CN115928497A - Preparation method and application of high-low temperature thermal response double-sided paper - Google Patents
Preparation method and application of high-low temperature thermal response double-sided paper Download PDFInfo
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Abstract
The invention discloses a preparation method and application of high-low temperature thermal response double-sided paper, which comprises the steps of firstly taking hydroxyapatite (HAP for short), graphene oxide (GO for short) and 3-aminopropyltriethoxysilane (APTES for short) as raw materials to obtain GO/APTES/HAP composite paper; HAP and 10, 12-pentacosadiynoic acid (PCDA for short) are used as raw materials to obtain PCDA polymer (polyPCDA/HAP for short) composite paper; and finally, assembling the GO/APTES/HAP composite paper and the polyPCDA/HAP composite paper by using a silica gel adhesive to obtain the double-sided paper. The double-sided paper can respond to low-temperature (< 100 ℃) and high-temperature (> 100 ℃) environments of early fire and send out fire early warning signals. The invention can provide a new idea for a sensitive and rapid fire early warning system.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a preparation method of high-low temperature thermal response double-sided paper and application of the high-low temperature thermal response double-sided paper in fire early warning.
Background
Fire accidents are one of the most devastating common disasters threatening public and property safety. For example, 6/14/2017, ignition of the combustible insulation material on the outer wall of the Lanfeldt, london caused a fire, resulting in the death of 79 persons and the loss of 58 persons. Effectively reducing fire incidents becomes a significant challenge worldwide. The traditional smoke sensor can work only when smoke reaches a certain concentration after a fire disaster occurs, so that serious early warning delay is caused; the infrared sensor is easily affected by heat sources, distances and the like, and the anti-interference capability is poor. Therefore, the development of a fast and reliable fire early warning system is urgent.
Graphite oxide alkene (GO) is electrical insulation at room temperature almost, and the oxygen-containing group on GO surface can be got rid of to conflagration high temperature environment, changes into the reduction GO of high conductivity, and this kind of conversion only needs several seconds just can accomplish, can send out conflagration early warning signal in the very short time. However, GO sensors suffer from two disadvantages: (1) the thermal stability is poor, so that the early warning time is short; (2) the early warning temperature of GO to early fires is higher (> 100 ℃). Aiming at the 2 key problems, the invention innovatively provides high-low temperature response double-sided paper which consists of GO/APTES/HAP composite paper and polyPCDA/HAP composite paper, wherein the GO/APTES/HAP composite paper responds to a high-temperature environment (100 ℃), and ATPES improves GO thermal stability and increases early warning duration; the polyPCDA/HAP composite paper can change color at low temperature (100 ℃) and send out an early warning signal; the HAP acts as a stable skeleton, keeping the double-sided paper structurally stable in simulated fires.
Disclosure of Invention
The invention aims to provide a preparation method of high-low temperature thermal response double-sided paper aiming at the defects of the existing fire early warning sensor, which uses GO/APTES/HAP composite paper and polyPCDA/HAP composite paper as construction units, can respond to low-temperature (< 100 ℃) and high-temperature (> 100 ℃) environments of early fires and sends out early warning signals through color and electrical property changes.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-low temperature thermal response double-sided paper is prepared by taking hydroxyapatite (HAP for short), graphene oxide (GO for short) and 3-aminopropyltriethoxysilane (APTES for short) as raw materials to obtain GO/APTES/HAP composite paper; HAP and 10, 12-pentacosadiynoic acid (PCDA for short) are used as raw materials to obtain PCDA polymer (polyPCDA/HAP for short) composite paper; and finally, assembling the GO/APTES/HAP composite paper and the polyPCDA/HAP composite paper by using a silica gel adhesive to obtain the double-sided paper. The double-sided paper can respond to low-temperature (< 100 ℃) and high-temperature (> 100 ℃) environments of early fire and send out fire early warning signals.
The preparation method of the high-low temperature thermal response double-sided paper specifically comprises the following steps:
(1) Weighing a proper amount of APTES, and mixing the APTES with absolute ethyl alcohol and water to obtain an APTES solution;
(2) Weighing a proper amount of GO and HAP, and respectively dispersing in water to prepare GO water dispersion and HAP water dispersion with certain concentrations;
(3) Adding a proper amount of APTES solution and HAP dispersion liquid into GO dispersion liquid, heating and stirring to uniformly mix, cooling, filtering, forming and drying to obtain GO/APTES/HAP composite paper;
(4) Adding a proper amount of PCDA and HAP dispersion liquid into a sodium hydroxide aqueous solution, heating and stirring to uniformly mix, cooling, irradiating the slurry by using an ultraviolet lamp, filtering, forming and drying to obtain polyPCDA/HAP composite paper;
(5) And assembling GO/APTES/HAP composite paper and polyPCDA/HAP composite paper together by using silica gel, and drying to obtain the high-low temperature thermal response double-sided paper.
Further, in step (1), the mass ratio of APETS: ethanol: water = 10.
Further, the concentrations of GO dispersion and HAP dispersion in step (2) were 1 mg/ml and 2 mg/ml, respectively.
Further, in the step (3), the dosage of the APTES solution is 1-5 ml, the dosage of the HAP dispersion liquid is 5-15 ml, and the dosage of the GO dispersion liquid is 5-15 ml; the heating temperature is 50-100 ℃, and the stirring time is 1-5 hours; the drying condition is oven drying, the drying temperature is 40-60 ℃, and the drying time is 0.5-12 hours.
Further, in the step (4), the concentration of the sodium hydroxide aqueous solution is 0.1 mol/L, the dosage is 5-10 ml, the dosage of the PCDA is 20-50 mg, and the dosage of the HAP dispersion liquid is 10-20 ml; the heating temperature is 50-100 ℃, and the stirring time is 1-5 hours; the wavelength of the ultraviolet lamp is 254 nanometers, and the irradiation time is 5-30 minutes; the drying condition is oven drying, the drying temperature is 40-60 deg.C, and the drying time is 0.5-12 hr.
Further, the drying condition in the step (5) is drying at room temperature.
The application comprises the following steps: the high-low temperature thermal response double-sided paper is applied to the field of fire early warning: the double-sided paper can respond to low temperature of <100 ℃ and high temperature of >100 ℃ of early fire and send out fire early warning signals.
The invention has the beneficial effects that:
(1) The invention innovatively provides a design strategy of double-sided paper, wherein one piece of composite paper (GO/APTES/HAP) responds to a high-temperature environment (> 100 ℃) of an early fire and sends out an early warning signal through electric signal conversion; the other type of composite paper (polyPCDA/HAP) responds to the low temperature environment (< 100 ℃) of early fires by giving an early warning signal by colour change.
(2) In the present invention, the components of the double-sided paper perform their respective functions: GO is used as an electric signal conversion sensor; the APTES contains N and Si elements and has a flame retardant effect, organic Si is thermally decomposed at high temperature to form a nano silicon dioxide structure, and the nano silicon dioxide structure covers the surface of GO and plays a role in blocking oxygen and heat, so that the APTES can obviously improve the thermal stability of GO and prolong the early warning time; polyPCDA as a color transition sensor; the HAP is used as a stable framework to keep the structure of the double-sided paper stable in simulated fire. Under the synergistic effect of all the components, the double-sided paper realizes the high-low temperature thermal response of early fire and the effect of continuous early warning in simulated fire.
(3) In the preparation method provided by the invention, the raw materials are easy to obtain, the price is low, the instruments and equipment are simple, the process operation is simple, and good economic and environmental benefits are achieved.
Drawings
FIG. 1 is a scanning electron micrograph of a sample prepared according to examples 1 to 3;
FIG. 2 is a low temperature response process of a sample prepared in example 2;
FIG. 3 is a high temperature response process of a sample prepared in example 3;
FIG. 4 is a vertical burn comparison of samples prepared in example 3 and comparative example 2;
fig. 5 shows the operation of the samples prepared in example 1 and comparative example 1 in a simulated fire.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
(1) Preparing 120 ml of aqueous solution containing 1.76 g of calcium chloride dihydrate, 120 ml of aqueous solution containing 6.00 g of sodium hydroxide and 60 ml of aqueous solution containing 1.68 g of sodium dihydrogen phosphate dihydrate; sequentially adding the three aqueous solutions into a mixed solvent of 64 g of oleic acid and 84 g of ethanol, transferring the mixed solution into a stainless steel reaction kettle with a teflon lining, and carrying out solvothermal reaction at the reaction temperature of 180 ℃ for 24 hours; the product was washed with water and absolute ethanol alternately 3 times and finally dispersed in water to obtain an aqueous dispersion of HAP (concentration 2 mg/ml).
(2) 30 mg of PCDA was weighed and added to 7 ml of 0.1 mol/l aqueous sodium hydroxide solution; heating the solution by using an oil bath under magnetic stirring, wherein the heating temperature is 70 ℃, and the stirring time is 0.5 hour; then 15 ml of HAP dispersion liquid is added, and stirring is continued for 2 hours; cooling to room temperature, and irradiating the mixed solution for 10 minutes by using 254 nanometer ultraviolet light; and carrying out vacuum filtration molding and drying in a 45 ℃ oven for 0.5 hour to obtain the polyPCDA/HAP composite paper.
(3) Preparing a mixed solution of APETS and ethanol, wherein the mass ratio of the APETS to the ethanol is =10 = 75, taking 2 ml of the mixed solution, adding the mixed solution into 10 ml of GO water dispersion with the concentration of 1 mg/ml, heating the solution by using an oil bath under magnetic stirring, wherein the heating temperature is 80 ℃, and the stirring time is 2 hours; adding 10 ml of HAP aqueous dispersion with the concentration of 2 mg/ml, and continuously heating and stirring for 2 hours; and cooling to room temperature, performing vacuum filtration molding, and drying in an oven at 45 ℃ for 0.5 hour to obtain GO/APTES/HAP composite paper.
(4) Coating silica gel on one surface of GO/APTES/HAP composite paper, placing the polyPCDA/HAP composite paper on the silica gel surface, and drying at room temperature to obtain the polyPCDA/HAP-GO/APTES/HAP high-low temperature thermal response double-sided paper.
Example 2
(1) Preparing 120 ml of aqueous solution containing 1.76 g of calcium chloride dihydrate, 120 ml of aqueous solution containing 6.00 g of sodium hydroxide and 60 ml of aqueous solution containing 1.68 g of sodium dihydrogen phosphate dihydrate; sequentially adding the three aqueous solutions into a mixed solvent of 64 g of oleic acid and 84 g of ethanol, transferring the mixed solution into a stainless steel reaction kettle with a teflon lining, and carrying out solvothermal reaction at 180 ℃ for 24 hours; the product was washed with water and absolute ethanol alternately 3 times and finally dispersed in water to obtain an aqueous dispersion of HAP (concentration 2 mg/ml).
(2) 30 mg of PCDA was weighed and added to 7 ml of 0.1 mol/l aqueous sodium hydroxide solution; heating the solution by using an oil bath under magnetic stirring, wherein the heating temperature is 70 ℃, and the stirring time is 0.5 hour; then 15 ml of HAP dispersion liquid is added, and stirring is continued for 2 hours; cooling to room temperature, and irradiating the mixed solution for 10 minutes by using 254 nanometer ultraviolet light; and carrying out vacuum filtration molding and oven drying at 45 ℃ for 0.5 hour to obtain the polyPCDA/HAP composite paper.
Example 3
(1) Preparing 120 ml of aqueous solution containing 1.76 g of calcium chloride dihydrate, 120 ml of aqueous solution containing 6.00 g of sodium hydroxide and 60 ml of aqueous solution containing 1.68 g of sodium dihydrogen phosphate dihydrate; sequentially adding the three aqueous solutions into a mixed solvent of 64 g of oleic acid and 84 g of ethanol, transferring the mixed solution into a stainless steel reaction kettle with a teflon lining, and carrying out solvothermal reaction at 180 ℃ for 24 hours; the product was washed with water and absolute ethanol alternately 3 times and finally dispersed in water to obtain an aqueous dispersion of HAP (concentration 2 mg/ml).
(2) Preparing a mixed solution of APETS and ethanol, wherein the mass ratio of the APETS to the ethanol is =10 = 75, taking 2 ml of the mixed solution, adding the mixed solution into 10 ml of GO water dispersion with the concentration of 1 mg/ml, heating the solution by using an oil bath under magnetic stirring, wherein the heating temperature is 80 ℃, and the stirring time is 2 hours; adding 10 ml of HAP aqueous dispersion with the concentration of 2 mg/ml, and continuously heating and stirring for 2 hours; and cooling to room temperature, performing vacuum filtration molding, and drying in an oven at 45 ℃ for 0.5 hour to obtain GO/APTES/HAP composite paper.
Comparative example 1
(1) Preparing 120 ml of aqueous solution containing 1.76 g of calcium chloride dihydrate, 120 ml of aqueous solution containing 6.00 g of sodium hydroxide and 60 ml of aqueous solution containing 1.68 g of sodium dihydrogen phosphate dihydrate; sequentially adding the three aqueous solutions into a mixed solvent of 64 g of oleic acid and 84 g of ethanol, transferring the mixed solution into a stainless steel reaction kettle with a teflon lining, and carrying out solvothermal reaction at 180 ℃ for 24 hours; the product was washed with water and absolute ethanol alternately 3 times and finally dispersed in water to obtain an aqueous dispersion of HAP (concentration 2 mg/ml).
(2) 30 mg of PCDA was weighed and added to 7 ml of 0.1 mol/l aqueous sodium hydroxide solution; heating the solution by using an oil bath under magnetic stirring, wherein the heating temperature is 70 ℃, and the stirring time is 0.5 hour; then 15 ml of HAP dispersion liquid is added, and stirring is continued for 2 hours; cooling to room temperature, and irradiating the mixed solution for 10 minutes by using 254 nanometer ultraviolet light; and carrying out vacuum filtration molding and oven drying at 45 ℃ for 0.5 hour to obtain the polyPCDA/HAP composite paper.
(3) Adding 10 ml of HAP aqueous dispersion with the concentration of 2 mg/ml into 10 ml of GO aqueous dispersion with the concentration of 1 mg/ml; heating the solution by using an oil bath under magnetic stirring, wherein the heating temperature is 80 ℃, and the stirring time is 2 hours; and cooling to room temperature, performing vacuum filtration molding, and drying in a 45 ℃ oven for 0.5 hour to obtain the GO/HAP composite paper.
(4) Coating silica gel on one surface of GO/HAP composite paper, placing the polyPCDA/HAP composite paper on the silica gel surface, and drying at room temperature to obtain the polyPCDA/HAP-GO/HAP double-sided paper.
Comparative example 2
(1) Preparing 120 ml of aqueous solution containing 1.76 g of calcium chloride dihydrate, 120 ml of aqueous solution containing 6.00 g of sodium hydroxide and 60 ml of aqueous solution containing 1.68 g of sodium dihydrogen phosphate dihydrate; sequentially adding the three aqueous solutions into a mixed solvent of 64 g of oleic acid and 84 g of ethanol, transferring the mixed solution into a stainless steel reaction kettle with a teflon lining, and carrying out solvothermal reaction at 180 ℃ for 24 hours; the product was washed with water and absolute ethanol alternately 3 times and finally dispersed in water to obtain an aqueous dispersion of HAP (concentration 2 mg/ml).
(2) Adding 10 ml of HAP aqueous dispersion with the concentration of 2 mg/ml into 10 ml of GO aqueous dispersion with the concentration of 1 mg/ml; heating the solution by using an oil bath under magnetic stirring, wherein the heating temperature is 80 ℃, and the stirring time is 2 hours; and cooling to room temperature, performing vacuum filtration molding, and drying in a 45 ℃ oven for 0.5 hour to obtain the GO/HAP composite paper.
Analysis of results
It can be observed from fig. 1 that: (1) in a of FIG. 1, it is shown that the polyPCDA has a lamellar structure, embedded in the HAP nanowire, and the color of the polyPCDA/HAP composite paper is purple; (2) b in FIG. 1 shows that APTES and GO wrap the HAP nanowire skeleton well, and the GO/APTES/HAP composite paper is dark black in color; (3) the cross-sectional view of the double-sided paper shown in c of fig. 1 shows the interface where tight bonding is formed between the polyPCDA/HAP composite paper and the silica gel, and between the GO/APTES/HAP composite paper and the silica gel, illustrating the feasibility of using the silica gel adhesive to prepare high and low temperature thermal response double-sided paper.
From fig. 2 it can be observed that: the polyPCDA/HAP composite paper is purple at 30 ℃ and turns red at 70 ℃, which shows that the low-temperature environment (< 100 ℃) of early fire can be detected by utilizing the thermochromic function of the polyPCDA/HAP composite paper, and an early warning signal is sent out in a color change mode.
It can be observed from fig. 3 that: the GO/APTES/HAP composite paper is placed in a high-temperature environment, the current passing through the composite paper is gradually increased from 159 ℃, an early warning lamp in a circuit sends out an early warning signal, and the early warning lamp is brighter and brighter along with the continuous rise of the temperature, so that the characteristic that the electrical property of the GO/APTES/HAP composite paper changes along with the temperature can be utilized to detect the high-temperature environment (> 100 ℃) of an early fire.
It can be observed from fig. 4 that: putting GO/HAP composite paper and GO/APTES/HAP composite paper in a simulated fire for a vertical combustion experiment, wherein the GO/HAP composite paper is changed from black to white within 10 seconds, white areas gradually increase along with the prolonging of combustion time, black substances are GO, which shows that the thermal stability is poor, white substances are HAP, which shows that the HAP is a framework material with thermal stability; the appearance of GO/APTES/HAP composite paper is almost unchanged in the long-time combustion process, which shows that APTES can improve the thermal stability of GO.
It can be observed from fig. 5 that: in the simulated fire, the current passing through the polyPCDA/HAP-GO/HAP double-sided paper reaches the maximum value in 6 seconds, and then the current is reduced, which shows that the GO structure is gradually damaged by flame, and becomes 0 in 24 seconds, namely the fire early warning performance is lost; on the other hand, the current through polyPCDA/HAP-GO/APTES/HAP double-sided paper is gradually increased and can be kept stable within 30 seconds, namely APTES improves the thermal stability of GO, and continuous early warning is realized.
It will be understood by those skilled in the art that the foregoing is merely a preferred embodiment of the invention, and is not intended to limit the invention, and that any modification, equivalent replacement or improvement made within the spirit and principle of the invention should be included within the scope of protection of the invention.
Claims (9)
1. A preparation method of high-low temperature thermal response double-sided paper is characterized by comprising the following steps: firstly, taking hydroxyapatite HAP, graphene oxide GO and 3-aminopropyltriethoxysilane APTES as raw materials to obtain GO/APTES/HAP composite paper; then HAP and 10, 12-pentacosadiynoic acid PCDA are used as raw materials to obtain polyPCDA/HAP composite paper; and finally, assembling the GO/APTES/HAP composite paper and the polyPCDA/HAP composite paper by using a silica gel adhesive to obtain the high-low temperature thermal response double-sided paper.
2. The method for preparing the high and low temperature thermal response double-sided paper according to claim 1, characterized by comprising the following steps:
(1) Weighing a proper amount of APTES, and mixing the APTES with absolute ethyl alcohol and water to obtain an APTES solution;
(2) Weighing a proper amount of GO and HAP, respectively dispersing in water to prepare GO dispersion liquid and HAP dispersion liquid with certain concentrations;
(3) Adding a proper amount of APTES solution and HAP dispersion liquid into GO dispersion liquid, heating and stirring to uniformly mix, cooling, filtering, forming and drying to obtain GO/APTES/HAP composite paper;
(4) Adding a proper amount of PCDA and HAP dispersion liquid into a sodium hydroxide aqueous solution, heating and stirring to uniformly mix, cooling, irradiating the slurry by using an ultraviolet lamp, filtering, forming and drying to obtain the polyPCDA/HAP composite paper;
(5) And (3) assembling GO/APTES/HAP composite paper and polyPCDA/HAP composite paper together by using a silica gel adhesive, and drying to obtain the high-low temperature thermal response double-sided paper.
3. The method for preparing the high and low temperature thermal response double-sided paper according to claim 2, characterized in that: in the step (1), the mass ratio of APETS to ethanol to water = 10.
4. The method for preparing the high and low temperature thermal response double-sided paper according to claim 2, characterized in that: the concentrations of GO dispersion and HAP dispersion in step (2) were 1 mg/ml and 2 mg/ml, respectively.
5. The method for preparing the high and low temperature thermal response double-sided paper according to claim 2, characterized in that: in the step (3), the dosage of the APTES solution is 1-5 ml, the dosage of the HAP dispersion liquid is 5-15 ml, and the dosage of the GO dispersion liquid is 5-15 ml; the heating temperature is 50-100 ℃, and the stirring time is 1-5 hours; the drying condition is oven drying, the drying temperature is 40-60 ℃, and the drying time is 0.5-12 hours.
6. The method for preparing the high and low temperature thermal response double-sided paper according to claim 2, characterized in that: in the step (4), the concentration of the sodium hydroxide aqueous solution is 0.1 mol/L, the dosage is 5-10 ml, the dosage of PCDA is 20-50 mg, and the dosage of HAP dispersion liquid is 10-20 ml; heating at 50-100 deg.C, and stirring for 0.5-5 hr; the wavelength of the ultraviolet lamp is 254 nanometers, and the irradiation time is 5-30 minutes; the drying condition is oven drying, the drying temperature is 40-60 ℃, and the drying time is 0.5-12 hours.
7. The method for preparing the high and low temperature thermal response double-sided paper according to claim 2, characterized in that: the drying condition in the step (5) is room temperature drying.
8. A high and low temperature thermal response double-sided paper prepared by the method of any one of claims 1 to 7.
9. Use of the high and low temperature thermally responsive double-sided paper as claimed in claim 8 in the field of fire early warning, wherein the double-sided paper can give a fire early warning signal in response to a low temperature of <100 ℃ and a high temperature environment of >100 ℃ in an early fire.
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