CN116695424A - Graphene oxide/nano carboxyl chitosan in-situ grafted fabric and preparation method thereof - Google Patents
Graphene oxide/nano carboxyl chitosan in-situ grafted fabric and preparation method thereof Download PDFInfo
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- 239000004744 fabric Substances 0.000 title claims abstract description 252
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 197
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 188
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 184
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000002608 ionic liquid Substances 0.000 claims abstract description 55
- TVEOIQKGZSIMNG-UHFFFAOYSA-N hydron;1-methyl-1h-imidazol-1-ium;sulfate Chemical compound OS([O-])(=O)=O.C[NH+]1C=CN=C1 TVEOIQKGZSIMNG-UHFFFAOYSA-N 0.000 claims abstract description 35
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- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 claims abstract description 5
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 2
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- 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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
- D06M10/10—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a graphene oxide/nano carboxyl chitosan in-situ grafted fabric and a preparation method thereof, wherein graphene oxide is dissolved in N-methylimidazole bisulfate ionic liquid ([ Hmim)]HSO 4 ) And then carrying out in-situ grafting reaction on the graphene oxide/nano carboxyl chitosan composite and a fabric in N-methylimidazole bisulfate ionic liquid by microwave radiation to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted fabric. The preparation method has the advantages of simple preparation flow, controllable reaction conditions, high in-situ grafting reaction rate, no use of chemical cross-linking agent and auxiliary agent, and the prepared modified fabric has antibacterial activityThe ultraviolet-proof and crease-resistant performances are obviously enhanced, the functional durability is good, the environment is protected, and the market prospect is wide.
Description
Technical Field
The invention relates to a preparation method of graphene oxide/nano carboxyl chitosan in-situ grafted fabric, and belongs to the technical field of functional finishing of textiles.
Background
In 2004, geim prepared graphene by mechanical exfoliation method, which has excellent electrical conductivity, thermal conductivity, mechanical properties and excellent electron mobility. As an ideal reinforcing agent for polymer materials, graphene is widely used for functional and reinforcing phases in composite materials. In recent years, a large number of graphene and derivatives thereof have been reported to be composited with a polymer matrix at home and abroad, and currently, polymer matrix materials commonly used at present include Polystyrene (PS), polyaniline (PANI), polyvinyl alcohol (PVA) and the like. The graphene is doped into the polymer fiber material to improve the tensile strength, impact toughness and thermal stability of the polymer fiber material. Graphene oxide is used as one of the derivatives of graphene, has excellent physical and chemical properties of graphene, contains a large number of oxygen-containing functional groups such as carboxyl, hydroxyl, carbonyl, epoxy groups and the like on the surface, and has good dispersibility and chemical reactivity. The unique structure and excellent performance of the graphene oxide have become the focus of research, and are widely applied to the fields of supercapacitors, sensing, biomedicine and the like. With the continuous research on graphene-based materials in recent years, application of graphene materials to textiles is also continuously explored. The research shows that the graphene material is applied to the textile fabric, and can endow the fabric with antistatic, antibacterial, anti-ultraviolet, sensing, anti-elastic performance and other performances [ Ren Yulan, song Hang, jiang Zhaoyu, and the like ], the graphene performance and the research progress, the university of Paeonia suffruticosa, and 2017 (3): 43-46]. These properties make graphene materials a research hotspot in the textile field, and are expected to develop more deeply in textiles.
Chitosan is widely found in nature and is obtained by deacetylation of chitin. Chitin is a natural polysaccharide with the content inferior to that of cellulose as a raw material of chitosan. Chitosan has good antibacterial properties and is harmless to the human body, and many researchers have used this property to modify fabrics. Chitosan has regular molecular chains and good crystallization performance due to strong hydrogen bonding in and between molecules, but also causes that chitosan is difficult to dissolve in water, alkali or organic solution and can only be dissolved in acid. Most of the acid solutions have extremely high volatility and high corrosiveness, thereby inhibiting the related application of chitosan. In addition, chitosan has a large molecular weight, and a layer of film is formed on the surface after the fabric is coated, so that the hand feeling is affected, the air permeability of the fabric is deteriorated, and the wearing is uncomfortable. In recent years, the development of nano materials expands the application range of chitosan. The nanometer chitosan has smaller particle size, obviously improved adsorption capacity and chemical reactivity, is easier to attach on the surface of the fabric, and the nanometer size can enable the nanometer chitosan to enter the inside of the fabric to realize functional filling without affecting the excellent wearability of the fabric.
At present, many researches report the preparation of graphene oxide and chitosan composite materials. Chen Shuhua and the like using graphene oxide and chitosan dispersed in DMF at N 2 After reaction in atmosphere, preparing GO-g-CS [ Chen Shuhua, armillariella tabescens, sun Tingting ] preparation of chitosan/chitosan grafted graphene oxide composite aerogel and performance study [ J ]]Chinese plastic, 2022,36 (9): 32-37]. Preparation of graphene composite Material by N-hydroxysuccinimide (NHS) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) as crosslinking agent for Shignjuan (Shignjuan, zhang Wen, yao Yuan, etc.. Graphene oxide-chitosan composite Material adsorbs pesticide in Water body [ J ]]Instructions from the university of Hebei science and technology, 2022,36 (2): 54-62]. The invention patent CN114213718A discloses a preparation method of oxidized chitosan-graphene oxide, which uses a cross-linking agent of 1-ethyl- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and a catalyst of N-hydroxysuccinimide to prepare a composite material. Above mentionedThe preparation steps of the graphene oxide/chitosan composite material are complex, the product yield is low, the cost is high, a large amount of catalysts and cross-linking agents are used, part of the materials have toxic effects on human bodies and the environment, environmental pollution exists, and meanwhile, the composite material lacks chemical cross-linking, has poor stability and is limited in application.
The invention drops the nano carboxyl chitosan dispersion liquid to the [ Hmim ] of the graphene oxide under the action of ultrasonic wave]HSO 4 In the ionic liquid solution, carboxyl and hydroxyl on the graphene oxide sheet layer and amino and aldehyde groups of the nano carboxyl chitosan respectively form amide bonds, hemi-acetal bonds and the like through an acidic ionic liquid catalytic reaction to obtain the graphene oxide/nano carboxyl chitosan compound. The prepared composite material has the advantages of good stability, high reaction activity, large specific surface area, capability of directly carrying out grafting reaction with cellulose or protein fiber fabrics, capability of obtaining textiles with multiple functions of antibiosis, ultraviolet resistance, antistatic, wrinkle resistance and the like, good affinity for human bodies, environmental friendliness, wide market prospect, strong stability, high catalytic reaction activity and easiness in recycling, and the ionic liquid is used as a solvent and a reaction medium.
Disclosure of Invention
The invention aims to provide a preparation method of graphene oxide/nano carboxyl chitosan in-situ grafted fabric, which is used for improving the comprehensive properties of ultraviolet resistance, antibacterial property, softness, moisture absorption, ventilation, wearing comfort, human body affinity and the like of the fabric.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the graphene oxide/nano carboxyl chitosan in-situ grafted fabric is characterized by comprising the following steps of: is prepared by dissolving graphene oxide in N-methylimidazole bisulfate ionic liquid ([ Hmim) ]HSO 4 ) In the method, nano carboxyl chitosan dispersion liquid is dripped under the action of ultrasonic waves to react with a graphene oxide lamellar layer to obtain a graphene oxide/nano carboxyl chitosan compound, and then the graphene oxide/nano carboxyl chitosan compound and a fabric are subjected to in-situ grafting reaction in N-methylimidazole bisulfate ionic liquid through microwave radiation to obtain the graphene oxide/nano carboxyl chitosan in-situ graftingA fabric.
Further, the graphene oxide/nano carboxyl chitosan composite is prepared according to the following steps:
stirring and dissolving nano carboxyl chitosan in acetic acid solution with volume concentration of 2% to prepare nano carboxyl chitosan dispersion liquid with mass concentration of 0.2-1.0%; dissolving graphene oxide in N-methylimidazole bisulfate ionic liquid (the pH value of which is preferably 3.4-4.6) at 80-90 ℃ to obtain graphene oxide ionic liquid solution; dripping nano carboxyl chitosan dispersion liquid into graphene oxide ionic liquid solution within 6-10 min under the action of 100-260W ultrasonic wave, performing ultrasonic chemical reaction for 1-2 h to form amide bonds, hemi-acetal bonds and the like between graphene oxide lamellar and nano carboxyl chitosan particles, and performing high-speed centrifugation for 15-20 min (the rotation speed of centrifugation is preferably 10000-12500 rpm) and vacuum freeze drying for 24-48 h to obtain the graphene oxide/nano carboxyl chitosan compound. The mass ratio of the graphene oxide to the nano carboxyl chitosan is 0.125-0.8:1. The nano carboxyl chitosan has the content of C6 aldehyde group of 28.15-41.69%, the content of C2 and C3 carboxyl groups of 19.57-40.92%, the deacetylation degree of 83.61-90.73%, the solubility in water of 11.94-22.86 g/100mL and the isoelectric point pH of 5.5-5.7, and has the following structural formula:
Preferably, the graphene oxide is prepared by a modified Hummers method, the crystal face spacing of the graphene oxide is 0.883-0.894 nm, the thickness of a slice layer is less than or equal to 1nm, the carboxyl content is 3.73-3.95 mmol/g, and the specific surface area is more than or equal to 462m 2 And/g, the structural formula is as follows:
the fabric provided by the invention is cellulose fiber fabric, protein fiber fabric, blended fabric of cellulose fiber and polyester fiber or blended fabric of protein fiber and polyester fiber.
The preparation method of the graphene oxide/nano carboxyl chitosan in-situ grafted fabric comprises the following steps:
(1) Adding the boiled or degummed fabric into N-methylimidazole bisulfate ionic liquid (the pH value of which is preferably 4.5-5.0), swelling for 20-30 min at 30-40 ℃ by using an ultrasonic probe (the power of the ultrasonic probe is preferably 60-100W), repeating for 2-3 times, and then immersing in absolute ethyl alcohol for 2-4 h to remove the ionic liquid to obtain an activated fabric;
(2) The graphene oxide/nano carboxyl chitosan compound is dissolved in N-methylimidazole bisulfate ionic liquid (the pH value of which is preferably 4.2-4.8) to prepare reaction liquid with the mass concentration of 0.2-0.8%; adding the activated fabric obtained in the step (1) into the reaction solution (the bath ratio of the activated fabric to the reaction solution is set to be 1g: 20-30 mL), and stirring and reacting for 20-90 min under the microwave radiation condition (the microwave radiation power is preferably 320-680W, and the microwave radiation temperature is preferably 25-40 ℃), so as to obtain the fabric after the grafting reaction;
(3) Padding the fabric subjected to the grafting reaction for 2-3 times to ensure that the liquid carrying rate of the fabric is 65-95 percent, then putting the fabric into a heat setting machine to be prebaked for 15-20 min at 30-40 ℃, heating to 100 ℃ to bake for 8-12 min, finally drying at 60 ℃ for 2-3 h, washing with clear water and airing to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted fabric.
Preferably, in the step (3), the heating method of the heat setting machine is intermittent heating, and the heat setting machine is suspended for 1min after heating to 10 ℃, wherein the heating rate is 5 ℃/min.
A series of functional fabrics with different graphene oxide/nano carboxyl chitosan compound grafting rates can be obtained by optimizing the mass ratio of graphene oxide to nano carboxyl chitosan, the pH value of N-methylimidazole bisulfate ionic liquid, the ultrasonic treatment time, the microwave radiation reaction temperature and the microwave radiation reaction time.
Compared with the prior art, the preparation principle and the beneficial effects of the graphene oxide/nano carboxyl chitosan in-situ grafted fabric are as follows:
1. the invention adopts the improved Hummers method to prepare the graphite oxideCompared with the traditional Hummers method, the alkene does not use nitric acid and sodium nitrate, avoids generating NO in the reaction process 2 Harmful gases are generated, so that the safety of the reaction is improved; and the steps of intercalation, oxidization and stripping of the graphene oxide can be realized only under the medium-low temperature condition without a high-temperature reaction stage, so that the reaction time is greatly shortened, the preparation efficiency is improved, and the obtained graphene oxide has high carboxyl content, fewer defects, regular structure, small thickness and large specific surface area.
2. In the invention, the crosslinking of graphene oxide and nano carboxyl chitosan is carried out in N-methylimidazole bisulfate ionic liquid, and N-methylimidazole bisulfate ([ Hmim)]HSO 4 ) [ HSO in acidic Ionic liquid 4 ] － Ionization to give H + The amino group of the nano carboxyl chitosan is positively charged, so that the probability of contact and nucleophilic reaction with the carboxyl group in the graphene oxide sheet is increased; and the pH of the N-methylimidazole bisulfate ionic liquid is lower than the pH (5.5-5.7) of the isoelectric point of the nano carboxyl chitosan, so that the nano carboxyl chitosan particles have positive charges, the electrostatic attraction between the nano carboxyl chitosan particles and electronegative groups carboxyl, hydroxyl and epoxy groups in the graphene oxide is greatly enhanced, the carboxyl chitosan nanoparticles are promoted to enter the middle of graphene oxide sheets, the uniform combination of the nano carboxyl chitosan particles and the graphene oxide is realized, and the stability of the composite material is improved. The middle part of the graphene oxide contains a large amount of epoxy groups, so that the material has the characteristics of hydrophilic edges and hydrophobic middle edges, the reaction of the nano carboxyl chitosan and the oxygen-containing functional groups at the edges of the graphene oxide is promoted by virtue of the ultrasonic wave, the ring-opening reaction rate of the amino groups of the nano carboxyl chitosan and the epoxy groups in the graphene oxide is accelerated, and the reaction product yield of the compound is improved; after the composite reaction with the nano carboxyl chitosan, the surface energy of the graphene oxide is reduced, the hydrophilicity of the middle part of the lamellar is improved, the dispersion effect is improved, and the defect that the lamellar adhesion of the graphene oxide is easy to occur due to the large specific surface area is effectively prevented, so that the graphene oxide/nano carboxyl chitosan composite material has a uniform structure and strong adsorption capacity, and is easy to react with fabric grafting.
3. According to the invention, the graphene oxide/nano carboxyl chitosan composite is subjected to vacuum freeze drying, water contained in the composite is frozen below a freezing point to be changed into ice, and then the ice crystal is sublimated into steam under higher vacuum to remove water. The original chemical composition and physical properties of the composite after vacuum freeze drying are maintained, so that the graphene oxide sheets in the composite have good dispersibility, are not sticky and have larger specific surface area; the carboxyl chitosan particles in the composite are promoted not to agglomerate, are uniformly distributed, and are favorable for the grafting reaction of graphene oxide/nano carboxyl chitosan composite and fabric; meanwhile, the energy consumption of the vacuum freeze drying method is obviously reduced compared with other drying methods.
4. According to the invention, the fabric is added into the N-methylimidazole bisulfate ionic liquid to carry out swelling, so that the hydrogen bond action among fiber molecules is weakened, the graphene oxide/nano carboxyl chitosan composite material is facilitated to permeate into the reaction sites inside the fibers to carry out catalytic grafting reaction, the reaction time is shortened, the grafting efficiency is improved, and the bonding fastness of the graphene oxide/nano carboxyl chitosan on the fabric is enhanced; simultaneously cavitation effect generated by the ultrasonic probe in liquid is utilized to form cavitation bubbles, instantaneous high temperature and high pressure are generated along with cavitation bubble vibration and violent explosion, and partial water molecules can be thermally dissociated to form OH free radicals and H atoms, so that active groups on the surface of the fabric are increased, and the accessibility and grafting rate of the reaction of the activated fabric with polar groups such as amino groups, carboxyl groups and aldehyde groups in the graphene oxide/nano carboxyl chitosan compound are improved.
5. According to the invention, the fabric is immersed in the N-methylimidazole bisulfate ionic finishing liquid for reaction under the microwave irradiation condition, and as the microwave irradiation heating speed is high, the reaction time is short and the uniformity is good, the composite particles can be fully contacted with the active sites of the fabric, the ionic liquid catalytic grafting rate is obviously accelerated, the condition that the nanoparticles are easy to agglomerate and disperse unevenly due to long-time treatment is effectively avoided, the composite is uniformly grafted on the surface of the fabric, and the defects of long reaction period, low grafting reaction rate, easiness in aggregation of the nanoparticles in the finishing liquid and uneven distribution on the surface of the fabric in the traditional water bath heating reaction process are overcome. Meanwhile, the pH value of the N-methylimidazole bisulfate ionic liquid serving as a reaction medium is 4.2-4.8 which is greater than the isoelectric point pH value of silk (about 3.5-4.2), so that the silk fabric presents electronegativity, and the electrostatic attraction and grafting reaction efficiency of the electropositive graphene oxide/nano carboxyl chitosan compound on cellulose fabrics such as negatively charged silk, cotton and the like can be remarkably improved, thereby greatly improving the grafting rate of the compound on the fabric and the antibacterial, ultraviolet-proof and crease-resistant performances.
6. Graphene oxide has sharp edges due to a lamellar structure, and can physically cut bacteria, destroy cell membranes of the bacteria, reduce membrane potential or leak electrolyte so as to inhibit bacterial growth. The nano carboxyl chitosan has positive charges on the surface, is easy to generate electrostatic action with negatively charged groups on the surfaces of fungi, bacteria and viruses, and the small-size effect enables the nano carboxyl chitosan particles to be easier to be contacted with bacteria, so that the fluidity and permeability of cell membranes are changed, nutrients are blocked from entering the cells to cause cell death, or the integrity of cell walls is damaged to enable the cell walls to tend to be dissolved, so that proteins and other components in the cells are leaked, and apoptosis is promoted. The graphene oxide/nano carboxyl chitosan composite can exert respective advantages, has double antibacterial activity, achieves lasting and efficient antibacterial effect after being chemically grafted with fabric, and has wide application.
7. The graphene oxide/nano carboxyl chitosan compound modified fabric surface can absorb ultraviolet rays with the wavelength smaller than 281nm and long-wave ultraviolet rays with the reflection wavelength larger than 281nm, so that the problems of aging, mechanical decline and the like of textiles caused by ultraviolet radiation of a traditional fabric can be effectively solved, and the graphene oxide of a sheet layer is firmly and chemically crosslinked on the fabric surface through nano carboxyl chitosan, so that the crease resistance of the fabric is remarkably enhanced.
8. The preparation process is simple and easy to implement, low in cost, good in reaction condition controllability, free of any cross-linking agent and auxiliary agent, environment-friendly, and the prepared graphene oxide/nano carboxyl chitosan in-situ grafted fabric is soft in hand feeling, moisture-absorbing and breathable, good in skin-friendly, high in efficiency and lasting in antibacterial, ultraviolet-resistant, crease-resistant and other functions, and huge in market potential.
Drawings
Fig. 1 is a diagram of a modification mechanism of graphene oxide/nano carboxyl chitosan in-situ grafted silk fabric.
Fig. 2 is an infrared spectrum of graphene oxide/nano carboxyl chitosan in-situ grafted silk fabric in test item 1 of the present invention.
Detailed Description
For a better understanding of the technical features, objects and advantages of the present invention, the present invention will be further described with reference to the drawings and the specific examples, but the present invention is not limited to the following examples.
1. Preparation of graphene oxide/nano carboxyl chitosan in-situ grafted fabric
Example 1
The nano carboxyl chitosan used in the embodiment is characterized in that: the aldehyde group content at the C6 position is 30.59%, the carboxyl groups at the C2 and C3 positions are 24.65%, the deacetylation degree is 86.31%, the solubility in water is 15.05g/100mL, and the isoelectric point pH is about 5.7.
The graphene oxide used in this example is prepared by a modified Hummers method, and is characterized in that: the interplanar spacing is 0.891nm, the thickness of the lamellar layer is 0.95nm, the carboxyl content is 3.77mmol/g, and the specific surface area is 475m 2 /g。
The graphene oxide/nano carboxyl chitosan compound of the embodiment is prepared according to the following steps: stirring and dissolving nano carboxyl chitosan in acetic acid solution with volume concentration of 2% to prepare nano carboxyl chitosan dispersion liquid with mass concentration of 0.4%; dissolving graphene oxide in N-methylimidazole bisulfate ionic liquid with pH of=3.8 at 80 ℃ to obtain graphene oxide ionic liquid solution; and (3) dropwise adding nano carboxyl chitosan dispersion liquid into the graphene oxide ionic liquid solution within 8min under the action of 150W ultrasonic waves, performing ultrasonic chemical reaction for 1h to form chemical bonds such as amide bonds, hemiacetal bonds and the like between the graphene oxide lamellar and nano carboxyl chitosan particles, and performing high-speed centrifugation (the rotating speed is 12000 rpm) for 18min and vacuum freeze drying for 36h to obtain the graphene oxide/nano carboxyl chitosan compound. Wherein the mass ratio of graphene oxide to nano carboxyl chitosan is 0.2:1.
The finishing method of the in-situ grafted fabric by using the prepared graphene oxide/nano carboxyl chitosan compound comprises the following steps:
(1) Adding the cotton fabric after scouring into N-methylimidazole bisulfate ionic liquid with pH=4.6, swelling for 25min at 35 ℃ by using an ultrasonic probe (70W), repeating for 3 times, and then immersing in absolute ethyl alcohol for 3 hours to remove the ionic liquid, thereby obtaining the activated cotton fabric.
(2) The prepared graphene oxide/nano carboxyl chitosan compound is dissolved in N-methylimidazole bisulfate ionic liquid with pH=4.3 to prepare a reaction solution with the mass concentration of 0.4%. Adding the activated cotton fabric (the bath ratio of the cotton fabric to the reaction solution is 1g:20 mL) obtained in the step (1) into the reaction solution, and stirring and reacting for 60min under the microwave radiation condition with the power of 400W and the temperature of 30 ℃ to obtain the fabric after the grafting reaction.
(3) Padding the fabric subjected to the grafting reaction for 3 times to ensure that the fabric belt liquid ratio is 80%, then placing the fabric into a heat setting machine (intermittently heating, suspending for 1min after heating to 10 ℃ each time, and heating rate is 5 ℃/min) for pre-drying for 20min at 30 ℃, heating to 100 ℃ for baking for 10min, finally drying at 60 ℃ for 2h, washing with clear water, and airing to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted cotton fabric (sample 13).
For comparison, the following samples were also prepared for this example:
sample 11: a raw cotton fabric.
Sample 12: the fabric subjected to the grafting reaction is obtained through the steps (1) and (2) in the finishing method of the embodiment, then the fabric is pre-baked for 20min at 30 ℃ in an oven, then baked for 10min at 100 ℃, finally dried for 2h at 60 ℃, washed with clear water and dried to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted cotton fabric.
Evaluation of textile antibacterial Properties according to GB/T3923.1-2013, determination of textile fabric fold recovery, GB/T3819-1997, section 3 of GB/T20944.3-2008, textile fabric tensile Properties: the vibration method and GB/T18830-2009 evaluation of ultraviolet resistance of textiles and other standards detect the mechanical properties, crease recovery, bacteriostasis rate on staphylococcus aureus and escherichia coli, and antibacterial and ultraviolet resistance of samples 11-13. The test results are shown in Table 1.
Table 1 physicochemical properties of graphene oxide/nano carboxyl chitosan in situ grafted cotton fabric
As can be seen from table 1, compared with the cotton fabric (sample 11), the graphene oxide/nano carboxyl chitosan in-situ grafted cotton fabric (samples 12 and 13) has significantly improved breaking strength, antibacterial property and ultraviolet resistance. The graphene oxide/nano carboxyl chitosan can be subjected to a hemiacetal reaction with cotton fabric, and is firmly combined on the surface of the fabric, so that the physicochemical properties of the cotton fabric are improved to a greater extent. The crease recovery performance of the fabric shows that the recovery performance of the fabric after folds are generated under the action of external force, is an important influence factor of the fabric clothing performance and the attractive appearance, and the table shows that the crease recovery angle of the graphene oxide/nano carboxyl chitosan in-situ grafted cotton fabric is obviously improved compared with that of the original cotton fabric, and the recovery angle reaches 190.3 degrees. After 50 times of water washing, the antibacterial rate of the modified cotton fabric (sample 13) is still above 86.9%, and the UPF value is kept at 61.85%, which shows that the functionality of the compound modified cotton fabric is durable. In addition, compared with the sample 12 (the whiteness and the air permeability are respectively reduced by 24.38 percent and 22.69 percent) which is subjected to the drying treatment by the oven, the grafting rate, breaking strength, moisture regain and whiteness of the sample 13 which is treated by the heat setting machine are higher, and the air permeability is reduced slightly (only reduced by 4.24 percent), which indicates that the graphene oxide/nano carboxyl chitosan compound grafted on the surface of the cotton fabric is uniformly distributed, does not gather to form a film on the surface of the fabric, and has good taking comfort.
Example 2
The nano carboxyl chitosan used in the embodiment is characterized in that: the content of aldehyde group at the C6 position is 34.28%, the content of carboxyl group at the C2 and C3 positions is 30.23%, the deacetylation degree is 88.21%, the solubility in water is 17.96g/100mL, and the isoelectric point pH is about 5.7.
The graphene oxide used in this example is prepared by a modified Hummers method, and is characterized in that: the interplanar spacing is 0.887nm, the thickness of the lamellar layer is 0.91nm, the carboxyl content is 3.81mmol/g, and the specific surface area is 492m 2 /g
The graphene oxide/nano carboxyl chitosan compound of the embodiment is prepared according to the following steps: stirring and dissolving nano carboxyl chitosan in acetic acid solution with volume concentration of 2% to prepare nano carboxyl chitosan dispersion liquid with mass concentration of 0.6%; dissolving graphene oxide in N-methylimidazole bisulfate ionic liquid with pH=4.0 at 80 ℃ to obtain graphene oxide ionic liquid solution; and (3) dropwise adding nano carboxyl chitosan dispersion liquid into the graphene oxide ionic liquid solution within 8min under the action of 180W ultrasonic waves, performing ultrasonic chemical reaction for 2h to form chemical bonds such as amide bonds, hemiacetal bonds and the like between the graphene oxide lamellar and nano carboxyl chitosan particles, and performing high-speed centrifugation (the rotating speed is 12000 rpm) for 18min and vacuum freeze drying for 36h to obtain the graphene oxide/nano carboxyl chitosan compound. Wherein the mass ratio of graphene oxide to nano carboxyl chitosan is 0.4:1.
The finishing method of the in-situ grafted fabric by using the prepared graphene oxide/nano carboxyl chitosan compound comprises the following steps:
(1) Adding the degummed silk fabric into N-methylimidazole bisulfate ionic liquid with pH=5.0, swelling at 35 ℃ for 25min by using an ultrasonic probe (80W), repeating for 3 times, and immersing in absolute ethyl alcohol for 3h to remove the ionic liquid, thereby obtaining the activated silk fabric.
(2) The prepared graphene oxide/nano carboxyl chitosan compound is dissolved in N-methylimidazole bisulfate ionic liquid with pH=4.5 to prepare a reaction solution with the mass concentration of 0.6%. Adding the activated silk fabric (the bath ratio of the silk fabric to the reaction solution is 1g:20 mL) obtained in the step (1) into the reaction solution, and stirring and reacting for 60min under the microwave radiation condition with the power of 460W and the temperature of 40 ℃ to obtain the fabric after the grafting reaction.
(3) Padding the fabric subjected to the grafting reaction for 3 times to ensure that the fabric belt liquid ratio is 90%, then placing the fabric into a heat setting machine (intermittently heating, suspending for 1min after heating to 10 ℃ each time, and heating rate is 5 ℃/min) for pre-drying for 20min at 35 ℃, heating to 100 ℃ for baking for 10min, finally drying at 60 ℃ for 2h, washing with clear water, and airing to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted silk fabric (sample 24).
For comparison, the following samples were also prepared for this example:
sample 21: silk fabric.
Sample 22: treating the unactivated silk fabric through the step (2) in the finishing method, pre-baking for 20min at 35 ℃ in an oven, baking for 10min at 100 ℃, drying for 2h at 60 ℃, washing with clear water, and airing to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted silk fabric.
Sample 23: the fabric subjected to the grafting reaction is obtained through the steps (1) and (2) in the finishing method of the embodiment, then the fabric is pre-baked for 20min at 35 ℃ in an oven, then baked for 10min at 100 ℃, finally dried for 2h at 60 ℃, washed with clear water and dried to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted silk fabric.
Evaluation of textile antibacterial Properties according to GB/T3923.1-2013, determination of textile fabric fold recovery, GB/T3819-1997, section 3 of GB/T20944.3-2008, textile fabric tensile Properties: the vibration method and GB/T18830-2009 evaluation of ultraviolet resistance of textiles and other standards detect the mechanical properties, crease recovery, bacteriostasis rate on staphylococcus aureus and escherichia coli, and antibacterial and ultraviolet resistance of the samples 21-24. The test results are shown in Table 2.
Table 2 physicochemical properties of graphene oxide/nano carboxyl chitosan in situ grafted silk fabric
As can be seen from Table 2, compared with the silk fabric (sample 21), the graphene oxide/nano carboxyl chitosan in-situ grafted silk fabric (samples 22-24) has obviously improved breaking strength, antibacterial property, wrinkle resistance and ultraviolet resistance. The graphene oxide/nano carboxyl chitosan can be subjected to a hemiacetal reaction with silk, so that the graphene oxide/nano carboxyl chitosan can be firmly combined on the surface of silk fabric, and the physicochemical property of the silk fabric is remarkably improved. The crease recovery property of the fabric indicates the recovery property of the fabric after crease is generated under the action of external force, is an important influence factor of the fabric wearability and the attractive appearance, and the table shows that the crease recovery angle of the oxidized graphene/nano carboxyl chitosan in-situ grafted silk fabric is obviously improved to 201.2 degrees compared with that of the original silk fabric. After 50 times of water washing, the antibacterial rate of the modified silk fabric (sample 24) is still above 92.2%, and the UPF value is kept at 91.78%, which shows that the antibacterial and ultraviolet-proof performances of the compound modified silk fabric are high-efficiency and durable. In addition, compared with the sample 23 (the whiteness and the air permeability are respectively reduced by 31.51 percent and 42.23 percent) subjected to the drying treatment of the oven, the grafting rate, breaking strength, moisture regain and whiteness of the sample 24 subjected to the heat setting machine are higher, and the air permeability is reduced slightly (only by 8.71 percent), which indicates that the graphene oxide/nano carboxyl chitosan compound grafted on the surface of the silk fabric is uniformly distributed, can not be crosslinked on the surface of the fabric to form a film, and has good taking comfort.
Example 3
The nano carboxyl chitosan used in the embodiment is characterized in that: the content of aldehyde group at the C6 position is 34.28%, the content of carboxyl group at the C2 and C3 positions is 30.23%, the deacetylation degree is 88.21%, the solubility in water is 17.96g/100mL, and the isoelectric point pH is about 5.7.
The graphene oxide used in this example is prepared by a modified Hummers method, and is characterized in that: the interplanar spacing is 0.887nm, the thickness of the lamellar layer is 0.91nm, the carboxyl content is 3.81mmol/g, and the specific surface area is 492m 2 /g。
The graphene oxide/nano carboxyl chitosan compound of the embodiment is prepared according to the following steps: stirring and dissolving nano carboxyl chitosan in acetic acid solution with volume concentration of 2% to prepare nano carboxyl chitosan dispersion liquid with mass concentration of 0.6%; dissolving graphene oxide in N-methylimidazole bisulfate ionic liquid with pH=4.0 at 80 ℃ to obtain graphene oxide ionic liquid solution; and (3) dropwise adding nano carboxyl chitosan dispersion liquid into the graphene oxide ionic liquid solution within 8min under the action of 180W ultrasonic waves, performing ultrasonic chemical reaction for 2h to form chemical bonds such as amide bonds, hemiacetal bonds and the like between the graphene oxide lamellar and nano carboxyl chitosan particles, and performing high-speed centrifugation (the rotating speed is 12000 rpm) for 18min and vacuum freeze drying for 36h to obtain the graphene oxide/nano carboxyl chitosan compound. Wherein the mass ratio of graphene oxide to nano carboxyl chitosan is 0.4:1.
The finishing method of the in-situ grafted fabric by using the prepared graphene oxide/nano carboxyl chitosan compound comprises the following steps:
(1) Adding the boiled 30% polyester fiber/70% silk blended fabric into N-methylimidazole bisulfate ionic liquid with pH value of 4.8, swelling for 25min at 40 ℃ by using an ultrasonic probe (90W), repeating for 3 times, and then immersing in absolute ethyl alcohol for 3 hours to remove the ionic liquid, thereby obtaining the activated blended fabric.
(2) The prepared graphene oxide/nano carboxyl chitosan compound is dissolved in N-methylimidazole bisulfate ionic liquid with pH=4.6 to prepare a reaction liquid with the mass concentration of 0.6%. Adding the activated polyester fiber/silk blended fabric (the bath ratio of the polyester fiber/cotton blended fabric to the reaction solution is 1g:25 mL) obtained in the step (1) into the reaction solution, and stirring and reacting for 60min under the microwave radiation condition with the power of 540W and the temperature of 40 ℃ to obtain the fabric after the grafting reaction.
(3) Padding the blended fabric subjected to the grafting reaction for 3 times to ensure that the fabric belt liquid ratio is 90%, then placing the blended fabric into a heat setting machine (intermittently heating, suspending for 1min after heating to 10 ℃ each time, and heating rate is 5 ℃/min) for pre-baking for 20min at 40 ℃, heating to 100 ℃ for baking for 10min, finally drying at 60 ℃ for 3h, washing with clear water, and airing to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted polyester fiber/silk blended fabric (sample 34).
For comparison, the following samples were also prepared for this example:
sample 31:30% polyester fiber/70% silk blend fabric.
Sample 32: and (3) treating the unactivated polyester fiber/silk blended fabric through the step (2) in the finishing method, pre-drying for 20min at 40 ℃ in a drying oven, baking for 10min at 100 ℃, drying for 3h at 60 ℃, washing with clear water, and airing to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted silk fabric.
Sample 33: the fabric subjected to the grafting reaction is obtained through the steps (1) and (2) in the finishing method of the embodiment, then the fabric is pre-baked for 20min at 40 ℃ in an oven, then baked for 10min at 100 ℃, finally dried for 3h at 60 ℃, washed with clear water and dried to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted polyester fiber/silk blended fabric.
Evaluation of textile antibacterial Properties according to GB/T3923.1-2013, determination of textile fabric fold recovery, GB/T3819-1997, section 3 of GB/T20944.3-2008, textile fabric tensile Properties: the vibration method and GB/T18830-2009 evaluation of ultraviolet resistance of textiles and other standards detect the mechanical properties, crease recovery, bacteriostasis rate on staphylococcus aureus and escherichia coli, and ultraviolet resistance of samples 31-34. The test results are shown in Table 3.
Table 3 physicochemical properties of graphene oxide/nano carboxyl chitosan in-situ grafted polyester fiber/silk blend fabric
As can be seen from Table 3, compared with the polyester fiber/silk blended fabric (sample 31), the graphene oxide/nano carboxyl chitosan in-situ grafting blended fabric (samples 32-34) has obviously improved breaking strength, antibacterial property, wrinkle resistance and ultraviolet resistance. The graphene oxide/nano carboxyl chitosan can be subjected to a hemiacetal reaction with the blended fabric, and is firmly combined on the surface of the blended fabric, so that the physicochemical properties of the blended fabric are remarkably improved. The crease recovery property of the blended fabric indicates the recovery property of the fabric after crease is generated under the action of external force, is an important influence factor of the fabric wearability and the attractive appearance, and the table shows that the crease recovery angle of the graphene oxide/nano carboxyl chitosan in-situ grafted blended fabric is obviously improved to 175.4 degrees compared with that of the original blended fabric. After 50 times of water washing, the antibacterial rate of the modified blend fabric (sample 34) is still above 90.2%, and the UPF value is kept at 69.26%, which shows that the antibacterial and ultraviolet-resistant performances of the compound modified blend fabric are high-efficiency and durable. In addition, compared with the sample 33 (the whiteness and the air permeability are respectively reduced by 24.68 percent and 30.72 percent) which is subjected to the drying treatment by the baking oven, the sample 34 which is subjected to the treatment by the heat setting machine has higher grafting rate, breaking strength, moisture regain and whiteness, and smaller air permeability (only reduced by 4.40 percent), which indicates that the graphene oxide/nano carboxyl chitosan compound grafted on the surface of the blended fabric is uniformly distributed, can not be agglomerated on the surface of the blended fabric to form a film, and has good taking comfort.
Example 4
The nano carboxyl chitosan used in the embodiment is characterized in that: the content of aldehyde group at C6 position is 38.14%, the content of carboxyl group at C2 and C3 positions is 31.82%, the deacetylation degree is 82.25%, the solubility in water is 21.82g/100mL, and the isoelectric point pH is about 5.7.
The graphene oxide used in this example is prepared by a modified Hummers method, and is characterized in that: the interplanar spacing is 0.884nm, the thickness of the lamellar layer is 0.85nm, the carboxyl content is 3.90mmol/g, and the specific surface area is 493m 2 /g。
The graphene oxide/nano carboxyl chitosan compound of the embodiment is prepared according to the following steps: stirring and dissolving nano carboxyl chitosan in acetic acid solution with volume concentration of 2% to prepare nano carboxyl chitosan dispersion liquid with mass concentration of 0.4%; dissolving graphene oxide in N-methylimidazole bisulfate ionic liquid with pH=4.2 at 85 ℃ to obtain graphene oxide ionic liquid solution; and (3) dropwise adding nano carboxyl chitosan dispersion liquid into the graphene oxide ionic liquid solution within 8min under the action of 150W ultrasonic waves, performing ultrasonic chemical reaction for 1h to form chemical bonds such as amide bonds, hemiacetal bonds and the like between graphene oxide sheets and nano carboxyl chitosan particles, and performing high-speed centrifugation (the rotating speed is 11000 rpm) for 15min and vacuum freeze drying for 40h to obtain the graphene oxide/nano carboxyl chitosan compound. Wherein the mass ratio of graphene oxide to nano carboxyl chitosan is 0.6:1.
The finishing method of the in-situ grafted fabric by using the prepared graphene oxide/nano carboxyl chitosan compound comprises the following steps:
(1) Adding the boiled 30% polyester fiber/70% viscose blended fabric into N-methylimidazole bisulfate ionic liquid with pH value of 4.8, swelling for 25min at 35 ℃ by using an ultrasonic probe (90W), repeating for 3 times, and then immersing in absolute ethyl alcohol for 3 hours to remove the ionic liquid to obtain an activated polyester fiber/viscose blended fabric;
(2) Dissolving the prepared graphene oxide/nano carboxyl chitosan compound in N-methylimidazole bisulfate ionic liquid with pH=4.5 to prepare a reaction solution with the mass concentration of 0.6%; adding the activated polyester fiber/viscose blended fabric (the bath ratio of the polyester fiber/viscose blended fabric to the reaction solution is 1g:30 mL) obtained in the step (1) into the reaction solution, and stirring and reacting for 70min under the microwave radiation condition with the power of 500W and the temperature of 40 ℃ to obtain the fabric after the grafting reaction.
(3) Padding the fabric subjected to the grafting reaction for 3 times to ensure that the fabric belt liquid ratio is 95%, then placing the fabric into a heat setting machine (intermittently heating, suspending for 1min after heating to 10 ℃ each time, and heating to 5 ℃/min) for pre-baking for 15min at 40 ℃, heating to 100 ℃ for baking for 12min, finally drying at 60 ℃ for 3h, washing with clear water, and airing to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted polyester fiber/viscose blended fabric (sample 43).
For comparison, the following samples were also prepared for this example:
sample 41:30% polyester fiber/70% viscose blend fabric.
Sample 42: the fabric subjected to the grafting reaction is obtained through the steps (1) and (2) in the finishing method of the embodiment, then the fabric is pre-baked in an oven at 40 ℃ for 15min, then baked at 100 ℃ for 12min, finally dried at 60 ℃ for 3h, and washed and dried by clear water, so that the graphene oxide/nano carboxyl chitosan in-situ grafted polyester fiber/viscose blended fabric is obtained.
Evaluation of textile antibacterial Properties according to GB/T3923.1-2013, determination of textile fabric fold recovery, GB/T3819-1997, section 3 of GB/T20944.3-2008, textile fabric tensile Properties: the vibration method and GB/T18830-2009 evaluation of ultraviolet resistance of textiles and other standards detect the mechanical properties, crease recovery, bacteriostasis rate on staphylococcus aureus and escherichia coli, and antibacterial and ultraviolet resistance of the samples 41-43. The test results are shown in Table 4.
Table 4 physicochemical properties of graphene oxide/nano carboxyl chitosan in-situ grafted polyester fiber/viscose blend fabric
As can be seen from Table 4, compared with the polyester fiber/viscose blended fabric (sample 41), the graphene oxide/nano carboxyl chitosan in-situ grafting blended fabric (samples 42-43) has obviously improved breaking strength, antibacterial property, wrinkle resistance and ultraviolet resistance. The graphene oxide/nano carboxyl chitosan can be subjected to a hemiacetal reaction with the blended fabric, and is firmly combined on the surface of the blended fabric, so that the physicochemical properties of the blended fabric are obviously improved. The crease recovery property of the blended fabric indicates the recovery property of the fabric after crease is generated under the action of external force, is an important influence factor of the fabric wearability and the attractive appearance, and the table shows that the crease recovery angle of the graphene oxide/nano carboxyl chitosan in-situ grafted blended fabric is obviously improved as compared with that of the original blended fabric, and reaches 169.4 degrees. After 50 times of water washing, the antibacterial rate of the modified blend fabric (sample 43) is still above 86.3%, and the UPF value is kept at 76.39%, which shows that the antibacterial and ultraviolet-resistant performances of the compound modified blend fabric are high-efficiency and durable. In addition, compared with the sample 42 (the whiteness and the air permeability are respectively reduced by 28.99 percent and 29.67 percent) which is subjected to the drying treatment by the baking oven, the sample 43 which is subjected to the treatment by the heat setting machine has higher grafting rate, breaking strength, moisture regain and whiteness, and smaller air permeability (only reduced by 6.82 percent), which shows that the graphene oxide/nano carboxyl chitosan compound grafted on the surface of the blended fabric is uniformly distributed, can not be aggregated on the surface of the blended fabric to form a film, and has good taking comfort.
Comparative example 1 (without addition of nano carboxyl chitosan)
The finishing method of the graphene oxide grafted fabric prepared by the embodiment comprises the following steps:
(1) Adding the degummed silk fabric into N-methylimidazole bisulfate ionic liquid with pH=5.0, swelling at 35 ℃ for 25min by using an ultrasonic probe (80W), repeating for 3 times, and immersing in absolute ethyl alcohol for 3h to remove the ionic liquid, thereby obtaining the activated silk fabric.
(2) Graphite oxide is oxidizedAlkene (interplanar spacing 0.887nm, lamellar thickness 0.91nm, carboxyl content 3.81mmol/g, specific surface 492 m) 2 /g) was dissolved in an N-methylimidazole bisulfate ionic liquid having ph=4.5 to prepare a reaction solution having a mass concentration of 0.6%. Adding the activated silk fabric (the bath ratio of the silk fabric to the reaction solution is 1g:20 mL) obtained in the step (1) into the reaction solution, and stirring and reacting for 60min under the microwave radiation condition with the power of 460W and the temperature of 40 ℃ to obtain the fabric after the grafting reaction.
(3) Padding the fabric subjected to the grafting reaction for 3 times to ensure that the fabric belt liquid ratio is 90%, then placing the fabric into a heat setting machine (intermittently heating, suspending for 1min after heating to 10 ℃ each time, and heating rate is 5 ℃/min) for pre-drying for 20min at 35 ℃, heating to 100 ℃ for baking for 10min, finally drying at 60 ℃ for 2h, washing with clear water, and airing to obtain the graphene oxide in-situ grafted silk fabric (sample 53).
The comparative example also prepared the following samples:
sample 51: silk fabric.
Sample 52: the fabric subjected to the grafting reaction is obtained through the steps (1) and (2) in the finishing method of the comparative example, then the fabric is pre-baked for 20min at 35 ℃ in an oven, then baked for 10min at 100 ℃, finally dried for 2h at 60 ℃, and washed and dried by clear water, so that the graphene oxide grafted silk fabric is obtained.
Evaluation of textile antibacterial Properties according to GB/T3923.1-2013, determination of textile fabric fold recovery, GB/T3819-1997, section 3 of GB/T20944.3-2008, textile fabric tensile Properties: the vibration method and GB/T18830-2009 evaluation of ultraviolet resistance of textiles and other standards detect the mechanical properties, crease recovery, bacteriostasis rate on staphylococcus aureus and escherichia coli, and antibacterial and ultraviolet resistance of the samples 51-53. The test results are shown in Table 5.
Table 5 physicochemical properties of graphene oxide grafted silk fabrics
As can be seen from table 5, the grafting rate, crease recovery angle, moisture regain, whiteness, mechanical properties, antibacterial property and ultraviolet resistance of the graphene oxide grafted silk fabric are obviously reduced compared with those of the graphene oxide/nano carboxyl chitosan in-situ grafted silk fabric in example 2 under the condition of not compositing with nano carboxyl chitosan. The graphene oxide/nano carboxyl chitosan composite in the embodiment 2 can exert respective advantages, has dual antibacterial activity, and nano carboxyl chitosan in the composite can be crosslinked with silk to generate amide bonds, semi-acetal bonds, schiff bases and the like, so that more graphene oxide sheets are uniformly grafted on the surface of the silk, the adhesion of the graphene oxide sheets is reduced, the modified fabric has stronger lasting function, aggregation adhesion of the sheets is easy to occur in the process of combining single graphene oxide with the silk, and grafting sites of the graphene oxide and the silk are fewer, so that the functionality and the wearability of the modified silk fabric are greatly reduced.
2. The sample obtained in the above example was subjected to a detection test
Test item 1: infrared spectrum characterization of graphene oxide/nano carboxyl chitosan in-situ grafted silk fabric
And (3) analyzing the condition of molecular groups in the graphene oxide/nano carboxyl chitosan in-situ grafted silk fabric by adopting infrared spectroscopy. Taking 3 parts of silk fabric samples: 1 part is a fabric A obtained by degumming silk fabric, 2 parts is a modified fabric with a grafting rate of 5.01% obtained by grafting silk fabric in situ with graphene oxide/nano carboxyl chitosan according to the method of sample 22 in example 2, 3 parts is a modified fabric C with a grafting rate of 10.58% obtained by grafting silk fabric in situ with graphene oxide/nano carboxyl chitosan according to the method of example 2, and the test results are shown in FIGS. 2 (A) to (C) in sequence.
As can be seen from FIG. 2, the infrared spectrum A of the degummed silk fabric is 2900-3400 cm -1 The nearby strong absorption peak is the characteristic peak of the telescoping of O-H and N-H in silk fibroin, and 1621.4cm -1 、1514.7cm -1 And 1227.3cm -1 Characteristic absorption bands of amide I, amide II and amide III, respectively belonging to silk fibroin. In the infrared curves B and C of the modified silk, after graphene oxide/nano carboxyl chitosan in-situ grafting silk fabric, 892.3cm -1 A vibration peak corresponding to the beta-pyranoside bond of the nano carboxyl chitosan in the complex appears nearby; compared with the original silk, the characteristic absorption peak of the modified silk has no obvious change of the amide characteristic peak of the fibroin, which indicates that the graphene oxide/nano carboxyl chitosan in-situ grafting does not damage the secondary structure of the fibroin; and at 1740.6cm -1 Is located at 2851.8cm -1 The c=o stretching vibration peak and the C-H stretching characteristic peak of aldehyde group are respectively appeared nearby, which are due to absorption bands caused by-COOH and-CHO in the graphene oxide/nano carboxyl chitosan composite grafted on the silk surface. Located at 1032.8cm -1 、1064.2cm -1 The C-O telescopic absorption peak of the carboxyl chitosan primary hydroxyl and secondary hydroxyl is also obvious, and the peak is 1227.3cm -1 The C-N characteristic peak intensity of the left and right amide III is improved along with the increase of the grafting rate of the compound, which shows that the graphene oxide/nano carboxyl chitosan compound and silk form more amide bond combinations. Meanwhile, the hydrogen bond absorption band of the raw silk is 3283.4cm -1 Move to 3274.9cm at low wave number of modified silk -1 And 3273.8cm -1 Nearby, this is due to the fact that the grafting reaction of the complex with the silk fabric enhances the forces between silk molecules to some extent. Infrared analysis shows that the graphene oxide/nano carboxyl chitosan compound is firmly combined with silk fabric through grafting reaction, and the high-efficiency durable functional modified textile is obtained.
In summary, the graphene oxide/nano carboxyl chitosan in-situ grafted fabric enables the graphene oxide/nano carboxyl chitosan to be uniformly grafted on the surface of the silk fabric through crosslinking of chemical bonds such as hemiacetal and amide bonds formed by aldehyde groups and carboxyl groups of the graphene oxide/nano carboxyl chitosan composite and the silk fabric, and the functional fabric which is high in grafting rate, durable, efficient, safe and comfortable in antibacterial and ultraviolet resistance is obtained. The invention adopts the graphene oxide/nano carboxyl chitosan in-situ grafted fabric technology, has simple process, durable fabric functionality, good serviceability, no use of chemical cross-linking agent, environmental protection, no environmental burden and huge practical application prospect.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A preparation method of graphene oxide/nano carboxyl chitosan in-situ grafted fabric is characterized by comprising the following steps: is prepared by dissolving graphene oxide in N-methylimidazole bisulfate ionic liquid ([ Hmim)]HSO 4 ) And then carrying out in-situ grafting reaction on the graphene oxide/nano carboxyl chitosan composite and a fabric in N-methylimidazole bisulfate ionic liquid by microwave radiation to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted fabric.
2. The preparation method of the graphene oxide/nano carboxyl chitosan in-situ grafted fabric according to claim 1, wherein the graphene oxide/nano carboxyl chitosan composite is prepared by the following steps:
stirring and dissolving nano carboxyl chitosan in acetic acid solution with volume concentration of 2% to prepare nano carboxyl chitosan dispersion liquid with mass concentration of 0.2-1.0%; dissolving graphene oxide in N-methylimidazole bisulfate ionic liquid at 80-90 ℃ to obtain graphene oxide ionic liquid solution;
dripping nano carboxyl chitosan dispersion liquid into graphene oxide ionic liquid solution within 6-10 min under the action of 100-260W ultrasonic waves, performing ultrasonic chemical reaction for 1-2 h to form chemical combination between graphene oxide lamellar and nano carboxyl chitosan particles, and performing high-speed centrifugation for 15-20 min and vacuum freeze drying for 24-48 h to obtain graphene oxide/nano carboxyl chitosan compound;
the mass ratio of the graphene oxide to the nano carboxyl chitosan is 0.125-0.8:1.
3. The method for preparing the graphene oxide/nano carboxyl chitosan in-situ grafted fabric according to claim 2, which is characterized in that: the nano carboxyl chitosan has the content of C6 aldehyde group of 28.15-41.69%, the content of C2 and C3 carboxyl groups of 19.57-40.92%, the deacetylation degree of 83.61-90.73%, the solubility in water of 11.94-22.86 g/100mL and the isoelectric point pH of 5.5-5.7, and has the following structural formula:
4. The preparation method according to claim 2, characterized in that: the pH value of the N-methylimidazole bisulfate ionic liquid is 3.4-4.6; the rotating speed of the high-speed centrifugation is 10000-12500 rpm; the graphene oxide is prepared by an improved Hummers method, the interplanar spacing of the graphene oxide is 0.883-0.894 nm, the thickness of a lamellar layer is less than or equal to 1nm, the carboxyl content is 3.73-3.95 mmol/g, and the specific surface area is more than or equal to 462m 2 /g。
5. The method for preparing the graphene oxide/nano carboxyl chitosan in-situ grafted fabric according to claim 1, which is characterized by comprising the following steps: the fabric is cellulose fiber fabric, protein fiber fabric, blended fabric of cellulose fiber and polyester fiber or blended fabric of protein fiber and polyester fiber.
6. The method for preparing the graphene oxide/nano carboxyl chitosan in-situ grafted fabric according to claim 1, which is characterized by comprising the following steps:
(1) Adding the boiled or degummed fabric into N-methylimidazole bisulfate ionic liquid, swelling for 20-30 min at 30-40 ℃ by using an ultrasonic probe, repeating for 2-3 times, and then immersing in absolute ethyl alcohol for 2-4 h to remove the ionic liquid to obtain an activated fabric;
(2) The graphene oxide/nano carboxyl chitosan compound is dissolved in N-methylimidazole bisulfate ionic liquid to prepare reaction liquid with the mass concentration of 0.2-0.8%; adding the activated fabric obtained in the step (1) into the reaction liquid, and stirring and reacting for 20-90 min under the condition of microwave radiation to obtain a fabric after grafting reaction;
(3) Padding the fabric subjected to the grafting reaction for 2-3 times to ensure that the liquid carrying rate of the fabric is 65-95 percent, then putting the fabric into a heat setting machine to be prebaked for 15-20 min at 30-40 ℃, heating to 100 ℃ to bake for 8-12 min, finally drying at 60 ℃ for 2-3 h, washing with clear water and airing to obtain the graphene oxide/nano carboxyl chitosan in-situ grafted fabric.
7. The method for preparing the graphene oxide/nano carboxyl chitosan in-situ grafted fabric according to claim 6, which is characterized in that: in the step (1), the power of the ultrasonic probe is 60-100W.
8. The method for preparing the graphene oxide/nano carboxyl chitosan in-situ grafted fabric according to claim 6, which is characterized in that: in the step (2), the pH value of the N-methylimidazole bisulfate ionic liquid is 4.2-4.8, the microwave radiation power is 320-680W, and the microwave radiation temperature is 25-40 ℃.
9. The method for preparing the graphene oxide/nano carboxyl chitosan in-situ grafted fabric according to claim 6, which is characterized in that: in the step (2), the bath ratio of the activated fabric to the reaction liquid is set to be 1 g:20-30 mL.
10. A graphene oxide/nano-carboxyl chitosan in-situ grafted fabric prepared by the preparation method of any one of claims 1 to 9.
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