CN112941896B - Multifunctional flame-retardant cotton fabric and preparation method and application thereof - Google Patents
Multifunctional flame-retardant cotton fabric and preparation method and application thereof Download PDFInfo
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- D06M10/02—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 ultrasonic or sonic; Corona discharge
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Abstract
The invention belongs to the field of flame-retardant modification of cotton fabrics, and discloses a multifunctional flame-retardant cotton fabric and a preparation method and application thereof. The method comprises the following steps: carrying out plasma treatment on the cotton fabric to obtain a pretreated cotton fabric; and (3) sequentially carrying out self-assembly on the two-dimensional layered nano material with the thermoelectric sensing characteristic and the polyhydroxy high molecular compound on the surface of the pretreated cotton fabric to obtain the multifunctional flame-retardant cotton fabric. The method is simple, mild in condition and environment-friendly; the prepared cotton fabric has excellent flame retardant property, has the functions of sensitive temperature sensing, fire early warning, piezoresistive sensing, electrothermal effect and the like, and can be widely applied to the fields of fire rescue, building decoration, traffic transportation, intelligent electronic skin and the like.
Description
Technical Field
The invention belongs to the field of flame-retardant modification of cotton fabrics, and particularly relates to a multifunctional flame-retardant cotton fabric and a preparation method and application thereof.
Background
The cotton fabric has excellent biodegradability, biocompatibility, air permeability, softness and comfort, so that the cotton fabric is widely applied to the fields of clothing fabrics, home decoration, transportation and the like. However, the main component of the cotton fabric is inflammable cellulose substance (the content is more than 90%), when the cotton fabric is subjected to high temperature or flame, the cotton fabric is very easy to be subjected to thermal cracking and oxidative degradation, a levoglucose monomer is generated, combustible gas is generated, and meanwhile, heat released in the combustion process is fed back to the surface of the cotton fabric to further promote the degradation of the cotton fabric, so that a combustion cycle is formed until the cotton fabric is completely burnt. In addition, once the cotton fabric is ignited, the cotton fabric can be violently burnt in a short time, the spreading speed is extremely high, and serious potential safety hazards exist. Therefore, how to effectively improve the fire safety of cotton fabrics and reduce casualties and property loss is a key problem to be solved urgently in the field of cotton fabric modification and application.
At present, researchers have conducted extensive research on flame retardant modification of cotton fabrics. The commonly used modification method is to construct a flame-retardant coating on the surface by chemical grafting, sol-gel, dipping method, layer-by-layer self-assembly and other techniques. Compared with the flame-retardant modification of the precursor, the surface modification of the fabric has the advantages that the coating agent covers the surface of the fabric, so that the fabric can quickly respond to external flame before contacting with the flame and undergoing thermal degradation, and the high-efficiency flame-retardant effect is realized. The fabric will not burn as long as the coating has good fire resistance. In addition, the flame-retardant coating does not damage the internal structure of the base material, and has little influence on the comprehensive performance of the fabric.
In recent years, with the rapid development of high and new technical fields such as artificial intelligence, internet of things, man-machine interaction, electronic skins and the like, people have higher requirements on the functionality and the intelligence of textiles. The temperature is one of the most common and important environmental factors, plays an irreplaceable role in the process of reflecting physiological activities, environmental influences and equipment running states, and accurate and reliable temperature sensing can provide key information for human health, motion state monitoring, device service life prolonging and other problems. More importantly, the fire disaster often starts from local abnormal high temperature, and if the abnormal high temperature can be monitored in the fire disaster germination period and early warning signals can be sent out in time, the probability of the fire disaster is greatly reduced, and casualties and property loss are effectively reduced. Meanwhile, the pressure plays a crucial role in sensing the motion state of the human body or the robot. For example, cotton fabric with piezoresistive sensing function is attached to joints such as fingers and wrists, and the health state of human body and the operation condition of equipment can be fed back according to the acquired piezoresistive change information. In addition, in the actual use process, if a lower voltage is applied, the temperature of the cotton fabric can be regulated, the effects of cold prevention, warm keeping, heating, deicing and snow melting are achieved, and the application in an extremely cold weather environment can be met. Therefore, on the basis of realizing the efficient flame retardance of the cotton fabric, the cotton fabric is further endowed with the functions of temperature sensing, fire early warning, piezoresistive sensing, electric heating effect and the like, so that the fireproof safety of the cotton fabric can be greatly improved, and the application range of the cotton fabric can be greatly expanded. However, the currently prepared flame-retardant cotton fabric is often single in function, can only delay the spread of fire in different degrees, cannot solve the problem of use safety of the cotton fabric from the source, and is difficult to meet the multifunctional use requirement.
Disclosure of Invention
The invention aims to provide a flame-retardant cotton fabric with temperature sensing and fire early warning functions and a preparation method thereof, aiming at the defects of flammability and single function of the existing cotton fabric. The invention overcomes the defects of flammability of cotton fabrics and adverse influence of traditional halogen and phosphorus flame retardants on the environment from the source, and realizes the purposes of green preparation, energy conservation, environmental protection and high-efficiency flame retardance. The flame-retardant cotton fabric has the functions of piezoresistive sensing, electrothermal effect and the like while greatly improving the use safety.
The multifunctional flame-retardant coating is constructed on the surface of cotton fabric by adopting a polyhydroxy macromolecular compound and a two-dimensional layered nano material with thermoelectric sensing characteristics as main raw materials and a layer-by-layer self-assembly method. As the two-dimensional layered nano material with the thermoelectric sensing characteristic has rich transition metal elements, the polyhydroxy high molecular compound in the two-dimensional layered nano material can be catalyzed to form a compact protective carbon layer in the heating process. Meanwhile, the two raw materials are oriented spontaneously and orderly in the drying process, so that the coating can present a stable, compact and orderly layered structure, the barrier to combustible gas and heat is effectively improved, and the efficient flame retardant effect is exerted. In addition, the ordered laminated structure is more beneficial to the interconnection between the laminated thermoelectric response materials and between the thermoelectric material and the front and back surfaces of the cotton fabric to form a stable multiple conductive path. When the cotton fabric is locally heated, current carriers in the thermoelectric material in the heated area can migrate to the low-temperature area along the layered conductive path, so that potential difference is generated at the cold end and the hot end of the coating, and the magnitude of the potential difference and the magnitude of the temperature difference at the cold end and the hot end of the coating form a stable direct proportional function relationship. The prepared multifunctional flame-retardant cotton fabric can realize sensitive sensing of abnormal temperature change and can send out timely alarm signals to dangerous temperatures. Meanwhile, due to the existence of multiple conductive paths, when the prepared multifunctional flame-retardant cotton fabric is stimulated by external pressure, the contact modes among the conductive paths can change in different degrees such as fiber contact and fiber bundle contact, the monitoring on different strain sizes is realized, and the multifunctional flame-retardant cotton fabric is endowed with an excellent piezoresistive sensing function. While the highly efficient conductive pathGiving it a low resistance, according to the joule heating effect (Q = U) when connected to an external power supply 2 t/R) can rapidly generate heat at a lower voltage, thereby achieving a highly efficient electrothermal effect. Therefore, the multifunctional flame-retardant cotton fabric provided by the invention can realize the temperature detection function on the surrounding environment, has the functions of fire early warning, piezoresistive sensing, electric heating effect and the like, and can be widely applied to the fields of fire rescue, building decoration, traffic transportation, intelligent electronic skin and the like with higher fire safety requirements.
The invention also aims to provide application of the multifunctional flame-retardant cotton fabric. The multifunctional flame-retardant cotton fabric provided by the invention has the temperature detection function on the surrounding environment, has the functions of fire early warning, piezoresistive sensing, electric heating effect and the like, and can be widely applied to the fields of fire rescue, architectural decoration, traffic transportation, intelligent electronic skin and the like with higher fire safety requirements.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a multifunctional flame-retardant cotton fabric comprises the following steps: carrying out plasma treatment on the cotton fabric to obtain a pretreated cotton fabric; and (3) sequentially carrying out self-assembly on the two-dimensional layered nano material with the thermoelectric sensing characteristic and the polyhydroxy high molecular compound on the surface of the pretreated cotton fabric to obtain the multifunctional flame-retardant cotton fabric.
The two-dimensional layered nano material with the thermoelectric sensing characteristic is more than one of titanium carbide nanosheets, nitrogen carbide nanosheets, niobium carbide nanosheets, molybdenum disulfide nanosheets, vanadium carbide nanosheets and molybdenum carbide nanosheets.
The layer size of the two-dimensional layered nano material is 0.2-10 mu m, and the interlayer spacing is 0.5-3 nm.
The polyhydroxy high molecular compound is more than one of hydroxy cellulose and derivatives thereof, hydroxypropyl methyl cellulose and derivatives thereof, polyvinyl alcohol, chitosan and derivatives thereof, potato starch, corn amylopectin, pullulan and hydroxyethyl methyl cellulose.
The hydroxy cellulose and its derivatives are more than one of hydroxyethyl cellulose, hydroxymethyl cellulose, sodium hydroxyethyl cellulose and hydroxypropyl cellulose.
The preparation method of the multifunctional flame-retardant cotton fabric specifically comprises the following steps:
1) Respectively preparing a two-dimensional layered nano material with thermoelectric sensing characteristics and a polyhydroxy high molecular compound into a dispersion liquid A and a dispersion liquid B; the dispersion liquid A is obtained by dispersing a two-dimensional layered nano material with thermoelectric sensing characteristics in a solvent; the dispersion liquid B is obtained by dissolving or dispersing a polyhydroxy high molecular compound in a solvent;
2) Carrying out plasma treatment on the cotton fabric to obtain a pretreated cotton fabric; dip-coating the pretreated cotton fabric with the dispersion liquid A, suspending the cotton fabric dipped with the dispersion liquid A or fixing the cotton fabric at a certain angle with a horizontal plane, and then drying; dip-coating the dispersion liquid B, namely hanging the cotton fabric dipped with the dispersion liquid B or fixing the cotton fabric at a certain angle with a horizontal plane, and drying; circulating and finally drying to obtain the multifunctional flame-retardant cotton fabric; fixing the cotton fabric dipped with the dispersion liquid A at a certain angle with a horizontal plane, wherein the certain angle is 45-135 degrees, preferably 75-105 degrees; the cotton fabric dipped with the dispersion liquid B is fixed at a certain angle with the horizontal plane, wherein the certain angle is 45-135 degrees, and preferably 75-105 degrees. The fixing means fixing two ends or four sides of the cotton fabric.
When the cotton fabric dipped with the dispersion liquid B is hung or fixed at a certain angle with the horizontal plane, the hung or fixed cotton fabric dipped with the dispersion liquid B rotates 180 degrees relative to the hung or fixed cotton fabric dipped with the dispersion liquid A, namely the fixed or hung upper end of the cotton fabric dipped with the dispersion liquid B is the fixed or hung lower end of the cotton fabric dipped with the dispersion liquid A, and the fixed or hung lower end of the cotton fabric dipped with the dispersion liquid B is the fixed or hung upper end of the cotton fabric dipped with the dispersion liquid A.
The circulation refers to dip-coating the dried cotton fabric dipped with the dispersion liquid A, hanging or fixing and drying; dip-coating the dispersion liquid B, suspending or fixing, drying, and circulating the operation; the number of cycles is 0 to 10.
When the pretreated cotton fabric is dipped and coated with the dispersion liquid A, the dipping and coating time is 2-10 min; the drying is blast drying or vacuum drying; the drying temperature is 50-60 ℃, and the drying time is 10-25 min;
when the dispersion liquid B is dip-coated, the dip-coating time is 5-15 min; the drying is blast drying or vacuum drying; the drying temperature is 50-70 ℃, and the drying time is 10-15 min.
The drying temperature for final drying is 45-55 ℃; the final drying is blast drying or vacuum drying; the vacuum drying time is 6-12 h.
The solvent in the dispersion liquid A in the step 1) is more than one of water, absolute ethyl alcohol, n-pentane and acetone.
In the step 1), the solvent in the dispersion liquid B is more than one of water, absolute ethyl alcohol and n-butyl alcohol.
The concentration of the dispersion liquid A in the step 1) is 10-20 mg/mL; the preparation of the dispersion liquid A adopts ultrasonic dispersion, the power of the ultrasonic dispersion is 100-500W, the temperature is-5 ℃, and the dispersion time is 0.5-3 h.
The concentration of the dispersion liquid B in the step 1) is 5-20 mg/mL; the preparation of the dispersion liquid B adopts a stirring mode, and the stirring time is 2-48 h.
Conditions of the plasma treatment in step 2): the processing pressure is 0.1-0.2 mbar, the processing atmosphere is oxygen atmosphere, and the processing time is 300-600 s.
The mass ratio of the two-dimensional layered nano material to the polyhydroxy high molecular compound is (10-20): (5-20).
The multifunctional flame-retardant cotton fabric is prepared by the preparation method.
The multifunctional flame-retardant cotton fabric can be applied to the fields of temperature sensing, fire early warning, piezoresistive sensing, electric heating effect and the like. When the prepared multifunctional flame-retardant cotton fabric is connected into a voltage detection circuit, when one end of the cotton fabric is heated, a stable and repeatable potential difference can be quickly formed between a cold end and a hot end, and the magnitude of the potential difference and the magnitude of the temperature difference form a functional relation, so that the prepared multifunctional flame-retardant cotton fabric can realize sensitive sensing on temperature change; meanwhile, if the alarm device is connected in series in the circuit, when the set potential difference is achieved, fire early warning can be triggered, an alarm signal is sent out, and a sensitive fire early warning function is achieved. If the prepared multifunctional flame-retardant cotton fabric is connected into a resistance detection circuit, the cotton fabric can analyze the health state of a human body and the operation condition of equipment according to the acquired piezoresistive change information, and the application in the piezoresistive sensing field is realized. In addition, if the prepared multifunctional flame-retardant cotton fabric is connected with a power supply, the electrothermal effect of electrifying and generating heat can be realized.
The multifunctional flame-retardant cotton fabric has the temperature detection function on the surrounding environment, has the functions of fire early warning, piezoresistive sensing and electric heating effect, and is applied to the fields of fire rescue, architectural decoration, transportation, intelligent electronic skin and the like with higher fire safety requirements
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the multifunctional flame-retardant cotton fabric provided by the invention can realize halogen-free and phosphorus-free green high-efficiency flame retardance through a simple preparation process, and has a wide market application prospect.
2. When the multifunctional flame-retardant cotton fabric provided by the invention encounters flame, the layered nano material in the multifunctional flame-retardant cotton fabric has excellent barrier property on one hand, and can quickly catalyze polyhydroxy high molecular compounds to carry out carbonization reaction on the other hand, so that a layered porous carbon layer with excellent thermal stability and heat insulation and oxygen isolation capability is generated, and the high-efficiency flame-retardant effect is exerted.
3. When the multifunctional flame-retardant cotton fabric provided by the invention is heated, current carriers in the two-dimensional layered nano thermoelectric material can migrate along the temperature gradient and form a stable potential difference at two ends of the cotton fabric, the magnitude of the potential difference and the magnitude of the temperature difference between the high and low temperature regions form a direct function relationship, and the function relationship is stable and repeatable, so that the cotton fabric is endowed with sensitive and repeatable temperature detection and fire early warning functions.
4. The multifunctional flame-retardant cotton fabric provided by the invention has good electrical conductivity, has a unique layered structure and a unique weaving structure, and under the action of different external stresses, contact points between layered materials and cotton fabrics can be changed to different degrees, so that the resistance is changed, the cotton fabric provided by the invention has excellent piezoresistive sensing performance, and meanwhile, the cotton fabric provided by the invention has excellent electrothermal effect due to an efficient conductive path constructed between the two-dimensional layered nano material and the cotton fabric.
Drawings
FIG. 1 is a micro calorimetric test result of the multifunctional flame-retardant cotton fabric prepared in example 1; modified-multifunctional flame-retardant cotton fabric, unmodified-cotton fabric;
FIG. 2 is a thermogravimetric curve of the multifunctional flame-retardant cotton fabric prepared in example 1 under a nitrogen atmosphere; modified-multifunctional flame-retardant cotton fabric, unmodified-cotton fabric;
FIG. 3 is a voltage-time change curve of the multifunctional flame-retardant cotton fabric prepared in example 1 at 200 ℃;
FIG. 4 is a real-time resistance change curve of the multifunctional flame-retardant cotton fabric prepared in example 1 under different strains;
FIG. 5 is a cycle stability curve of the electrothermal effect of the multifunctional flame-retardant cotton fabric prepared in example 1 under a direct current voltage of 3.5V.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following drawings and examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Preparation of dispersion a: ultrasonically dispersing 8g of titanium carbide nanosheets (with the lamella size of about 5 mu m and the interlayer spacing of about 0.5 nm) and 50mL of absolute ethyl alcohol in ice-water bath (at 0 ℃) for 2 hours to form uniform dispersion liquid A, and properly adjusting the solid content of the uniform dispersion liquid A to 15mg/mL for later use;
(2) Preparation of dispersion B: mechanically stirring 35g of hydroxy cellulose (hydroxyethyl cellulose) and 300mL of deionized water at room temperature for 48 hours to form uniform mixed dispersion liquid B, and properly adjusting the solid content of the uniform mixed dispersion liquid B to 10mg/mL for later use;
(3) Preparing a multifunctional flame-retardant cotton fabric: respectively taking 10mL of two dispersions, immersing the cotton fabric subjected to oxygen plasma treatment for 500s (the treatment pressure is 0.2mbar, the power is 500W, each surface is treated for 1 time) in the dispersion A for 10min, vertically suspending the dipped cotton fabric, spontaneously orienting and drying in a blowing oven at 50 ℃ for 25min, then immersing the cotton fabric in the dispersion B for 10min (the dried cotton fabric rotates 180 degrees along the vertical direction, namely the lowest point of the cotton fabric rotates to the highest point, then immersing in the dispersion B for 10 min), vertically suspending in the oven (the suspended cotton fabric dipped with the dispersion B rotates 180 degrees relative to the suspended cotton fabric dipped with the dispersion A, namely the suspension end of the cotton fabric dipped with the dispersion B is the lower end of the cotton fabric dipped with the dispersion A when the cotton fabric is suspended), then drying in the blowing oven at 50 ℃ for 15min, repeating the above self-assembly for 2 cycles (the 2 cycles means that the pre-treated cotton fabric is dipped in the dispersion A, suspended, dried, then suspended in the flame-retardant dispersion B, dried, and finally drying in a multifunctional suspension oven to obtain the dip-coated cotton fabric, and finally drying the suspension and the dip-coated cotton fabric. The prepared multifunctional flame-retardant cotton fabric is subjected to vertical combustion, micro calorimetric measurement, thermal stability, temperature sensing, fire early warning, piezoresistive sensing and electrothermal effect testing, and the results are shown in tables 1 and 2 and figures 1-5.
FIG. 1 is a micro calorimetric test result of the multifunctional flame-retardant cotton fabric prepared in example 1; FIG. 2 is a thermogravimetric curve of the multifunctional flame-retardant cotton fabric prepared in example 1 under a nitrogen atmosphere; FIG. 3 is a voltage-time change curve of the multifunctional flame-retardant cotton fabric prepared in example 1 at 200 ℃; FIG. 4 is a real-time resistance change curve of the multifunctional flame-retardant cotton fabric prepared in example 1 under different strains; fig. 5 is a cycle stability curve of an electrothermal effect of the multifunctional flame-retardant cotton fabric prepared in example 1 under a direct current voltage of 3.5V.
From the micro calorimetric curve (figure 1) and the thermal weight loss curve (figure 2), the thermal release rate of the modified cotton fabric is obviously reduced, the thermal stability is also obviously improved, and the use safety of the cotton fabric is greatly improved. As can be seen from Table 1, if only layered nanomaterial was attached to the surface of cotton fabric (comparative example 2) or only polyhydroxy high molecular compound was attached (comparative example 3), the fabric burned vigorously during the vertical burning test until completely burned out. In contrast, this example shows excellent flame retardant performance throughout the test, especially with a carbon residue length of only 35mm. The reason is that when the coating meets flame, the polyhydroxy high molecular compound can quickly generate carbonization reaction to bond the layered nanometer materials together, and the coating surface can be kept compact and complete even if the coating is burned by the flame for a long time. Meanwhile, the gasification product generated during the carbonization of the polyhydroxy high molecular compound can expand the interior of the coating to form a honeycomb porous structure, so that the coating has excellent heat insulation and oxygen insulation capability and has efficient flame retardant effect on internal cotton fabrics.
If the prepared multifunctional flame-retardant cotton fabric is connected into a voltage detection circuit to enable one end of the cotton fabric to be heated, a stable and repeatable potential difference can be rapidly formed between the cold end and the hot end of the cotton fabric, and meanwhile, the formed potential difference and the temperature gradient present a direct proportional function relationship, which shows that the prepared cotton fabric has a sensitive temperature sensing function. As can be seen from figure 3, when one end of the prepared cotton fabric is placed on a hot table at 200 ℃, the potential difference between the cold end and the hot end can reach 1mV within 2.8s, thereby triggering the alarm device. Therefore, the multifunctional flame-retardant cotton fabric provided by the invention can play a sensitive temperature detection function in the fire germination stage, can prevent the cotton fabric from not being burnt, and improves the use safety of the cotton fabric from the source.
Meanwhile, as can be seen from table 2, the multifunctional flame-retardant cotton fabric prepared by the embodiment has a repeatable fire early warning function. The fire alarm device can be triggered only 2.2 seconds after the fire is met, and meanwhile, the fire alarm device can be triggered when the fire is met for the second time and the third time, which shows that the cotton fabric prepared by the invention can still sensitively give an early warning even under the condition of fire re-ignition. In contrast, if only the layered nano material with the thermoelectric sensing characteristic is attached to the surface of the cotton fabric (comparative example 2), the triggering can be carried out only once, and the triggering time is longer. As can be seen from the table 1, the reason that the fire behavior can rapidly spread when the fabric meets fire in the comparative example 2, so that the conductive path is damaged, therefore, the polyhydroxy high molecular compound and the layered nano material with the thermoelectric sensing characteristic are assembled on the surface of the cotton fabric simultaneously, so that the fabric not only can endow the fabric with excellent flame retardant performance, but also can be used as a fire early warning sensor to effectively monitor the fire behavior development condition of a fire scene.
If the multifunctional flame-retardant cotton fabric prepared by the embodiment is connected into the resistance detection circuit, the cotton fabric can analyze the health state of a human body and the operation condition of equipment according to the acquired piezoresistive change information, and the application in the piezoresistive sensing field is realized. Fig. 4 is a graph showing the real-time variation of resistance under different strain levels. It can be seen from the figure that under different strains of 1.5-4.5%, the multifunctional flame-retardant cotton fabric provided by the invention shows different resistance change rates and response recovery times, and the larger the strain is, the larger the resistance change rate is, and the longer the response recovery time is. And after different pressure and release cycles, the resistivity of the alloy hardly changes, and the alloy shows excellent fatigue resistance and stability.
In addition, if the multifunctional flame-retardant cotton fabric prepared by the embodiment is connected with a power supply, the electric heating application of electrifying to generate heat can be realized. In the actual use process, if a lower voltage is applied, the temperature of the cotton fabric can be regulated and controlled, the electric heating deicing and snow melting are realized, the influence of liquid environments (such as water, ice and snow and other conditions) on the conductive network and the sensing performance is greatly avoided, and the excellent electric heating performance is endowed to effectively prolong the service life of the device. FIG. 5 is a circulation stability curve of the prepared multifunctional flame-retardant cotton fabric which is electrified for 30s under the voltage of 3.5V and cooled for 30 s. As can be seen from the figure, the surface temperature of the multifunctional flame-retardant cotton fabric prepared under the voltage of 3.5V can be rapidly increased to about 35 ℃ in a short time, and meanwhile, the temperature can still be kept stable after 10 times of circulation. Therefore, the cotton fabric provided by the invention has great potential application value in the fields of firefighter protective clothing, robot electronic skin and the like.
Example 2
(1) Preparation of dispersion a: ultrasonically dispersing 8g of molybdenum carbide nanosheets (with the lamella size of about 8 microns and the interlayer spacing of about 2 nm) and 50mL of acetone in an ice water bath (at 0 ℃) for 1h to form uniform mixed dispersion liquid A, and properly adjusting the solid content of the uniform mixed dispersion liquid A to 15mg/mL for later use;
(2) Preparation of dispersion B: mechanically stirring 20.0g of chitosan derivative (carboxymethyl chitosan) and 300mL of deionized water at room temperature for 36h to form uniform mixed dispersion liquid B, and properly adjusting the solid content of the uniform mixed dispersion liquid B to 5mg/mL for later use;
(3) Preparing a multifunctional flame-retardant cotton fabric: respectively taking 10mL of two dispersions, immersing the cotton fabric subjected to oxygen plasma treatment for 500s (the treatment pressure is 0.2mbar, the treatment times are 1 time) in the dispersion A for 10min, suspending in an oven, performing spontaneous orientation drying in a forced air oven at 50 ℃ for 25min, then rotating 180 degrees in the vertical direction, immersing in the dispersion B for 10min, suspending in the oven vertically, and then drying in the forced air oven at 50 ℃ for 15min (after the cotton fabric dipped with the dispersion B is suspended, the cotton fabric dipped with the dispersion B rotates 180 degrees relative to the suspended cotton fabric dipped with the dispersion A, namely the suspension end of the cotton fabric dipped with the dispersion B is the lower end when the cotton fabric dipped with the dispersion A is suspended); and repeating the assembly for 4 cycles, and drying in a vacuum oven at 55 ℃ for 12 hours after the final assembly is finished, thereby obtaining the multifunctional flame-retardant cotton fabric. The test method of this example is the same as example 1.
By comparing the present embodiment with example 1, it is found that the heat release rate can be greatly reduced and the thermal stability can be improved by using the molybdenum carbide nanosheet and the chitosan derivative. As can be seen from Table 1, the prepared cotton fabric immediately self-extinguished after the flame was removed by 12s of ignition, the smoldering time was also only 1.5s, and the carbon residue length was only 25mm. Meanwhile, the temperature sensing performance of the cotton fabric material is tested, so that the cotton fabric material prepared by the embodiment has a sensitive temperature sensing function, when the cotton fabric material is connected with an alarm to form an alarm device, the multifunctional cotton fabric material is found to send an alarm signal only within 2.8s after encountering flames, so that people are reminded to evacuate timely, and the second and third triggering times are respectively 12.7s and 14.2s (shown in table 2). Besides, piezoresistive sensing and electrothermal performance tests show that the piezoresistive sensing and electrothermal effects are still stable and repeatable.
Example 3
(1) Preparation of dispersion a: ultrasonically dispersing 8.0g of titanium carbide nanosheets (with the lamella size being about 5 microns and the interlayer spacing being about 0.5 nm) and 50mL of deionized water in an ice-water bath (at 0 ℃) for 0.5h to form uniform mixed dispersion liquid A, and properly adjusting the solid content of the uniform mixed dispersion liquid A to 15mg/mL for later use;
(2) Preparation of dispersion B: mechanically stirring 95.0g of chitosan derivative (carboxymethyl chitosan) and 300mL of deionized water at room temperature for 48 hours to form uniform mixed dispersion liquid B, and properly adjusting the solid content of the mixed dispersion liquid B to 20mg/mL for later use;
(3) Preparing a multifunctional flame-retardant cotton fabric: respectively taking 10mL of the two dispersions, immersing the cotton fabric subjected to oxygen plasma treatment for 500s (the treatment pressure is 0.2mbar, the treatment times are 1 time) in the dispersion A for 10min, performing spontaneous orientation drying in a forced air oven at 50 ℃ for 25min, then rotating the cotton fabric in the vertical direction for 180 degrees, immersing in the dispersion B for 10min, and then drying in the forced air oven at 50 ℃ for 15min; and repeating the assembly for 4 cycles, and drying in a vacuum oven at 45 ℃ for 10 hours after the final assembly is finished, thereby obtaining the multifunctional flame-retardant cotton fabric. The test method of this example is the same as example 1.
Compared with the embodiment 1, the heat release rate of the multifunctional flame-retardant cotton fabric prepared by the embodiment is greatly reduced, and the thermal stability and the vertical burning test response are improved. In addition, the multifunctional flame-retardant cotton fabric prepared by the embodiment has more excellent conductivity, so that the temperature sensing performance, the fire early warning performance, the piezoresistive sensing performance and the electrothermal effect of the multifunctional flame-retardant cotton fabric are improved to different degrees. This is probably due to the fact that the increase of the content of the polyhydroxy compound in the system leads to the corresponding increase of the content of the titanium carbide nanosheet in the assembling process, and the layers are combined more tightly.
Example 4
(1) Preparation of dispersion a: ultrasonically dispersing 10.0g of vanadium carbide (with the lamella size of about 7 mu m and the interlayer spacing of about 3 nm) and 50mL of deionized water at 5 ℃ for 3 hours to form uniform mixed dispersion liquid A, and properly adjusting the solid content of the uniform mixed dispersion liquid A to 20mg/mL for later use;
(2) Preparation of dispersion B: adding polyvinyl alcohol (M) into a container w 9000-10000) and potato starch (mass ratio is 1) and 300mL of n-butanol, mechanically stirring at room temperature for 48 hours to form uniform mixed dispersion liquid B, and properly adjusting the solid content of the mixed dispersion liquid B to 10mg/mL for later use;
(3) Preparing a multifunctional flame-retardant cotton fabric: firstly, placing cotton fabric under the condition that the treatment pressure is 0.1mbar for 3 times of oxygen plasma treatment, wherein the treatment time is 600s each time, and obtaining the cotton fabric treated by the plasma; then respectively taking 10mL of two dispersion solutions, immersing the cotton fabric subjected to plasma treatment into the dispersion solution A for 10min, suspending the cotton fabric in an oven, performing spontaneous orientation drying in a blast oven at 60 ℃ for 10min, then rotating the cotton fabric by 180 degrees in the vertical direction, immersing the cotton fabric into the dispersion solution B for 10min, and drying the cotton fabric in the blast oven at 50 ℃ for 15min; and repeating the assembly for 2 cycles, and drying in a vacuum oven at 55 ℃ for 12 hours after the final assembly is finished, thereby obtaining the multifunctional flame-retardant cotton fabric. The test method of this example is the same as example 1.
The multifunctional flame-retardant cotton fabric prepared by the embodiment is also found to have outstanding flame-retardant performance through a micro calorimetric test, a thermal stability test and a vertical combustion test, and the flammability characteristic of the cotton fabric material can be greatly improved. The sensitivity was found to be almost indistinguishable from example 1 by temperature sensing tests. It can be seen from table 2 that the fire warning function is more sensitive, the trigger time is only 1.1s for the first ignition, and the trigger time is only 9.8s and 10.6s for the second and third repeated ignitions. The piezoresistive sensing and electrothermal effect tests show that the sensor still has controllable sensing characteristics and electrothermal effect.
Example 5
(1) Preparation of dispersion a: ultrasonically dispersing 10g of vanadium carbide (with the lamella size of about 10 mu m and the interlayer spacing of about 3 nm) and 50mL of a mixed solvent of deionized water and ethanol (the volume ratio is 1;
(2) Preparation of dispersion B: adding 100.0g of corn amylopectin and 400mL of a mixed solvent of deionized water and ethanol (volume ratio is 1;
(3) Preparing a multifunctional flame-retardant cotton fabric: respectively taking 15mL of the two dispersions, immersing the cotton fabric subjected to plasma treatment for 600s in an atmosphere of 0.1mbar into the dispersion A for 5min, vertically hanging the cotton fabric in a blast oven, and drying the cotton fabric for 25min at 50 ℃; then, the mixture is rotated by 180 degrees in the vertical direction, immersed in the dispersion liquid B for 15min, vertically hung in a blast oven, and spontaneously oriented and dried for 10min at 60 ℃ (namely 1 cycle of repeated assembly); and finally, drying the cotton fabric in a vacuum drying oven at 50 ℃ for 10 hours, thereby self-assembling the cotton fabric layer by layer into the multifunctional flame-retardant cotton fabric. The test method of this example is the same as example 1.
The embodiment finds that the multifunctional flame-retardant cotton fabric prepared by only assembling one cycle has excellent flame retardance, temperature sensing, fire early warning, piezoresistive sensing and electrothermal effects. For example, it can be seen from table 1 that the after-flame time and smoldering time of the multifunctional flame-retardant cotton fabric prepared in the embodiment are both 0s, the length of the carbon residue is only 32mm, and it can be seen from table 2 that the alarm device can be triggered only 1.6s after encountering flame, and meanwhile, the alarm device can be triggered quickly after the second and third ignition, and the piezoresistive sensing performance and the electric heating performance are not affected. The reason is probably that the larger interlayer spacing improves the dispersibility of the vanadium carbide nanosheets in the solvent, and the larger lamella size enables the action area of the vanadium carbide nanosheets and the cotton fabric to be larger, so that the vanadium carbide nanosheets can be better protected, and a more efficient conductive path can be formed.
Example 6
(1) Preparation of dispersion a: performing ultrasonic dispersion on 6g of molybdenum disulfide (the size of a lamella is about 10 mu m, and the interlayer distance is about 1.3 nm) and 50mL of n-pentane at the temperature of-5 ℃ for 3 hours to form a uniform mixed dispersion liquid A, and adjusting the solid content to 10mg/mL for later use;
(2) Preparation of dispersion B: adding 100.0g of hydroxypropyl methyl cellulose and 400mL of absolute ethyl alcohol into a container, mechanically stirring for 24h at room temperature to form uniform mixed dispersion liquid B, and properly adjusting the solid content of the mixed dispersion liquid B to 20mg/mL for later use;
(3) Preparing a multifunctional flame-retardant cotton fabric: respectively taking 30mL of the dispersion liquid A and 30mL of the dispersion liquid B, and simultaneously carrying out oxygen plasma treatment on the cotton fabric for 3 times under the condition of 0.1mbar, wherein each time of treatment is 300s, so as to obtain the cotton fabric treated by the plasma; and then, soaking the cotton fabric into the dispersion liquid A for 2min, drying the cotton fabric in a blowing oven at 60 ℃ for 15min, rotating the cotton fabric in the vertical direction for 180 degrees, soaking the cotton fabric into the dispersion liquid B for 5min, drying the cotton fabric in the blowing oven at 70 ℃ for 10min, repeatedly assembling the cotton fabric for 5 cycles, and drying the cotton fabric in a vacuum drying oven at 55 ℃ for 6h after the final assembly is finished, so that the multifunctional flame-retardant cotton fabric is self-assembled layer by layer. The test method of this example is the same as example 1.
The heat release rate, the thermal stability and the vertical burning test of the multifunctional flame-retardant cotton fabric prepared by the embodiment are compared, and the multifunctional flame-retardant cotton fabric also has good flame-retardant performance, particularly, as can be seen from the table 1, after hydroxypropyl methyl cellulose and molybdenum disulfide nanosheets are attached to the surface of the cotton fabric, after the flame is removed in 12 seconds of ignition, the flame is immediately extinguished, no smoldering phenomenon occurs, and the length of carbon residue is only 32mm. Meanwhile, the preparation process has almost no influence on the conductivity of the conductive film, so that the performances of temperature sensing, fire early warning, piezoresistive sensing, electrothermal effect and the like of the conductive film can be maintained in the same range as that of the conductive film in the embodiment 1.
Example 7
(1) Preparation of dispersion a: adding 10g of vanadium carbide (with the lamella size of about 10 μm and the interlayer spacing of about 3 nm) and 50mL of a mixed solvent of deionized water and ethanol (with the volume ratio of 1;
(2) Preparation of dispersion B: adding 100g of Prussian blue polysaccharide and a mixed solvent of 400mL of deionized water and ethanol (volume ratio is 1;
(3) Preparing a multifunctional flame-retardant cotton fabric: respectively taking 15mL of the two dispersions, immersing the cotton fabric which is subjected to plasma treatment for 600s (the treatment times are 1 time) in an atmosphere of 0.1mbar into the dispersion A for 5min, vertically hanging the cotton fabric in a blast oven, and drying the cotton fabric for 25min at 50 ℃; then, rotating the dispersion liquid B by 180 degrees in the vertical direction, immersing the dispersion liquid B in the dispersion liquid B for 15min, vertically hanging the dispersion liquid B in a blast oven, performing spontaneous orientation drying for 10min at 60 ℃, and repeating the assembly for 3 cycles; and finally, drying the cotton fabric in a vacuum drying oven at 50 ℃ for 10 hours, thereby self-assembling the cotton fabric layer by layer into the multifunctional flame-retardant cotton fabric. The test method of this example is the same as example 1.
The multifunctional flame-retardant cotton fabric prepared by the embodiment is subjected to performance tests, and the fact that the prussian blue polysaccharide is adopted in addition to the cellulose, the chitin and the starch polyhydroxy compound can achieve good flame-retardant performance and multiple functions. Flame retardant tests (including micro calorimetric, thermal stability and vertical combustion tests) find that the polysaccharide polyol and the two-dimensional layered nano material with the thermoelectric sensing characteristic have good synergistic effect. Particularly, the thermal stability is improved more remarkably. Meanwhile, the temperature sensing, fire early warning, piezoresistive sensing and electric heating performances of the sensor are not obviously different from those of the embodiment 1.
Example 8
(1) Preparation of dispersion a: ultrasonically dispersing 10g of a nitrogen carbide nanosheet (with the lamella size of about 0.2 mu nm and the interlayer spacing of about 0.5 nm) and a mixed solvent of 50mL of deionized water and ethanol (with the volume ratio of 1: 1) in an ice-water bath (at 0 ℃) for 0.5h to form a uniform mixed dispersion liquid A, and adjusting the solid content to 20mg/mL for later use;
(2) Preparation of dispersion B: adding 100g of corn amylopectin and 400mL of a mixed solvent of deionized water and ethanol (volume ratio is 1;
(3) Preparing a multifunctional flame-retardant cotton fabric: respectively taking 15mL of the two dispersions, immersing the cotton fabric subjected to plasma treatment for 600s in an atmosphere of 0.1mbar into the dispersion A for 5min, vertically hanging the cotton fabric in a blast oven, and drying the cotton fabric for 25min at 50 ℃; then, immersing the dispersion liquid B in the dispersion liquid B for 15min, rotating the dispersion liquid B in a vertical direction for 180 degrees, vertically hanging the dispersion liquid B in a blast oven, performing spontaneous orientation drying for 10min at 60 ℃, and repeating the assembly for 5 cycles; and finally, drying the cotton fabric in a vacuum drying oven at 50 ℃ for 10 hours, thereby self-assembling the multifunctional flame-retardant cotton fabric layer by layer. The test method of this example is the same as example 1.
The embodiment discovers that the multifunctional flame-retardant cotton fabric material with excellent flame-retardant property and good conductivity can be prepared by performing multifunctional modification on pure cotton fabric by adopting the nitrogen carbide nanosheet and the corn amylopectin.
Example 9
(1) Preparation of dispersion a: adding 5.0g of niobium carbide nanosheets (with the lamella size of about 0.4 μm and the interlayer spacing of about 0.5 nm) and 15.0g of molybdenum disulfide nanosheets (with the lamella size of about 10 μm and the interlayer spacing of about 1.3 nm) and a mixed solvent of 75mL of deionized water and ethanol (with the volume ratio of 1;
(2) Preparation of dispersion B: adding 100.0g of corn amylopectin and 400mL of a mixed solvent of deionized water and ethanol (volume ratio is 1;
(3) Preparing a multifunctional flame-retardant cotton fabric: respectively taking 15mL of the two dispersions, immersing cotton fabrics subjected to plasma treatment for 600s in an atmosphere of 0.1mbar into the dispersion A for 5min, vertically suspending in a blast oven, and drying at 50 ℃ for 25min; then, it was rotated 180 ° in the vertical direction, immersed in dispersion B for 15min, hung vertically in a forced air oven, and dried spontaneously for 10min at 60 ℃ (i.e., assembly was repeated for 1 cycle); and finally, drying the cotton fabric in a vacuum drying oven at 50 ℃ for 10 hours, thereby self-assembling the cotton fabric layer by layer into the multifunctional flame-retardant cotton fabric. The test method of this example is the same as example 1.
It is found by comparing example 1 that when niobium carbide nanosheets and molybdenum disulfide nanosheets are adopted simultaneously, the heat release rate is slightly increased, the self-extinguishing performance in the vertical burning test is slightly reduced, but the self-extinguishing performance is still far smaller than that of comparative examples 1-3, and the thermal stability and the temperature sensing performance are almost similar to those of example 1. The test on the piezoresistive sensing performance shows that the resistance change rate is improved when the same strain is applied, and meanwhile, the test on the cycle stability of electrifying the electrothermal performance for 30s and cooling for 30s shows that the multifunctional flame-retardant cotton fabric prepared by the embodiment can still maintain constant temperature after 15 cycles.
Comparative example 1
In order to verify that the multifunctional flame-retardant cotton fabric prepared by the invention has excellent flame-retardant performance, untreated pure cotton fabric is used as comparison. The test method was the same as in example 1.
Comparative example 2
In order to verify that the two-dimensional layered nano-material and the polyhydroxy high molecular compound have excellent synergistic flame retardant effect, cotton fabrics processed by the two-dimensional layered nano-material are used as a contrast. The test method was the same as in example 1.
The specific procedure of comparative example 2:
(1) Preparation of dispersion a: adding 8.0g of titanium carbide nanosheets (with the lamella size being about 5 mu m and the interlayer spacing being about 0.5 nm) and 50mL of absolute ethyl alcohol into a container, ultrasonically dispersing for 2 hours in ice-water bath (at 0 ℃) to form uniform dispersion liquid A, and properly adjusting the solid content of the uniform dispersion liquid A to 15mg/mL for later use;
(2) Preparing a flame-retardant cotton fabric: 10mL of dispersion A were taken and cotton fabric which had been subjected to oxygen plasma treatment for 500s (treatment pressure 0.2 mbar) was immersed in dispersion A for 10min, spontaneously oriented dried in a forced air oven at 50 ℃ for 25min, subsequently rotated 180 ℃ in the vertical direction, immersed in dispersion A for 10min and then dried in a forced air oven at 50 ℃ for 15min. And repeating the assembling for 2 cycles, and drying in a vacuum oven at 55 ℃ for 12 hours after the final assembling is finished, thereby obtaining the flame-retardant cotton fabric.
Comparative example 3
In order to verify that the two-dimensional layered nano material adopted by the invention has excellent synergistic flame retardant effect with the polyhydroxy high molecular compound, cotton fabrics treated by only using the polyhydroxy high molecular compound are used as comparison. The test method was the same as in example 1.
Specific procedure for comparative example 3:
(1) Preparation of dispersion B: adding 35.0g of hydroxy cellulose (hydroxyethyl cellulose) and 300mL of deionized water into a container, mechanically stirring at room temperature for 48 hours to form uniform mixed dispersion liquid B, and properly adjusting the solid content of the mixed dispersion liquid B to 10mg/mL for later use;
(2) Preparing a flame-retardant cotton fabric: 10mL of dispersion B were taken and the cotton fabric which had been treated with oxygen plasma for 500s (treatment pressure 0.2 mbar) was immersed in dispersion B for 10min, spontaneously orientation-dried in a forced air oven at 50 ℃ for 25min, subsequently rotated 180 ℃ in the vertical direction and immersed in dispersion B for 10min and then dried in a forced air oven at 50 ℃ for 15min. And repeating the assembly for 2 cycles, and drying in a vacuum oven at 55 ℃ for 12 hours after the final assembly is finished, thereby obtaining the flame-retardant cotton fabric.
Test method
1. Vertical burning test: a300 mm x 80mm sample was placed in a vertical burning test chamber according to GB/T5455-2014 vertical method for testing burning Performance of textiles, exposed to a Bunsen burner flame having a height of 40mm for 12s, removed, observed for testing phenomena and recorded for afterflame time and smoldering time.
2. Microcalorimetry test (MCC): weighing 10-12mg of sample in a micro calorimeter, carrying out pyrolysis in a nitrogen atmosphere at 100-600 ℃, wherein the heating rate is 1K/s, and the gas subjected to pyrolysis is oxidized in a combustion chamber at 900 ℃.
3. Thermogravimetric Testing (TG): weighing 5-10mg of pure cotton fabric or modified cotton fabric, placing the pure cotton fabric or modified cotton fabric in an alumina crucible, and measuring a thermal weight loss curve in a thermogravimetric analyzer under the nitrogen atmosphere. The heating rate is 20K/min, the air flow rate in the furnace is 30mL/min, and the test temperature range is 35-800 ℃.
4. And (3) temperature perception test: copper wires were glued to both ends of the cotton fabric using silver paste and connected to a digital multimeter (DMM 6500 6/2, keithley instruments, usa) while connected in parallel to a temperature controlled thermal table, and voltage time curves at different temperatures were recorded, with the dimensions of the sample being 50mm x 20mm x 6mm.
5. And (3) fire early warning test: a40 mm multiplied by 20mm multiplied by 6mm sample is connected with a voltage alarm through a lead, then the sample is placed 20mm above an alcohol lamp and is exposed to the flame of the alcohol lamp with the height of 40mm, the flame is removed after 30s, the early warning voltage is set to be 1mV, and the voltage curve of the sample and the early warning response time are recorded.
6. And (3) testing an electrothermal effect: the method comprises the steps of adhering two ends of a cotton fabric modified by copper wires by using silver paste, connecting the copper wires with the positive pole and the negative pole of a direct-current voltage source respectively, and recording the change of the surface temperature of a sample along with time in the testing process by using an infrared thermal imager, wherein the size of the sample is 20mm multiplied by 10mm multiplied by 6mm.
7. And (3) piezoresistive sensing test: the method comprises the steps of adhering two ends of a modified cotton fabric by using silver paste, connecting a copper wire with a four-probe resistivity measurement system (RTS-9, 4 probe, china) and a digital multimeter (DMM 65006 1/2, keithley instrument in the United states), applying a certain pressure on a sample to enable the sample to deform to a certain degree, and recording the change of resistance in the pressure application process, wherein the size of the sample is 20mm multiplied by 10mm multiplied by 6mm.
The performance test data for the flame retardant cotton fabric prepared in each example and comparative example are shown in tables 1 and 2.
Table 1 vertical burning test data of flame retardant cotton fabric of examples 1 to 9 and comparative examples 1 to 3
Table 2 fire early warning test data of flame retardant cotton fabric of examples 1 to 9 and comparative examples 1 to 3
It can be seen from the examples 1 to 9 in tables 1 and 2 that the multifunctional flame-retardant cotton fabric prepared by using different layered nano materials with thermoelectric sensing characteristics, polyhydroxy high molecular compounds and solvents under different process conditions has excellent flame retardant performance, temperature sensing, fire warning, piezoresistive sensing and electrothermal effects.
The analysis of the embodiment 1-9 shows that the preparation method adopted by the invention can effectively overcome the defects of flammability of cotton fabrics and avoidance of traditional flame retardant treatment, and achieves the purposes of green preparation, energy conservation, environmental protection and high-efficiency flame retardant. Meanwhile, the cotton fabric can be endowed with the functions of temperature sensing, fire early warning, piezoresistive sensing and electric heating effect, the use safety of the cotton fabric can be greatly improved, and the cotton fabric is widely applied to the fields of fire rescue, architectural decoration, transportation, intelligent electronic skin and the like with higher fire safety requirements.
The results are shown in Table 1, table 2, and FIGS. 1 to 5
When the cotton fabric is subjected to plasma treatment in the preparation process of the multifunctional flame-retardant cotton fabric, the two sides of the cotton fabric are subjected to plasma treatment, and the plasma treatment time of one side is 300-600 s. The power of the plasma treatment is 100-1000W. The number of plasma treatments is 1 to 3. The number of treatments indicates that both sides were treated 1 time and the number of treatments was 1; both sides were treated 2 times indicating that the number of plasma treatments was 2 times. The plasma RF frequency was 13.56MHz.
The molecular weight of polyvinyl alcohol in the polyhydroxy high molecular compound adopted by the invention is 6000-12000 (M) w ) (ii) a The chitosan and its derivatives include chitosan, carboxymethyl chitosan, glycol chitosan, hydroxypropyl chitosan, methyl chitosan, etc.
In addition, when the multifunctional flame-retardant cotton fabric is dipped in the dispersion liquid in the preparation process, the cotton fabric can be randomly placed in the dispersion liquid and does not need to be vertically placed in the dispersion liquid. The cotton fabric, when dry, cannot be parallel to a horizontal plane, preferably perpendicular to a horizontal plane. When the cotton fabric dipped with the dispersion liquid A and the cotton fabric dipped with the dispersion liquid B are dried after being hung or fixed, the upper ends of the cotton fabric dipped with the dispersion liquid A and the lower ends of the cotton fabric dipped with the dispersion liquid B are opposite, namely the upper end of the cotton fabric dipped with the dispersion liquid A is the lower end of the cotton fabric dipped with the dispersion liquid B, and the lower end of the cotton fabric dipped with the dispersion liquid A is the upper end of the cotton fabric dipped with the dispersion liquid B. The mode is suspended or fixed, and the effect is better.
Claims (4)
1. A preparation method of a multifunctional flame-retardant cotton fabric is characterized by comprising the following steps: the method comprises the following steps:
1) Respectively preparing a two-dimensional layered nano material with thermoelectric sensing characteristics and a polyhydroxy high molecular compound into a dispersion liquid A and a dispersion liquid B; the dispersion liquid A is obtained by dispersing a two-dimensional layered nano material with thermoelectric sensing characteristics in a solvent; the dispersion liquid B is obtained by dissolving or dispersing a polyhydroxy high molecular compound in a solvent;
2) Carrying out plasma treatment on the cotton fabric to obtain a pretreated cotton fabric; dip-coating the pretreated cotton fabric with the dispersion liquid A, suspending the cotton fabric dipped with the dispersion liquid A or fixing the cotton fabric at a certain angle with a horizontal plane, and then drying; dip-coating the dispersion liquid B, namely suspending the cotton fabric dip-coated with the dispersion liquid B or fixing the cotton fabric dip-coated with the dispersion liquid B at a certain angle with a horizontal plane, and drying; circulating and finally drying to obtain the multifunctional flame-retardant cotton fabric; fixing the cotton fabric dipped with the dispersion liquid A at a certain angle with a horizontal plane, wherein the certain angle is 75-105 degrees; fixing the cotton fabric dipped with the dispersion liquid B at a certain angle with a horizontal plane, wherein the certain angle is 75-105 degrees; the fixation means that two ends or the periphery of the cotton fabric are fixed;
when the cotton fabric dipped with the dispersion liquid B is hung or fixed at a certain angle with the horizontal plane, the hung or fixed cotton fabric dipped with the dispersion liquid B rotates 180 degrees relative to the hung or fixed cotton fabric dipped with the dispersion liquid A, namely the fixed or hung upper end of the cotton fabric dipped with the dispersion liquid B is the fixed or hung lower end of the cotton fabric dipped with the dispersion liquid A, and the fixed or hung lower end of the cotton fabric dipped with the dispersion liquid B is the fixed or hung upper end of the cotton fabric dipped with the dispersion liquid A;
the circulation is to dip-coat the dispersion liquid A after drying the cotton fabric dipped with the dispersion liquid B, hang or fix the cotton fabric and dry the cotton fabric; dip-coating the dispersion liquid B, suspending or fixing, drying, and circulating the operation; the number of the circulation is 1 to 5;
the mass ratio of the two-dimensional layered nano material to the polyhydroxy high molecular compound is (10 to 20): (5 to 20);
the two-dimensional layered nano material with the thermoelectric sensing characteristic is more than one of a titanium carbide nano sheet, a nitrogen carbide nano sheet, a niobium carbide nano sheet, a molybdenum disulfide nano sheet, a vanadium carbide nano sheet and a molybdenum carbide nano sheet;
the polyhydroxy high molecular compound is more than one of hydroxycellulose and derivatives thereof, hydroxypropyl methylcellulose and derivatives thereof, polyvinyl alcohol, chitosan and derivatives thereof, potato starch, corn amylopectin, pullulan and hydroxyethyl methylcellulose;
the concentration of the dispersion liquid A in the step 1) is 10 to 20mg/mL;
the concentration of the dispersion liquid B in the step 1) is 5-20 mg/mL.
2. The preparation method of the multifunctional flame-retardant cotton fabric according to claim 1, characterized in that: the hydroxy cellulose and the derivative thereof are more than one of hydroxyethyl cellulose, hydroxymethyl cellulose, sodium hydroxyethyl cellulose and hydroxypropyl cellulose;
the chitosan and its derivatives comprise more than one of chitosan, carboxymethyl chitosan, glycol chitosan, hydroxypropyl chitosan, and methyl chitosan.
3. The preparation method of the multifunctional flame-retardant cotton fabric according to claim 1, characterized in that: in the step 1), the solvent in the dispersion liquid A is more than one of water, absolute ethyl alcohol, n-pentane and acetone;
in the step 1), the solvent in the dispersion liquid B is more than one of water, absolute ethyl alcohol and n-butyl alcohol;
conditions of the plasma treatment in step 2): the processing pressure is 0.1 to 0.2mbar, the processing atmosphere is oxygen atmosphere, and the processing time is 300 to 600s.
4. The method for preparing a multifunctional flame-retardant cotton fabric according to claim 1, which is characterized in that:
when the pretreated cotton fabric is dip-coated with the dispersion liquid A, the dip-coating time is 2-10min; the drying is blast drying or vacuum drying; the drying temperature is 50 to 60 ℃, and the drying time is 10 to 25min;
when the dispersion liquid B is dip-coated, the dip-coating time is 5 to 15min; the drying is forced air drying or vacuum drying; the drying temperature is 50 to 70 ℃, and the drying time is 10 to 15min;
the drying temperature for final drying is 45 to 55 ℃; the final drying is forced air drying or vacuum drying; the vacuum drying time is 6 to 12 hours;
the layer size of the two-dimensional layered nano material is 0.2 to 10 mu m, and the interlayer distance is 0.5 to 3nm.
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