method for measuring breaking strength:
the tensile properties (breaking strength and elongation at break) of the fibers were tested using a single fiber tensile tester (YG004D, second textile instrumentation, japan). The tensile properties of the fibers were measured after conditioning the fibers in a standard atmosphere of 21 ℃ and 65% relative humidity for at least 24 hours. A gauge length of 20mm and a crosshead speed of 20mm/min were used. Tensile properties of at least 100 fibers were tested separately.
The testing method of the wet mechanical property of the fiber comprises the following steps:
referring to the above method for measuring breaking strength, the fiber is soaked in deionized water for one minute before the test.
The detection method of the antibacterial performance comprises the following steps:
according to the AATCC 100-.
The water-resistant stability measuring method comprises the following steps:
(1) water retention:
some of the fibers were immersed in deionized water at ambient temperature for 24 hours, then the fibers were placed in filter centrifuge tubes and centrifuged at 4000 Xg for 10 minutes using a high speed Avanti J-E refrigerated centrifuge (Beckman Coulter, USA). The wet samples were weighed, then dried in an oven at 105 ℃ and cooled in a desiccator. Water retention was then calculated using equation (1).
In the formula: wwf-wet weight of fiber after centrifugation;
Wdf-dry weight of dried fiber.
(2) Moisture regain:
respectively weighing three groups of pure chitosan fiber and chitosan/gallnut tannin composite fiber of about 3g, placing the three groups in a constant temperature and humidity chamber for pre-conditioning to constant weight, and weighing the weight of a sample. Then dried in an oven at 105 ℃ to a constant weight, and after cooling, the dry weight of the sample is weighed. Calculating the moisture regain according to the following formula, and then taking the average value of the three groups to obtain the moisture regain value.
Calculating the formula:
W(％)＝(G-G0)/G0*100
in the formula: w is the moisture regain of the fiber;
g0 — dry weight of fiber;
g is the conditioned weight of the fiber.
The present invention will be described below with reference to the accompanying drawings.
Example 1:
the chitosan gallnut tannin composite fiber is prepared by the following method, which comprises the following steps:
the method comprises the following steps: preparing spinning solution
(1) Dissolving chitosan in 2% acetic acid solution at 25 deg.C for 7 hr under mechanical stirring;
(2) adding gallnut tannin into chitosan acetic acid solution in an amount of 5%, 7.5%, 10%, 12.5% and 15% of the chitosan, respectively, mechanically stirring for 28h at 25 ℃ to fully dissolve the gallnut tannin and uniformly mixing with the chitosan;
(3) carrying out ultrasonic treatment on the chitosan and gallnut tannin mixed solution for 17min under the ultrasonic condition with the frequency of 20KHz to remove bubbles in the solution, so as to obtain a spinning solution;
step two: preparation of coagulating bath
Preparing a NaOH aqueous solution with the mass concentration of 4%, and adding ethanol, wherein the dosage of the ethanol is 38% of that of the NaOH aqueous solution;
step three: chitosan/gallnut tannin composite spinning
Injecting the spinning solution prepared in the first step into a reaction tank of a wet spinning machine, extruding and spinning the spinning solution by a metering pump under the pressure of 0.2MPa, wherein the spinning temperature is 30 ℃, the number of holes of a spinneret plate is 100, the aperture is 880 mu m, the coagulation bath draft ratio is 0.95, and the washing draft ratio is 1.6; washing the fiber to be neutral;
step four: dry fiber
Soaking the washed composite fiber in 1% glycerol water solution for 4h, taking out, freezing at-80 deg.C in ultra-low temperature refrigerator for 1.5h, and drying in a freeze drier at-54 deg.C and vacuum degree of 18Pa to obtain chitosan/Galla chinensis tannin composite fiber (Galla chinensis tannin addition amount is 5%, 7.5%, 10%, 12.5%, 15%).
Comparing the performance of the obtained chitosan/gallnut tannin composite fiber with that of pure chitosan fiber:
(1) mechanical properties
The addition amount of the gallnut tannin is as follows: 0%, 5%, 7.5%, 10%, 12.5%, 15%: the weight percentage of the gallnut tannin relative to the chitosan is respectively.
The results are shown in FIG. 1. The results show that the addition amount of the gallnut tannin is as follows: the breaking strength of the fiber is respectively as follows at 0%, 5%, 7.5%, 10%, 12.5% and 15%: 0.529cN/dtex, 0.657cN/dtex, 0.651cN/dtex, 0.759cN/dtex, 0.688cN/dtex, 0.585 cN/dtex.
When the additive amount of the gallnut tannin is 10 percent, the chitosan/gallnut tannin composite fiber has the maximum breaking strength and better mechanical property, and the breaking strength of the chitosan/gallnut tannin composite fiber is improved by 43.4 percent compared with that of pure chitosan fiber.
(2) Antibacterial property
The addition amount of the gallnut tannin is as follows: the antibacterial properties of the prepared fibers at 0%, 5%, 7.5%, 10%, 12.5%, 15% are shown in table 1.
TABLE 1 antibacterial Properties of pure chitosan fiber and chitosan/Galla chinensis tannin composite fiber
The results show that: compared with the antibacterial capacity of pure chitosan fiber to staphylococcus aureus and candida albicans respectively, the chitosan/gallotannin composite fiber with the additive amount of 10% of gallotannin has greatly improved antibacterial property, especially has extremely strong antibacterial capacity to staphylococcus aureus, and the bacterial reduction rate reaches 99.7%.
(3) Fluorescent properties
As shown in fig. 2, the composite fiber and the pure chitosan fiber are respectively treated by blue light, green light and ultraviolet light (from left to right) of an excitation light source, and the specific treatment is as follows: the three excitation light sources of the user irradiate the fibers respectively, and the fibers are observed through a fluorescence inverted microscope and a fluorescence micrograph is taken.
Fluorescence micrographs of pure chitosan fibers and chitosan/gallotannin composite fibers were taken using an inverted fluorescence microscope Ti-S (Nikon Eclipse inc., Japan) with a high pressure mercury lamp as an excitation source. A filter set of FITC was used for fluorescence measurements. The microscope was combined with Nikon digital Vision DS-Filch. All fluorescence images were taken at room temperature in the dark.
The wavelength ranges for the fluorescence filters are shown in Table 2.
TABLE 2 wavelength ranges of use of the fluorescent filters
The results show that: when the excitation light sources are blue light and green light respectively, the pure chitosan fiber and the chitosan/gallnut tannin composite fiber can respectively generate green fluorescence and red fluorescence, and as can be seen from fig. 2, the intensity of the green fluorescence and the red fluorescence generated by the chitosan/gallnut tannin composite fiber is far higher than that of the pure chitosan fiber (as shown in table 3), which indicates that the gallnut tannin enhances the fluorescence effect of the composite fiber. Meanwhile, when the excitation light source in fig. 2 is ultraviolet light, the fluorescence intensity generated by the chitosan/gallnut composite fiber is obviously lower than that of the pure chitosan fiber, which indicates that the chitosan/gallnut tannin composite fiber absorbs a large amount of ultraviolet light and has an ultraviolet resistant effect (as shown in table 3). The composite fiber has great application potential in the fields of clothing and medical health.
TABLE 3 fluorescence intensity
FIG. 3 is a FT-IR chart of chitosan fibers and chitosan/gallotannin composite fibers with different amounts of gallotannin added; as can be seen in FIG. 3, the chitosan fiber was 3297cm-1Shows a broad absorption peak due to the overlapping of multiple absorption peaks of stretching vibration of O-H and N-H. And 2872cm-1And 1374cm-1Then symmetric and asymmetric stretching vibrations due to C-H. In addition, 1645cm-1The peak corresponds to the absorption peak of the chitosan amide I group (C ═ O) in the range of 1587cm-1The position corresponds to the vibration absorption peak of the amide II group (N-H). In the FTIR spectrum of the chitosan/gallnut tannin composite fiber, the position of the characteristic peak of the carbon chain is basically unchanged, and the overlapping peak of the O-H and N-H stretching vibration multiple absorption of the chitosan is obviously widened and moves to a low wavenumber region and shifts to 3287cm-1Nearby. This phenomenon is mainly attributed to that the hydrogen bonding between the phenolic hydroxyl group of gallnut and the amino group of chitosan lowers the chemical bond force constant of the hydroxyl group participating in the hydrogen bonding, so that the absorption frequency thereof shifts to the low wavenumber direction. In addition, the increase of the absorption peak intensity is attributed to the fact that the hydrogen bond interaction between the gallnut and the chitosan leads to the increase of the change of dipole moment when the hydroxyl group vibrates.
FIG. 4 is a TG curve of gallotannins, chitosan fibers and chitosan/gallotannins composite fibers (gallotannins added in an amount of 10%); as can be seen from FIG. 4, the initial thermal decomposition temperature of Galla chinensis is obviously higher than that of chitosan fiber, and the decomposition temperature of the chitosan/Galla chinensis tannin composite fiber after Galla chinensis is added is increased due to the self characteristics of Galla chinensis, the surface-to-surface affinity of hydrophobic groups with chitosan and the hydrogen bonding effect, so that the thermal decomposition temperature of the composite fiber is increased, and the thermal stability is improved.
FIG. 5 is a DTG graph of Galla chinensis tannin, chitosan fiber and chitosan/Galla chinensis tannin composite fiber (Galla chinensis tannin added amount 10%). As can be seen from FIG. 5, it is clear that at the highest thermal decomposition rate, the temperature corresponding to the chitosan/gallotannin composite fiber is also increased, which indicates that intermolecular interactions do occur between gallotannin molecules and chitosan molecules, and the intermolecular interactions are two kinds, namely, surface-to-surface affinity interactions between benzene rings in gallotannin structure and hydrocarbon chains of chitosan molecular chains, and between two kinds of hydrophobic groups; the other is that hydrogen bonds are generated between a large amount of phenolic hydroxyl groups in the gallnut tannin and chitosan molecules. The two intermolecular interactions jointly improve the thermal stability of the chitosan.
Tables 4 and 5 compare the dry and wet strength, elongation at break, moisture regain and water retention of pure chitosan fibers and chitosan/gallotannin composite fibers with 10% addition of gallotannin.
TABLE 4 comparison of dry and wet strength and elongation at break of pure chitosan fiber and chitosan/gallnut tannin composite fiber
Remarking: the reduction rate is a reduction rate of the wet-state breaking strength or elongation at break relative to the dry state.
TABLE 5 moisture regain and Water Retention of pure Chitosan fiber and Chitosan/Galla chinensis tannin composite fiber
Example 2:
the chitosan gallnut tannin composite fiber is prepared by the following method, which comprises the following steps:
the method comprises the following steps: preparing spinning solution
(1) Dissolving chitosan in an acetic acid solution with the mass concentration of 2%, wherein the mass concentration of the chitosan in the solution is 3%, and the dissolving temperature is room temperature, and mechanically stirring for 8 hours;
(2) adding gallnut tannin into chitosan acetic acid solution with the amount of 10% of the chitosan mass, and mechanically stirring for 36h at room temperature to fully dissolve the gallnut tannin and uniformly mix the gallnut tannin with the chitosan;
(3) carrying out ultrasonic treatment on the chitosan and gallnut tannin mixed solution for 15min under the ultrasonic condition with the frequency of 20KHz to remove bubbles in the solution, so as to obtain a spinning solution;
step two: preparation of coagulating bath
Preparing a NaOH aqueous solution with the mass concentration of 5%, and adding ethanol, wherein the dosage of the ethanol is 50% of that of the NaOH aqueous solution;
step three: chitosan/gallnut tannin composite spinning
Injecting the spinning solution prepared in the first step into a reaction tank of a wet spinning machine, extruding and spinning the spinning solution by a metering pump under the pressure of 0.1-0.3MPa, wherein the spinning temperature is room temperature-60 ℃, the number of spinneret holes is 50-200, the aperture is 60-120 mu m, the coagulation bath draft ratio is 0.75-1.05, and the washing draft ratio is 1.1-2.0; washing the fiber to be neutral;
step four: dry fiber
Soaking the washed composite fiber in 1% glycerol water solution for 3h, taking out, freezing at-80 deg.C in ultra-low temperature refrigerator for 1h, and drying in a freeze drier at-54 deg.C and vacuum degree of 18Pa to obtain chitosan/Galla chinensis tannin composite fiber.
The composite fiber prepared in this example was subjected to a performance test in the same manner as in example 1, and the results showed that: the breaking strength is 0.760cN/dtex, the sterilization capacity to Staphylococcus aureus is 99.8%, and the sterilization capacity to Candida albicans is: 35.2%, the green fluorescence intensity was 222, and the red fluorescence intensity was 254.
Example 3:
the chitosan gallnut tannin composite fiber is prepared by the following method, which comprises the following steps:
the method comprises the following steps: preparing spinning solution
(1) Dissolving chitosan in 2% acetic acid solution at 40 deg.C for 6 hr, wherein the mass concentration of chitosan in the solution is 5%;
(2) adding gallnut tannin into chitosan acetic acid solution at the amount of 10% of the chitosan mass, and mechanically stirring for 20h at 40 ℃ to fully dissolve the gallnut tannin and uniformly mix the gallnut tannin with the chitosan;
(3) carrying out ultrasonic treatment on the chitosan and gallnut tannin mixed solution for 20min under the condition of ultrasonic wave with the frequency of 20KHz to remove bubbles in the solution, so as to obtain spinning solution;
step two: preparation of coagulating bath
Preparing a NaOH aqueous solution with the mass concentration of 2%, and adding ethanol, wherein the dosage of the ethanol is 25% of that of the NaOH aqueous solution;
step three: chitosan/gallnut tannin composite spinning
Injecting the spinning solution prepared in the first step into a reaction tank of a wet spinning machine, extruding and spinning the spinning solution by a metering pump under the pressure of 0.1-0.3MPa, wherein the spinning temperature is room temperature-60 ℃, the number of spinneret holes is 50-200, the aperture is 60-120 mu m, the coagulation bath draft ratio is 0.75-1.05, and the washing draft ratio is 1.1-2.0; washing the fiber to be neutral;
step four: dry fiber
Soaking the washed composite fiber in 1% glycerol water solution for 4h, taking out, freezing at-80 deg.C in ultra-low temperature refrigerator for 2h, and drying in a freeze drier at-54 deg.C and vacuum degree of 18Pa to obtain chitosan/Galla chinensis tannin composite fiber.
The composite fiber prepared in this example was subjected to a performance test in the same manner as in example 1, and the results showed that: the breaking strength is 0.761cN/dtex, the sterilization capability to staphylococcus aureus is 99.7%, and the sterilization capability to candida albicans is as follows: 35.3%, the green fluorescence intensity was 221, and the red fluorescence intensity was 253.
Claims (10)
1. A chitosan composite fiber is characterized in that the chitosan composite fiber is a chitosan/gallnut tannin composite fiber prepared by blending gallnut tannin and chitosan; wherein the addition amount of the gallnut tannin is 5-15% of the mass of the chitosan.
2. The chitosan composite fiber according to claim 1, wherein the amount of the gallnut tannin added is 7.5% -15%.
3. The chitosan composite fiber according to claim 1, wherein the preparation of the composite fiber comprises: fully mixing gallnut tannin with a chitosan solution to prepare a spinning solution; and (3) carrying out wet spinning on the spinning solution, and washing, freezing and drying to obtain the chitosan/gallnut tannin composite fiber.
4. The chitosan composite fiber according to claim 3, wherein the spinning solution is prepared by: dissolving chitosan in acetic acid solution to obtain chitosan acetic acid solution, and mechanically stirring; the mass concentration of the chitosan in the solution is 3-5%; adding the gallnut tannin into a chitosan acetic acid solution in an amount of 5-15% of the mass of the chitosan, stirring to fully dissolve the gallnut tannin, and uniformly mixing the gallnut tannin with the chitosan; and (3) carrying out ultrasonic treatment on the mixed solution of chitosan and gallnut tannin to remove air bubbles in the solution, thus obtaining the spinning solution.
5. The chitosan composite fiber according to claim 3, wherein the wet spinning is specifically: injecting the spinning solution into a reaction tank of a wet spinning machine, extruding and spinning the spinning solution by a metering pump under the pressure of 0.1-0.3MPa, wherein the spinning temperature is from room temperature to 60 ℃, the number of spinneret holes is 50-200, the aperture is 60-120 mu m, the coagulation bath draft ratio is 0.75-1.05, and the washing draft ratio is 1.1-2.0; the fiber was washed to neutral.
6. A textile prepared by using the chitosan/gallotannin composite fiber of claim 1.
7. The textile product of claim 6, wherein the textile product is: any one of yarn, blanket, woven fabric, knitted fabric, thermal insulating wadding, filling material, non-woven fabric, medical and sanitary articles, special work clothes and the like.
8. Use of the chitosan composite fiber of claim 1.
9. Use according to claim 8, characterized in that it is used in the field of clothing or medical hygiene.
10. Use according to claim 8 or 9, for the preparation of garments with health care functions, for the preparation of garments with fluorescent effects, for the preparation of medical sutures, for the preparation of medical dressings, for the preparation of artificial skin, for the preparation of drug release materials, etc.
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