CN115948938B - Flame-retardant rice paper with fire disaster early warning function and preparation method thereof - Google Patents
Flame-retardant rice paper with fire disaster early warning function and preparation method thereof Download PDFInfo
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- 235000007164 Oryza sativa Nutrition 0.000 title claims abstract description 65
- 235000009566 rice Nutrition 0.000 title claims abstract description 65
- 239000003063 flame retardant Substances 0.000 title claims abstract description 61
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 240000007594 Oryza sativa Species 0.000 title 1
- 241000209094 Oryza Species 0.000 claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 229920001661 Chitosan Polymers 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000002086 nanomaterial Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 26
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 7
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002070 nanowire Substances 0.000 claims description 7
- 235000002949 phytic acid Nutrition 0.000 claims description 7
- 229940068041 phytic acid Drugs 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000002048 multi walled nanotube Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000002109 single walled nanotube Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 5
- 239000000467 phytic acid Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000011282 treatment Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005316 response function Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention discloses flame-retardant rice paper with a fire disaster early warning function and a preparation method thereof, and the specific method comprises the following steps: s1: uniformly dispersing a carbon-based nano material in a water/chitosan solution to obtain a positively charged carbon-based nano dispersion liquid, and marking the positively charged carbon-based nano dispersion liquid as a solution A; s2: uniformly dispersing a carbon-based nanomaterial in a water/flame retardant solution to obtain a negatively charged flame-retardant carbon-based nano dispersion liquid, and marking the negatively charged flame-retardant carbon-based nano dispersion liquid as a solution B; s3: sequentially soaking/spraying the Xuan paper into the solution A and the solution B, and repeating the steps for 3 to 100 times to obtain flame-retardant Xuan paper; s4: and (3) soaking/spraying the dispersion liquid containing the odor-response nano material on the flame-retardant rice paper of the step (S3), and drying to obtain the flame-retardant rice paper with the odor response. The flame-retardant rice paper disclosed by the invention not only can realize the change of resistance along with the change of external temperature, but also can monitor the change of smell in real time, and can realize the ultrafast and early fire early warning of the flame-retardant rice paper.
Description
Technical Field
The invention relates to the technical field of rice paper, in particular to flame-retardant rice paper with a fire early warning function and a preparation method thereof.
Background
The rice paper is used as a common carrier for painting and calligraphy, improves the fireproof safety of the rice paper, and has very important significance for the preservation and inheritance of traditional Chinese cultures and excellent works of art.
An effective way to improve the fire safety of rice paper at present is to use a fire early warning system to monitor in real time, and once a fire occurs, an alarm is sent out rapidly, so that the loss caused by the fire can be reduced to the minimum. Although there are a large number of commercial fire alarm systems on the market, including smoke detectors and infrared flame detectors, their early warning and fire protection effects are not ideal. The existing fire detector is located at a certain distance from the combustion source, and can be triggered only when the smoke concentration or the infrared detection temperature reaches a critical value. Therefore, the fire early warning response is insensitive (most of the response time exceeds 100 s), so that the time for optimally controlling the fire is missed, and the fire extinguishing difficulty is increased. The rice paper with the fire early warning response function is prepared, and real-time monitoring of the rice paper can be realized. Therefore, the rice paper with the functions of flame retardance and fire early warning has very important significance for improving the fireproof safety of the rice paper.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides the flame-retardant rice paper with the fire disaster early warning function and the preparation method thereof, and the functional coating with the flame-retardant fire disaster early warning function is constructed on the surface of the rice paper, so that not only can the change of resistance along with the change of external temperature be realized, but also the change of smell can be monitored in real time, and the ultrafast and early fire disaster early warning of the flame-retardant rice paper can be realized.
The invention provides a preparation method of flame-retardant rice paper with a fire disaster early warning function, which comprises the following steps:
s1: preparation of positively charged carbon-based nanodispersions
Uniformly dispersing a carbon-based nano material in a water/chitosan solution to obtain a positively charged carbon-based nano dispersion liquid, and marking the positively charged carbon-based nano dispersion liquid as a solution A;
s2: preparation of negatively charged carbon-based nanodispersions
Uniformly dispersing a carbon-based nanomaterial in a water/flame retardant solution to obtain a negatively charged flame-retardant carbon-based nano dispersion liquid, and marking the negatively charged flame-retardant carbon-based nano dispersion liquid as a solution B;
s3: preparation of flame-retardant rice paper
Sequentially soaking/spraying the Xuan paper into the solution A and the solution B, and repeatedly treating for a plurality of times to obtain flame-retardant Xuan paper;
s4: preparation of flame-retardant rice paper with smell response
And (3) soaking/spraying the dispersion liquid containing the odor-response nano material on the flame-retardant rice paper of the step (S3), and drying to obtain the flame-retardant rice paper with the odor response.
Preferably, the carbon-based nanomaterial is one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, hydroxylated single-walled carbon nanotubes, hydroxylated multi-walled carbon nanotubes, aminated single-walled carbon nanotubes, aminated multi-walled carbon nanotubes, graphitized carbon nanotubes, single-layer graphene oxide, multi-layer graphene oxide, and MXene.
Preferably, the flame retardant is one or more of phytic acid, ammonium phytate, carboxylated chitosan, hexachlorocyclotriphosphazene, hexaphenoxy cyclotriphosphazene, ammonium polyphosphate and montmorillonite.
Preferably, the concentration of the chitosan solution in S1 is 0.1-2wt%, the pH is 4-6, and the mass ratio of the carbon-based nanomaterial to the chitosan is 0.5-2:1.
Preferably, the concentration of the flame retardant solution in the S2 is 0.5-20wt%, and the mass ratio of the carbon-based nanomaterial to the flame retardant is 0.5-2:1.
Preferably, the number of repeated treatments in S3 is 3-100.
Preferably, the rice paper in S3 is soaked for 1-240min each time, and is dried for 3-60min at 40-120 ℃ after each soaking/spraying.
Preferably, the nanomaterial of odor response in S4 is one or more of tin dioxide nanoparticles, tin dioxide nanowires, titanium dioxide nanoparticles, titanium dioxide nanowires, zinc dioxide nanoparticles, and zinc dioxide nanowires.
Preferably, the S4 contains the odor-responsive nanomaterial dispersion at a concentration of 0.1-5wt%, soaking time of 1-240min, drying temperature of 40-120deg.C, and drying time of 3-60min.
The flame-retardant rice paper with the fire disaster early warning function is prepared by the method.
The beneficial technical effects of the invention are as follows:
according to the invention, the coating with fire early warning and flame retarding functions is constructed on the surface of the rice paper in a layer-by-layer assembly mode, so that the resistance of the rice paper can be changed along with the change of the external temperature, the change of smell can be monitored in real time, and the ultrafast and early fire early warning of the rice paper can be realized.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
(1) 200mg of Graphene Oxide (GO) powder was dispersed into 200mL of deionized water to form a stable dispersion. 200mg HPTCP was then dissolved in 20mL ethanol and the HPTCP solution was slowly added to the GO dispersion with continuous stirring to prepare GO - @ HPTCP dispersion. 200mg of Chitosan (CS) was dissolved in 200mL deionized water and the pH was adjusted to 4 with acetic acid. Subsequently, 200mg Carbon Nanotubes (CNTs) were dispersed into the above chitosan solution, followed by ultrasonic dispersion for 20 min. Thereby obtaining CNTs@CS + And (3) a dispersion.
(2) The fire early warning flame-retardant rice paper is prepared by adopting a layer-by-layer self-assembly method. Soaking rice paper in CNTs@CS + The dispersion was kept for 5min, then washed in deionized water for 1 min and oven dried at 80℃for 10min. Then soaking the treated rice paper in GO - The @ HPTCP dispersion was run for 5min and then subjected to the same washing and drying process as described above. The above process was repeated until 10, 20, 30 times were reached.
(3) 1g of tin dioxide nanowires are dispersed into 100mL of deionized water, and the dispersion is treated by ultrasonic for 10min to obtain 1% tin dioxide stable dispersion. Spraying the treated rice paper with 1% tin dioxide stable dispersion liquid to prepare the flame-retardant rice paper with fire early warning function.
Example 2
(1) 200mg of Graphene Oxide (GO) powder was dispersed into 200mL of deionized water to form a stable dispersion. Then preparing 3% Phytic Acid (PA) solution, and slowly adding the PA solution into GO dispersion liquid under the condition of continuous stirring to prepare GO - Dispersion @ PA. 200mg of Chitosan (CS) was dissolved in 200mL deionized water and the pH was adjusted to 4 with acetic acid. Subsequently, 200mg Carbon Nanotubes (CNTs) were dispersed into the above chitosan solution, followed by ultrasonic dispersion for 20 min. Thereby obtaining CNTs@CS + And (3) a dispersion.
(2) The fire early warning flame-retardant rice paper is prepared by adopting a layer-by-layer self-assembly method. Soaking rice paper in CNTs@CS + Dispersing for 5minThen rinsed in deionized water for 1 minute and oven dried at 80 c for 10 minutes. Then soaking the treated rice paper in GO - The same washing and drying process as described above was then carried out in the @ PA dispersion for 5min and repeated until 10, 20, 30 times were reached.
(3) 1g of tin dioxide nanowires are dispersed into 100mL of deionized water, and the dispersion is treated by ultrasonic for 10min to obtain 1% tin dioxide stable dispersion. Spraying the treated rice paper with 1% tin dioxide stable dispersion liquid to prepare the flame-retardant rice paper with fire early warning function.
Example 3
(1) 200mg of Mxene powder is dispersed into 20mL deionized water, firstly, ultrasonic dispersion is carried out for 10min, then magnetic stirring is carried out for 2h, and the mixture is fully dispersed to form stable Mxene dispersion liquid. 200mg of Chitosan (CS) was dissolved in 200mL deionized water and the pH was adjusted to 4 with acetic acid. Subsequently, 200mg Carbon Nanotubes (CNTs) were dispersed into the above chitosan solution, followed by ultrasonic dispersion for 20 min. Thereby obtaining CNTs@CS + And (3) dispersing liquid.
(2) The fire early warning flame-retardant rice paper is prepared by adopting a layer-by-layer self-assembly method. Soaking rice paper in CNTs@CS + The dispersion was kept for 5min, then washed in deionized water for 1 min and oven dried at 80℃for 10min. Then the treated rice paper is soaked in Mxene dispersion liquid for 5min, and then the same cleaning and drying process is carried out, and the process is repeated until reaching 10, 20 and 30 times.
(3) 1g of tin dioxide nanowires are dispersed into 100mL of deionized water, and the dispersion is treated by ultrasonic for 10min to obtain 1% tin dioxide stable dispersion. Spraying the treated rice paper with 1% tin dioxide stable dispersion liquid to prepare the flame-retardant rice paper with fire early warning function.
The fire-retardant rice paper with fire early-warning function prepared in examples 1-3 was tested for fire-retardant performance by limiting oxygen index method, and the fire early-warning response of rice paper was tested, and the results are shown in table 1.
Wherein: the flame retardant property test method refers to GB/T5454-1997 fabrics burning property test-oxygen index method; the fire early warning response test method comprises the following steps: the fire-retardant rice paper is connected to a circuit with a small bulb (1.5 v) and a direct current power supply through testing, the rice paper is ignited and burnt under the fire-retardant rice paper by an alcohol lamp, the voltage of the direct current power supply when the small bulb is turned on in the rice paper burning process is measured to reflect the resistance of the rice paper, and the length of time required for the flame of the alcohol lamp to start to contact the rice paper until the small bulb is turned on reflects the fire early warning response sensitivity of the fire-retardant rice paper.
Table 1 Xuan paper Performance test
As can be seen from Table 1, examples 1-3 showed a gradual increase in oxygen index of the flame retardant Xuan paper with an increase in the number of treatments, indicating a gradual increase in flame retardant property, and when the treatment is performed more than 30 times, the oxygen index of the flame retardant Xuan paper can reach more than 27, and the flame retardant property is better, especially the oxygen index of example 2 can reach more than 30, and the flame retardant property is excellent. And as the treatment times are increased, the response voltage of the flame-retardant rice paper is gradually reduced, which shows that the resistance of the treated rice paper is gradually reduced. The fire early warning response time of the treated rice paper gradually decreases along with the increase of the treatment times, which shows that the early warning response sensitivity gradually increases, and especially the embodiment 3 can reach 0.25s after 30 times of treatment, and shows excellent early warning response sensitivity.
Claims (4)
1. The preparation method of the flame-retardant rice paper with the fire disaster early warning function is characterized by comprising the following steps:
s1: preparation of positively charged carbon-based nanodispersions
Uniformly dispersing a carbon-based nano material in a water/chitosan solution to obtain a positively charged carbon-based nano dispersion liquid, and marking the positively charged carbon-based nano dispersion liquid as a solution A;
s2: preparation of negatively charged carbon-based nanodispersions
Uniformly dispersing a carbon-based nanomaterial in a water/flame retardant solution to obtain a negatively charged flame-retardant carbon-based nano dispersion liquid, and marking the negatively charged flame-retardant carbon-based nano dispersion liquid as a solution B;
s3: preparation of flame-retardant rice paper
Sequentially soaking/spraying the Xuan paper into the solution A and the solution B, and repeating the steps for 3 to 100 times to obtain flame-retardant Xuan paper;
s4: preparation of flame-retardant rice paper with smell response
Soaking/spraying a dispersion liquid containing the odor-responsive nano material on the flame-retardant rice paper of the step S3, and drying to obtain the flame-retardant rice paper with the odor response;
the flame retardant is one or more of phytic acid, ammonium phytate, carboxylated chitosan, hexachlorocyclotriphosphazene, hexaphenoxy cyclotriphosphazene, ammonium polyphosphate and montmorillonite;
the nano material of the odor response in the S4 is one or more of tin dioxide nano particles, tin dioxide nano wires, titanium dioxide nano particles, titanium dioxide nano wires, zinc dioxide nano particles and zinc dioxide nano wires;
the concentration of the chitosan solution in the S1 is 0.1-2wt%, the pH is 4-6, and the mass ratio of the carbon-based nanomaterial to the chitosan is 0.5-2:1;
the concentration of the flame retardant solution in the S2 is 0.5-20wt%, and the mass ratio of the carbon-based nanomaterial to the flame retardant is 0.5-2:1;
s4, the concentration of the dispersion liquid containing the odor response nano material is 0.1-5wt%, the soaking time is 1-240min, the drying temperature is 40-120 ℃, and the drying time is 3-60min.
2. The method for preparing flame-retardant rice paper with fire disaster early warning function according to claim 1, wherein the carbon-based nanomaterial is one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, hydroxylated single-walled carbon nanotubes, hydroxylated multi-walled carbon nanotubes, aminated single-walled carbon nanotubes, aminated multi-walled carbon nanotubes, graphitized carbon nanotubes, single-layer graphene oxide, multi-layer graphene oxide and MXene.
3. The method for preparing fire-retardant rice paper with fire early warning function according to claim 1, wherein the rice paper in S3 is soaked for 1-240min each time, and dried for 3-60min at 40-120 ℃ each time after soaking/spraying.
4. The fire-retardant rice paper with fire early warning function prepared by the method according to any one of claims 1-3.
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