CN114150505A - Antibacterial antigen fibrillated lyocell fiber and preparation method thereof - Google Patents
Antibacterial antigen fibrillated lyocell fiber and preparation method thereof Download PDFInfo
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- 108091007433 antigens Proteins 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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Images
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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
- D06M13/322—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 nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
-
- 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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- 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
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to an antibacterial antigen fibrillated lyocell fiber and a preparation method thereof, wherein the antibacterial antigen fibrillated lyocell fiber comprises the following raw material components in parts by weight: 200 portions of lyocell fiber 100-. The level-dyeing property and dyeing property of the modified lyocell fiber are improved compared with the level-dyeing property and dyeing property of the unmodified lyocell fiber.
Description
Technical Field
The invention belongs to the field of functional lyocell fibers and preparation thereof, and particularly relates to an antibacterial antigen fibrillated lyocell fiber and a preparation method thereof.
Background
The lyocell fiber is a green textile garment fabric, has the characteristics of comfort, good hand feeling, easy dyeing and the like of natural fiber cotton, and also has the environmental protection advantage which is not possessed by the traditional viscose fiber. The lyocell fiber takes reproducible pulp formed by smashing bamboo, wood and the like as raw materials, the lyocell fiber can completely reproduce the natural characteristics of the wood pulp, can be biodegraded even if the fiber is burnt and rotten, and has no waste or by-product; the advanced process enables the solvent recovery rate to reach 99.7 percent, and the method is energy-saving, environment-friendly and sustainable in development. However, lyocell fibers are very prone to fibrillation, which results in fuzzing and pilling of the lyocell fibers, affecting fabric gloss and hand. In addition, the textile is a loose and porous structure, sweat and grease secreted by a human body are easily adhered to the surface of the textile, and the lyocell fiber has good hydrophilicity, so that the lyocell fabric is more likely to become a hotbed for bacterial reproduction and growth. Bacteria multiply on textiles and may cause health hazards to the human body through the skin, respiratory tract, digestive tract, etc. of the human body. Meanwhile, the propagation of a large amount of bacteria and mold can also cause bacterial plaque on the surface of the textile, form black or yellow spots and seriously damage the aesthetic feeling of the textile. Therefore, it is necessary to research the antibacterial antigen fibrillated lyocell fiber.
The lyocell fiber has mercerizing and warm-keeping effects comparable to silk, and has good hydrophilic and skin-friendly properties, so that the lyocell fiber is widely used for high-grade and high-grade bedding, but the fibrillation can lead lyocell fabric to be fluffed and pilling and influence the color and luster of the fiber. And meanwhile, the dyeing property of the lyocell fiber is reduced, and particularly when the lyocell fiber is woven into a deep yarn dyed fabric, a frosty and white appearance with dull luster appears, so that the subsequent processing difficulty becomes great. Therefore, fibrillation of lyocell fibers greatly limits the range of applications of lyocell fibers, and thus it is necessary to perform an antigen fibrillation treatment. However, although the method of improving the production process, polymer blend spinning, alkali treatment, bio-enzyme treatment, high-energy particle treatment, etc. can improve the anti-fibrillation function of the lyocell fabric, the mechanical strength of the fiber is damaged, and the anti-fibrillation effect is not permanent. Therefore, the use of the cross-linking agent method to obtain the permanent fibrillation effect is the best choice at present. The fibrillation of the lyocell fibers is mainly caused by the fact that the lyocell fibers have high degree of orientation and crystallinity, and thus the fibers have few amorphous regions, low force acting on the amorphous regions, poor force acting between fibrils, wet expansion of the fibers under wet conditions, and easy splitting caused by friction or mechanical action. And the crosslinking agent can be connected with hydroxyl on the lyocell fibers, so that the acting force between fibrils is increased, the fibers are not easy to split to generate fibrils, and the wetting expansion ratio of the fibers can be reduced.
In addition, the textile is of a loose and porous structure, sweat and grease secreted by a human body are easily adhered to the surface of the textile, and therefore the textile becomes a hotbed for bacterial reproduction and growth. Bacteria multiply on textiles and may cause health hazards to the human body through the skin, respiratory tract, digestive tract, etc. of the human body. Meanwhile, the propagation of a large amount of bacteria and mold can also cause bacterial plaque on the surface of the textile, form black or yellow spots and seriously damage the aesthetic feeling of the textile. In addition, the microorganisms also produce large amounts of chemicals during rapid propagation, which can produce irritating odor gases and impair the mechanical strength of the fabric. Therefore, an antibacterial fabric capable of resisting microbial reproduction to meet the requirements of human health is a great demand in the textile and clothing industry, especially in the medical textile and sports clothing industry.
The antibacterial fabric is generally woven by antibacterial fibers obtained by finishing with an antibacterial finishing agent or is directly subjected to after-finishing by the antibacterial finishing agent, and the fabric can inhibit or kill microorganisms attached to textiles. The antimicrobial agent used in textiles should meet the following requirements: the antibacterial agent has good antibacterial effect; secondly, the fabric still has good antibacterial ability after being washed for many times; the antibacterial agent does not influence the mechanical strength, color, luster and other physical and chemical properties of the textile; fourthly, the antibacterial agent cannot cause damage to the human body; the antibacterial agent can be used together with other finishing agents, namely other post-finishing processes of the textile are not influenced; the antibacterial agent is preferably low in cost and simple in process.
The quaternary ammonium salt antibacterial finishing agent is considered to be the better antibacterial finishing agent applied at present because of good safety and durability. The quaternary ammonium salt is an amphoteric surfactant, and has an antibacterial effect of absorbing bacteria into internal gaps through electrostatic adsorption to cause wrinkling of bacterial biofilms, and meanwhile, long-chain alkyl groups can also penetrate into the bodies of the bacteria to cause overflowing of cytoplasm to sterilize. Therefore, the antibacterial agent adopting quaternary ammonium salt can endow the fabric with antibacterial performance and meet the requirement of human health.
Chinese patent publication No. CN111893749 adopted C2～C6One or more than two mixtures of dialdehyde compounds are used as a cross-linking agent and a latent acid catalyst to carry out antigen fibrillation treatment on the lyocell fiber, thereby obtaining better anti-fibrillation treatment effect. However, the use of polyaldehyde crosslinking agents can emit irritating toxic formaldehyde gases during processing and use. China's patent publication No. CN1119030A utilizes polyethylene glycol as a cross-linking agent to prepare non-fibrillated lyocell fibers, but the method requires drying the fibers at a high temperature of 170 ℃ for 20min, which not only has a long industrial time and flow, but also causes the strength of the fibers to be reduced by drying at a high temperature. Chinese patent publication No. CN103306136A discloses a process for preparing a mixture of an oligomeric polybasic acid and C2～C6The polybasic acid combination is used as a cross-linking agent to cross-link the lyocell fiber, so that the anti-fibrillation performance of the lyocell fiber is improved. However, fabrics treated with polycarboxylic acids tend to yellow upon heating, affecting the appearance of the fabric. The Chinese patent with publication number CN98801507.2 uses an auxiliary agent with two reactive groups, preferably 2, 4-dichloro-6-hydroxy triazine sodium salt as a cross-linking agent for cross-linking, so as to obtain a good cross-linking effect. Chinese patent publication No. CN110172754 obtains antigen fibrillated lyocell fiber with good durability by treating washed silk with a crosslinking agent having a group capable of forming a covalent bond with a cellulose hydroxyl group, a group capable of self-crosslinking reaction, and a group capable of forming a hydrogen bond with a cellulose hydroxyl group. The Chinese patent with publication number CN110924153A is to immerse wet fiber in the mixed solution of cross-linking agent and assistant, take out the fiber, roll the fiber, and catalyze the fiber with microwave to obtain non-fibrillating fiber. The cross-linking agent is preferably a triazine compound, the auxiliary agent is a basic compound, and the lyocell fiber with better performance indexes such as strength, elongation and the like and better fibrillation resistance is obtained. But the fiber needs to be made by the methodThe microwave catalysis is required, so that the technological process and power consumption of product preparation are increased, the fiber performance is reduced by long-time microwave catalysis, and the fiber is yellow and crisp.
The Chinese patent with publication number CN110331582A discloses a method for preparing super-hydrophilic antibacterial cellulose fiber, which is characterized in that a graft copolymerization method is adopted to carry out super-hydrophilic modification on cellulose fiber, silver ions are reduced into nano silver by a reducing agent and the nano silver is immobilized on the surface of the fiber, so that antibacterial treatment is carried out on the cellulose fiber after graft modification, and the super-hydrophilic antibacterial cellulose fiber is prepared. However, the nano silver adopted by the method is forbidden to be used in textiles in the United states at present, and the durability of the antibacterial treatment performed by the method is poor. The Chinese patent with publication number CN111778713A is that the proportion of amorphous area of fiber is increased by soda boiling of cellulose, so that the antibacterial agent can enter the amorphous area of cellulose fiber more easily, and the used antibacterial agent is mainly metal ion. However, the antibacterial cellulose obtained by the method is difficult to persist. The Chinese patent with publication number CN109983172A is to treat regenerated cellulose with quaternary ammonium salt and dry to obtain antibacterial cellulose fiber, but the antibacterial performance of the antibacterial fiber obtained by an impregnation method cannot be durable and cannot be washed.
CN 112281483A discloses a method for preparing anti-fibrillation cellulose fiber of a quick cross-linking agent of cellulose fiber, which mainly comprises the following steps of carrying out antigen fiber treatment on lyocell fiber: and (3) spraying the cut lyocell fibers paved into a blanket by using a cross-linking agent solution, then heating the treated fibers by using microwave, heating the fibers by using steam, and finally washing and drying the fibers to obtain the antigen fibrillated lyocell fibers. However, this technique has some drawbacks: the method uses the lyocell fiber which is cut and paved into a blanket, the method needs to cut the lyocell filament and pave the blanket for crosslinking, and the production continuity is poor. Secondly, the antigen fibrillated lyocell fibers obtained by spraying the lyocell blanket have inconsistent infiltration degree and poor product stability. The invention adopts the dipping mode to produce the antigen fibrillated lyocell fiber, which can not only carry out the antibacterial antigen fibrillation treatment before the filament production winding process, thereby improving the production continuity; and the fibrillation performance of the lyocell antibacterial antigen obtained by impregnation is more stable, and the consistency of the product is good.
Disclosure of Invention
The invention aims to solve the technical problem of providing an antibacterial antigen fibrillated lyocell fiber and a preparation method thereof, overcoming the defects of the prior art that firstly, the antibacterial and antigen fibrillated treatment can not be finished synchronously, the original production method needs to be carried out separately, the production flow of products is increased, and the production speed is reduced. Secondly, the defect that the original process method needs to cut the lyocell filaments and then spread the lyocell filaments into a blanket for cross-linking, and the production continuity is poor is overcome. Thirdly, the problem that the original production method adopts the mode of spraying the lyocell blanket to obtain the antigen fibrillated lyocell fiber which has poor product stability due to inconsistent infiltration degree is overcome.
The invention relates to an antibacterial antigen fibrillation fiber which comprises the following raw material components in parts by weight: 200 portions of lyocell fiber 100-.
The cross-linking agent is a hydroxyl cross-linking agent; the long carbon chain alkyl tertiary amine is
Wherein n is 10 to 18.
The cross-linking agent is one or more of a multi-oxazine cross-linking agent and an aziridine cross-linking agent.
The length of the long carbon chain containing the alkanol carbon chain is 3-10.
The invention discloses a preparation method of antibacterial antigen fibrillated fibers, which comprises the following steps:
(1) mixing long-carbon-chain alkyl tertiary amine, long-carbon-chain alkanol and ethanol, and performing reflux reaction to obtain an antibacterial agent;
(2) adding the lyocell fibers and the cross-linking agent into an alkaline aqueous solution, reacting for 3-10 minutes at 65-80 ℃, adding the antibacterial agent, continuing to react for 3-10 minutes, taking out the fibers, and drying to obtain the antibacterial antigen fibrillated fibers.
The reflux reaction in the step (1) is specifically as follows: introducing nitrogen for 15min at 65-80 ℃, and then carrying out condensation reflux reaction for 15-25 h.
And (3) the pH value of the alkaline aqueous solution in the step (2) is 9-13.
The preparation of the alkaline aqueous solution in the step (2) adopts one or more of sodium hydroxide, potassium hydroxide, alkaline metal salt and metal oxide.
And (3) drying at 50-70 ℃ in the step (2).
The content of the cross-linking agent in the step (2) is 1-10 wt%.
The concentration of the antibacterial agent in the step (2) is preferably 0.2-1.0 g/L.
The application of the antibacterial antigen fibrillated fiber provided by the invention is that the lyocell fiber has smooth hand feeling, silky luster and heat preservation performance comparable to wool. Therefore, the lyocell fiber has wide market prospect, can be used as high-grade women's clothing, underwear, bedding and the like, but is easy to fibrillate, so that the lyocell fiber is restricted in the aspects of wear resistance and printing and dyeing, meanwhile, the textile is of a loose and porous structure, sweat and grease secreted by a human body are very easy to adhere to the surface of the textile, and the textile becomes a hotbed for bacterial reproduction and growth. Bacteria multiply on textiles and may cause health hazards to the human body through the skin, respiratory tract, digestive tract, etc. of the human body. Therefore, it is necessary to impart antibacterial fibrillation resistance to lyocell fibers with high efficiency and long duration.
According to the invention, the hydroxyl-containing quaternary ammonium salt antibacterial agent is prepared by adopting the long-carbon-chain alkyl tertiary amine and the long-carbon-chain alkanol chloride, then the hydroxyl crosslinking agent and the lyocell fiber are reacted for 3-10 minutes under an alkaline condition, and then the hydroxyl-containing antibacterial agent is added, so that the antibacterial agent can be grafted on the lyocell fiber through the crosslinking agent, and meanwhile, the hydroxyl on the macromolecular chain of the lyocell fiber can be crosslinked to obtain an antigen fibrillation effect, so that the safe, efficient and durable antibacterial antigen fibrillated lyocell fiber is obtained, and the leveling property and dyeing property of the modified lyocell fiber are improved compared with those of unmodified lyocell fiber.
Advantageous effects
(1) The antibacterial antigen fibrillated lyocell prepared by the invention has high and durable antibacterial effect and outstanding antigen fibrillated effect.
(2) The antibacterial antigen fibrillated lyocell fiber prepared by the invention has the advantages of mild reaction conditions, short process flow, low energy consumption and easy production and use.
(3) The antibacterial agent adopted by the antibacterial antigen fibrillated lyocell fiber prepared by the invention is safe, nontoxic and good in compatibility with human bodies.
(4) The level-dyeing property of the antibacterial antigen fibrillated lyocell fiber prepared by the invention is obviously improved.
(5) Macromolecular chains in the lyocell fibers prepared by the method reduce fibrillation tendency through chemical bond crosslinking, and meanwhile, the antibacterial agent is grafted on the lyocell fibers through chemical bonds to provide excellent and durable antibacterial performance for the lyocell fibers. The preparation method of the antibacterial antigen fibrillated lyocell fiber has the advantages of mild conditions, short process flow, easy industrial production, low energy consumption and no pollution, and the obtained antibacterial antigen fibrillated lyocell fiber has good biocompatibility and no toxic or harmful effect on human bodies.
Drawings
FIG. 1 is a diagram showing the preparation of quaternary ammonium alcohol;
FIG. 2 is a schematic diagram of the preparation of an antibacterial antigen fibrillated lyocell fiber.
FIG. 3 shows FT-IR spectra of DAM12, QAS10-OH, QAS12-OH, QAS 16-OH;
FIG. 4 is a QAS12-1H-NMR spectrum of OH;
FIG. 5 is a TOF-MS spectrum of QAS 12-OH.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
(1) Raw materials
| Name of medicine | Purity of | Manufacturer of the product |
| Anhydrous ethanol | 99.7％ | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| N, N-dimethyldecylamine | 95％ | Shanghai Mairuier Chemical Technology Co., Ltd. |
| Dodecyl dimethyl Tertiary amine | 97％ | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Hexadecyl dimethyl tertiary amine | 98％ | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Acetone (II) | 99％ | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| 3-chloro-1-propanol | 99.5％ | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Ethyl acetate | 99.5％ | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Anhydrous diethyl ether | 99.5％ | SHANGHAI TITAN TECHNOLOGY Co.,Ltd. |
| Nutrient agar culture medium | —— | Hangzhou microbial agents Co Ltd |
| Nutrient broth culture medium | —— | Hangzhou microbial agents Co Ltd |
| Escherichia coli | ATCC 8099 | Nanjing feces inspection Biotechnology Ltd |
| Staphylococcus aureus | ATCC 6538 | Nanjing feces inspection Biotechnology Ltd |
(2) Correlation test standards and methods
The antibacterial method adopted is mainly based on GB/T20944.3-2008 and is slightly changed. The method comprises the following specific steps: preparing bacterial liquid and agar culture medium according to standard method, diluting cultured bacteria to 3-4 × 105CFU/mL. 0.75g of modified and unmodified fibers was added to the Erlenmeyer flask, and 70mg of PBS buffer was added to the Erlenmeyer flask, followed by 5mL of diluted bacterial cultureThe cells were incubated for 24 hours in a constant temperature shaker. And then continuously diluting the bacterial liquid in the conical flask for 7 times, wherein the dilution multiple of each time is 10, then sucking 1mL of bacterial liquid from the bacterial liquid diluted each time, adding the bacterial liquid into an agar culture dish, adding 15mL of agar, shaking up, and putting the bacterial liquid into a biological incubator for culturing for 18-24 hours after the bacterial liquid is solidified. Colonies on the agar plate were then counted and the antibacterial performance was calculated.
The dyeing method comprises placing 1g fiber into 80mL deionized water, adding 8mg dye, placing in a constant temperature shaking water bath at 70 deg.C and shaking frequency of 150min-1Adding 1.6g NaCl (20g/L) into the dye solution after the temperature is kept for 15min, and continuing adding 1.2g Na into the dye solutions of methyl orange, acid light yellow and methylene blue after the temperature is kept for 15min2CO3(15g/L) but no Na is added to the cationic brilliant red2CO3Then, the temperature is kept for 40 min. In the dyeing process, 1mL of dye is respectively sucked at 0min, 10min, 20min, 40min, 55min and 70min, and the dye-uptake rate are characterized by an ultraviolet spectrophotometer. And (3) washing and drying the dyed fiber, testing the K/S value of the fiber by a color transmission spectrocolorimeter, testing 10 times of different places and taking the average value as a result, and taking the standard deviation of the K/S value as the evaluation effect of the levelling property. Wherein the dye uptake is calculated according to the following formula:
I0is the absorbance of the dye stock solution;
Iais the absorbance of the dye raffinate;
n0is the dilution multiple of the dye stock solution;
nais the dilution multiple of the dye residual liquid.
The used experimental method of the fibrillation of the antigen is a wet friction method specified in appendix A of FZ/T52019-2018, and the specific steps are as follows: placing the fiber on a motor for wet friction, wherein the diameter of the motor shaft is 1cm, sleeving a seamless plain cloth sleeve on the motor shaft, testing the included angle of the fiber and the motor shaft to be 45 degrees, the pre-tension of the fiber is 0.1cN, dripping water on the cloth sleeve every 30s to keep the cloth sleeve wet, recording the time of the fiber in the motor for friction, calculating the wet friction times of the lyocell fiber through the warp and weft density and the diameter of the cloth sleeve and the rotating speed of the motor shaft, and measuring the antigen fibrillation performance of the fiber.
Performance test criteria and methods for breaking strength and elongation at break:
the mechanical properties of the fibers were measured using a single fiber strength tester according to GB/T14337-2008 and FZ/T98009 and 2011 to compare the changes in mechanical properties after modification of the fibers. The fiber holding distance was 20mm, the drawing speed was 20mm/min, and the additional tension was 0.1 cN.
Example 1
(1) Adding 10g of hexadecyl dimethyl tertiary amine and 10g of 3-chloro-1-propanol into 50mL of ethanol solution, carrying out reflux reaction at 80 ℃ for 20h, evaporating the solvent after the reaction is finished, then precipitating with ethyl acetate, and drying to obtain the antibacterial monomer.
(2) Putting 1g of cellulose into 100mL of a cross-linking agent solution, wherein the pH value of the cross-linking agent solution is 11 and the concentration of the cross-linking agent solution is 10g/L, reacting at 75 ℃ for 3min, adding 40mg of an antibacterial agent, reacting at 75 ℃ for 3min, cleaning and drying the fiber, and thus obtaining the antibacterial antigen fibrillated lyocell fiber.
Test results show that the antibacterial performance of the antibacterial antigen fibrillated lyocell fiber which adopts the hexadecyl dimethyl tertiary amine as the raw material to escherichia coli and staphylococcus aureus can reach 99.08 percent and 99.75 percent respectively, and the antibacterial efficiency can still be kept above 95 percent after 5 times of washing. In addition, compared with unmodified fiber, the wet friction frequency of the modified lyocell fiber is increased by 10.2 times, the breaking strength and breaking strength are reduced by about 10.7%, the breaking elongation is reduced by 3.4%, and the tensile strength and breaking elongation are slightly reduced, so that the antibacterial antigen fibrillated lyocell fiber with good performance is obtained.
Example 2
(1) 10g of hexadecyl dimethyl tertiary amine and 10g of 3-chloro-1-propanol were added to 50mL of an ethanol solution, and the mixture was refluxed at 80 ℃ for 20 hours without evaporating the solvent after the completion of the reaction, at which the concentration of the antibacterial agent was about 20% by weight.
(2) Putting 1g of cellulose into 100mL of a cross-linking agent solution, wherein the pH value of the cross-linking agent solution is 11 and the concentration of the cross-linking agent solution is 10g/L, reacting at 75 ℃ for 3min, adding 200mg of an antibacterial agent solution, reacting at 75 ℃ for 3min, cleaning and drying the fiber, and thus obtaining the antibacterial antigen fibrillated lyocell fiber.
The method is mainly used for reducing the process flow of preparing the antibacterial antigen fibrillated lyocell fiber. The test result of the method shows that the antibacterial performance of the antibacterial antigen fibrillated lyocell fiber which adopts the hexadecyl dimethyl tertiary amine as the raw material to escherichia coli and staphylococcus aureus can reach 98.69 percent and 99.21 percent respectively, and the antibacterial efficiency can still be kept above 95 percent after 5 times of washing. In addition, compared with unmodified fiber, the wet friction frequency of the modified lyocell fiber is improved by 9.7 times, the breaking strength and breaking strength are reduced by about 9.2%, the breaking elongation is reduced by 2.6%, and the tensile strength and breaking elongation are slightly reduced, so that the antibacterial antigen fibrillated lyocell fiber with good performance is obtained.
Example 3
(1) Adding 10g of dodecyl dimethyl tertiary amine and 10g of 3-chloro-1-propanol into 50mL of ethanol solution, carrying out reflux reaction at 80 ℃ for 20h, evaporating the solvent after the reaction is finished, then precipitating with ethyl acetate, and drying to obtain the antibacterial monomer.
(2) Putting 1g of cellulose into 100mL of a cross-linking agent solution, wherein the pH value of the cross-linking agent solution is 11 and the concentration of the cross-linking agent solution is 10g/L, reacting at 75 ℃ for 3min, adding 40mg of an antibacterial agent, reacting at 75 ℃ for 3min, cleaning and drying the fiber, and thus obtaining the antibacterial antigen fibrillated lyocell fiber.
Test results show that the antibacterial performance of the antibacterial antigen fibrillated lyocell fiber taking the dodecyl dimethyl tertiary amine as the raw material to escherichia coli and staphylococcus aureus can reach 97.54% and 98.43% respectively, and the antibacterial efficiency can still be kept above 95% after 5 times of washing. In addition, compared with unmodified fiber, the wet friction frequency of the modified lyocell fiber is increased by 10.4 times, the breaking strength and breaking strength are reduced by about 11.4%, the breaking elongation is reduced by 3.7%, and the tensile strength and breaking elongation are slightly reduced, so that the antibacterial antigen fibrillated lyocell fiber with good performance is obtained.
Further, as shown in FIG. 3, dodecyl dimethyl tertiary amine (DMA12), QAS10-OH、QAS12-OH、QAS16Fourier Infrared Spectrum of-OH from which QAS can be seen10-OH、QAS12-OH、QAS16the-OH content is 3270-3300 cm compared with that of dodecyl dimethyl tertiary amine-1Has a stretching vibration peak of hydroxyl, and QAS10-OH、QAS12-OH、QAS16OH at 1050cm-1It also has a sharp and narrow peak, which is the C-O stretching vibration peak in primary alcohols.
1H NMR test results
From FIG. 4, it can be seen that the chemical shift δ is 4.8 and D2Solvent peak of O, H atom in terminal hydroxyl group as active hydrogen, in D2O reagent cannot be characterized, and the number ratio of the rest H atoms is1The peak area ratios in the H NMR spectrum are basically consistent, which proves that QAS12-OH was successfully synthesized.
TOF-MS mass spectrometry as shown in FIG. 5.
From the time-of-flight mass spectra it can be seen that the mass-to-charge ratio (m/z) of the sample is predominantly 272.2972 and 273.3002. QAS with quaternary ammonium alcohol of test sample12The theoretical m/z ratio of-OH can be considered consistent, thus 272.2972 and 273.3002 are both cationic moiety relative molecular masses. The mass spectrometry results demonstrate QAS12-OH is synthesized, and the purity of the-OH is high after recrystallization.
Example 4
(1) Adding 10g of hexadecyl dimethyl tertiary amine and 10g of 3-chloro-1-propanol into 50mL of ethanol solution, carrying out reflux reaction at 80 ℃ for 20h, evaporating the solvent after the reaction is finished, then precipitating with ethyl acetate, and drying to obtain the antibacterial monomer.
(2) Putting 1g of cellulose into 100mL of a cross-linking agent solution, wherein the pH value of the cross-linking agent solution is 11, the concentration of the cross-linking agent solution is 18g/L, reacting at 75 ℃ for 3min, adding 40mg of an antibacterial agent, reacting at 75 ℃ for 3min, cleaning and drying the fiber, and thus obtaining the antibacterial antigen fibrillated lyocell fiber.
Test results show that the antibacterial performance of the antibacterial antigen fibrillated lyocell fiber which adopts the hexadecyl dimethyl tertiary amine as the raw material to escherichia coli and staphylococcus aureus can reach 99.54 percent and 99.93 percent respectively, and the antibacterial efficiency can still be kept above 95 percent after 5 times of washing. In addition, compared with unmodified fiber, the wet friction frequency of the modified lyocell fiber is increased by 15.4 times, the breaking strength and breaking strength are reduced by about 15.6%, the breaking elongation is reduced by 3.8%, and the tensile strength and breaking elongation are slightly reduced, so that the antibacterial antigen fibrillated lyocell fiber with good performance is obtained.
Example 5
(1) Adding 10g of hexadecyl dimethyl tertiary amine and 10g of 3-chloro-1-propanol into 50mL of ethanol solution, carrying out reflux reaction at 80 ℃ for 20h, evaporating the solvent after the reaction is finished, then precipitating with ethyl acetate, and drying to obtain the antibacterial monomer.
(2) Putting 1g of cellulose into 100mL of a cross-linking agent solution, wherein the pH value of the cross-linking agent solution is 11, the concentration of the cross-linking agent solution is 18g/L, reacting at 75 ℃ for 3min, adding 20mg of an antibacterial agent, reacting at 75 ℃ for 3min, cleaning and drying the fiber, and thus obtaining the antibacterial antigen fibrillated lyocell fiber.
Test results show that the antibacterial performance of the antibacterial antigen fibrillated lyocell fiber taking the hexadecyl dimethyl tertiary amine as the raw material on escherichia coli and staphylococcus aureus can reach 75.7% and 68.3% respectively, the wet friction frequency of the modified lyocell fiber is improved by 10.6 times compared with that of unmodified fiber, the breaking strength and breaking strength of the modified lyocell fiber are reduced by 11.6%, the breaking elongation of the modified lyocell fiber is reduced by 3.5%, and the modified lyocell fiber is slightly reduced, so that the antibacterial antigen fibrillated lyocell fiber with good performance is obtained.
TABLE 1 mechanical Properties and results of the antigen fibrillation test
Example 6
(1) Adding 10g of dodecyl dimethyl tertiary amine and 10g of 3-chloro-1-propanol into 50mL of ethanol solution, carrying out reflux reaction at 80 ℃ for 20h, evaporating the solvent after the reaction is finished, then precipitating with ethyl acetate, and drying to obtain the antibacterial monomer.
(2) Putting 1g of cellulose into 100mL of a cross-linking agent solution, wherein the pH value of the cross-linking agent solution is 11 and the concentration of the cross-linking agent solution is 10g/L, reacting at 80 ℃ for 3min, adding 40mg of an antibacterial agent, reacting at 80 ℃ for 3min, cleaning and drying the fiber, and thus obtaining the antibacterial antigen fibrillated lyocell fiber.
(3) The obtained antibacterial antigen fibrillated lyocell fiber and unmodified lyocell fiber are dyed by 0.8% o.w.f acid bright yellow dye, and the dye uptake, K/S values before and after modification and level-dyeing property of the dye are represented.
The results show that the dye uptake of the acid light yellow dye on the lyocell fibers before and after modification is respectively 17.5% and 70.5%, the K/S value of the unmodified lyocell fibers after dyeing is 0.39, the standard deviation is 0.15, and the K/S value of the antibacterial antigen fibrillated lyocell fibers is 1.12, the standard deviation is 0.02. This shows that the modified lyocell fiber has better anionic dye adsorption effect than the original fiber, and the dyeing effect and level-dyeing property are improved. Fibrils appear on the surface of the unmodified lyocell fiber, so that after dyeing, the diffuse reflection is increased, the luster is dull, and the dyeing is uneven. But the fibril degree is reduced, the diffuse reflection is reduced, the level-dyeing property is increased and the chroma is improved after the fiber is subjected to the fibrillation modification by the antibacterial antigen. Meanwhile, the dyeing rate and the dyeing depth of the modified lyocell are improved by modification of the cations, and the dyeing performance of the modified lyocell is greatly improved by the synergistic effect of the two.
Example 7
(1) Adding 10g of dodecyl dimethyl tertiary amine and 10g of 3-chloro-1-propanol into 50mL of ethanol solution, carrying out reflux reaction at 80 ℃ for 20h, evaporating the solvent after the reaction is finished, then precipitating with ethyl acetate, and drying to obtain the antibacterial monomer.
(2) Putting 1g of cellulose into 100mL of a cross-linking agent solution, wherein the pH value of the cross-linking agent solution is 11 and the concentration of the cross-linking agent solution is 10g/L, reacting at 80 ℃ for 3min, adding 40mg of an antibacterial agent, reacting at 80 ℃ for 3min, cleaning and drying the fiber, and thus obtaining the antibacterial antigen fibrillated lyocell fiber.
(3) The obtained antibacterial antigen fibrillated lyocell fiber and unmodified lyocell fiber are dyed by 0.8% o.w.f methyl orange dye, and the dye uptake, K/S values before and after modification and level-dyeing property of the dye are represented.
The results showed that the dye uptake of methyl orange dye to lyocell fibers before and after modification was 51.3% and 56.8%, respectively, the K/S value of unmodified lyocell fiber after dyeing was 0.44 with a standard deviation of 0.13, and the K/S value of antibacterial antigen fibrillated lyocell fiber was 4.02 with a standard deviation of 0.01. This shows that the modified lyocell fiber has better anionic dye adsorption effect than the original fiber, and the dyeing effect and level-dyeing property are improved.
Example 8
(1) Adding 10g of dodecyl dimethyl tertiary amine and 10g of 3-chloro-1-propanol into 50mL of ethanol solution, carrying out reflux reaction at 80 ℃ for 20h, evaporating the solvent after the reaction is finished, then precipitating with ethyl acetate, and drying to obtain the antibacterial monomer.
(2) Putting 1g of cellulose into 100mL of a cross-linking agent solution, wherein the pH value of the cross-linking agent solution is 11 and the concentration of the cross-linking agent solution is 10g/L, reacting at 80 ℃ for 3min, adding 40mg of an antibacterial agent, reacting at 80 ℃ for 3min, cleaning and drying the fiber, and thus obtaining the antibacterial antigen fibrillated lyocell fiber.
(3) The obtained antibacterial antigen fibrillated lyocell fiber and unmodified lyocell fiber are dyed by methylene blue dye of 0.8% o.w.f, and the dye uptake, K/S values before and after modification and level-dyeing property of the dye are represented.
The results showed that the uptake of the methylene blue dye to the lyocell fibers before and after modification was 93.6% and 94.0%, respectively, the K/S value of the unmodified lyocell fiber after dyeing was 0.98 with a standard deviation of 0.11, and the K/S value of the antibacterial antigen fibrillated lyocell fiber was 1.02 with a standard deviation of 0.02. This shows that the modified lyocell fiber has no obvious inhibition effect on the adsorption of cationic dye and no obvious change in dyeing depth, but has greatly improved level-dyeing property, compared with the original fiber.
Claims (10)
1. The antibacterial anti-fibrillation fiber is characterized by comprising the following raw materials in parts by weight: 200 portions of lyocell fiber 100-.
2. The fiber of claim 1, wherein the crosslinking agent is a hydroxyl crosslinking agent; the long carbon chain alkyl tertiary amine is
Wherein n is 10 to 36.
3. The fiber of claim 2, wherein the crosslinking agent is one or more of a multi-oxazine crosslinking agent and an aziridine crosslinking agent.
4. The fiber of claim 1, wherein the long carbon chain of the chloroalkanol-containing carbon chain has a length of 3 to 10.
5. A method for preparing antibacterial anti-fibrillation fibers comprises the following steps:
(1) mixing long-carbon-chain alkyl tertiary amine, long-carbon-chain alkanol and ethanol, and performing reflux reaction to obtain an antibacterial agent;
(2) adding the lyocell fibers and the cross-linking agent into an alkaline aqueous solution, then reacting for 3-10 minutes at 65-80 ℃, then adding the antibacterial agent, continuing to react for 3-10 minutes, taking out the fibers, steaming and drying to obtain the antibacterial antigen fibrillated fibers.
6. The preparation method according to claim 5, wherein the reflux reaction in the step (1) is specifically: introducing nitrogen for 15min at 65-80 ℃, and then carrying out condensation reflux reaction for 15-25 h.
7. The method according to claim 5, wherein the pH of the aqueous alkaline solution in the step (2) is 9 to 13.
8. The preparation method according to claim 5, wherein the alkaline aqueous solution in the step (2) is prepared from one or more of sodium hydroxide, potassium hydroxide, alkaline metal salts and metal oxides.
9. The preparation method according to claim 5, wherein the steaming in the step (2) is performed at 90-110 ℃ for 3-10 min; the drying is carried out at 50-70 ℃.
10. Use of the antibacterial antifibrillation fiber of claim 1.
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