CN116462888A - Preparation method and application of efficient smoke suppression and attenuation hybrid material - Google Patents
Preparation method and application of efficient smoke suppression and attenuation hybrid material Download PDFInfo
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- CN116462888A CN116462888A CN202310540004.8A CN202310540004A CN116462888A CN 116462888 A CN116462888 A CN 116462888A CN 202310540004 A CN202310540004 A CN 202310540004A CN 116462888 A CN116462888 A CN 116462888A
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000779 smoke Substances 0.000 title claims description 110
- 230000001629 suppression Effects 0.000 title claims description 50
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 55
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 55
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 40
- 230000001988 toxicity Effects 0.000 claims description 22
- 231100000419 toxicity Toxicity 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
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- 238000001354 calcination Methods 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
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- 239000002105 nanoparticle Substances 0.000 claims description 9
- 239000002135 nanosheet Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000969 carrier Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 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 abstract description 11
- 239000003063 flame retardant Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
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- 238000012545 processing Methods 0.000 abstract description 4
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- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000781 heat-release-rate curve Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- 229910001151 AlNi Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002468 ceramisation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2293—Oxides; Hydroxides of metals of nickel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method and application of a high-efficiency smoke-suppressing and toxicity-reducing hybrid material, which abandons the formulation composition of the traditional smoke-suppressing and toxicity-reducing material, adopts alumina with different structures as a carrier, loads active component nickel oxide as the high-efficiency smoke-suppressing and toxicity-reducing hybrid material, and performs scientific interface regulation and control to realize the synergistic effect between the active component and the carrier, thereby comprehensively exerting the barrier effect and the catalytic effect, and achieving good smoke-suppressing, toxicity-reducing and flame-retardant effects when the high-efficiency smoke-suppressing and toxicity-reducing hybrid material is used in the processing process of thermoplastic polyurethane.
Description
Technical Field
The invention belongs to the field of polymer high-filling systems, and particularly relates to a preparation method and application of a high-efficiency smoke suppression and attenuation hybrid material. The addition of the high-efficiency smoke suppression and attenuation hybrid material of the invention can comprehensively reduce the smoke toxicity of the composite material, and achieve good smoke suppression, attenuation and flame retardance.
Background
The high molecular material is a high molecular compound with high molecular weight, can be used for preparing various materials and products, but the frequency of fire accidents is continuously increased due to the fact that most high molecular materials are easy to burn. Among them, thermoplastic Polyurethane (TPU) is a widely used polymer material, and its excellent elasticity, abrasion resistance and corrosion resistance make it widely used in various fields such as sports shoes, car seats, medical supplies, etc. However, TPU's release large amounts of fumes and harmful gases during processing and use. Therefore, improving the smoke suppression performance of the TPU is very important to ensure the safety of production sites. At present, the method for improving the smoke suppression performance of the TPU mainly comprises the steps of adding smoke suppression agents, changing material structures and the like. The addition of smoke suppressants can effectively reduce smoke and harmful gases generated when TPU burns, and halogen-free smoke suppressants are receiving more and more attention. Meanwhile, changing the microstructure and morphology of the TPU material is also an important way for improving the smoke suppression performance of the TPU material. In the future, the development of environment-friendly and efficient TPU smoke suppression technology is a research hot spot, and a more environment-friendly and efficient method is continuously explored and is widely applied to the fields of intelligent manufacturing, sustainable development and the like.
In order to ensure personnel safety and environmental sanitation, improving the smoke suppression performance of the TPU becomes an important research direction. In the related art, there have been several patent applications related to the technology and methods of suppressing smoke in TPU. Some of these patents provide methods of adding smoke suppressants to improve the smoke suppression performance of TPU, such as layered titanium carbide-molybdenum trioxide hybrid flame retardant (CN 111849145A), functionalized graphene surface nitrogen doped flame retardant (CN 109988411 a), aluminum hypophosphite hybrid flame retardant (CN 107312199 a), and the like. These techniques aim at achieving the smoke suppression goal of the TPU by adding specific compounds or increasing the proportion of specific ingredients in the material. Still other patents contemplate starting from the material structure itself to improve the smoke suppression properties of the TPU. For example, the flame retardant polypropylene and TPU composite material is added to reduce the combustion smoke generation of TPU (CN 104072977A), or the TPU is modified by ceramization to improve the smoke suppression performance (CN 107286636A). However, the above work has many disadvantages. Such as complex material preparation processes (requiring modification pretreatment of the TPU surface) and the use of organic solvents. Meanwhile, the prepared composite material has good flame retardant effect, but the smoke suppression and toxicity reduction effects are generally poor. Therefore, the design of the efficient smoke suppression and toxicity reduction hybrid material is particularly important for flame retardance and smoke suppression and toxicity reduction of the TPU material.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a preparation method and application of an efficient smoke suppression and attenuation hybrid material. The smoke-suppressing and toxicity-reducing hybrid material has the characteristics of high efficiency smoke suppression, toxicity reduction, flame retardance, greenness and the like, and can achieve good smoke suppression, toxicity reduction and flame retardance when used in the processing process of thermoplastic polyurethane.
The preparation method of the efficient smoke suppression and toxicity reduction hybrid material adopts alumina with different structures as a carrier, and loads active component nickel oxide as the efficient smoke suppression and toxicity reduction hybrid material, and specifically comprises the following steps:
step 1: firstly, synthesizing alumina nano particles, alumina nano sheets and alumina nano microspheres as carriers of smoke suppression and attenuation hybrid materials;
step 2: then uniformly dispersing the alumina carrier into normal hexane, dripping completely dissolved nickel nitrate aqueous solution into the system under the stirring condition, and continuously stirring and mixing for a certain time after the dripping is finished to finish the loading of active components;
step 3: and (2) drying the mixed solution obtained in the step (2) in a blast oven, and calcining at a high temperature in a muffle furnace after drying to obtain the high-efficiency smoke-suppressing and toxicity-reducing hybrid material.
Further, in the efficient smoke suppression and toxicity reduction hybrid material, the active center nickel oxide accounts for 10 weight percent of the total mass.
In the step 1, the alumina nano-particles are prepared by a coprecipitation method, and the size of the alumina nano-particles is in the range of 50-100 nm; the alumina nano-sheet is prepared by a hydrothermal method, and the size of the alumina nano-sheet is in the range of 5-30 mu m; the alumina nanometer microsphere is prepared by a template method, and the size of the alumina nanometer microsphere is in the range of 200-500 nm.
In the step 2, the mixing and stirring speed is 300rpm, and the stirring time is 30-60min; the concentration of the nickel nitrate aqueous solution is 0.1mol/L, and the nickel loading is 10%.
In the step 3, the drying temperature is 80-120 ℃ and the drying time is 6-12h; the calcination temperature is 400-600 ℃, and the calcination time is 6-10h.
The application of the efficient smoke suppression and attenuation hybrid material is that the smoke suppression and attenuation hybrid material is used as an additive to be added into thermoplastic polyurethane, so that the flame retardance and smoke suppression performance of the composite material are improved.
Furthermore, when the smoke suppression and attenuation hybrid material is used as an additive to be added into thermoplastic polyurethane, a solvent method is adopted to construct a composite material.
Further, the addition amount of the smoke suppression and attenuation hybrid material is 1-3wt%, such as 1wt%, 2wt%, 3wt% and the rest is thermoplastic polyurethane elastomer.
The beneficial effects of the invention are as follows:
1. the invention abandons the formulation composition of the traditional smoke suppression and attenuation materials, adopts the catalyst impregnation preparation technology to prepare the high-efficiency smoke suppression and attenuation agents with different structures, and realizes the comprehensive effect of the active components and the carrier through the metal-carrier interaction between the active components nickel and the carrier alumina by scientific interface regulation, thereby achieving good flame retardance and smoke suppression effects when the active components and the carrier are used for preparing polyurethane composite materials.
2. The invention prepares the high-efficiency smoke-suppressing and toxicity-reducing hybrid material with different structures by using a catalyst impregnation technology, prepares the composite material by a solvent method, has the advantages of easily available raw materials, short process route and controllable process, and is suitable for industrial production. The flame-retardant and smoke-suppressing material is used for processing and producing thermoplastic polyurethane elastomer, can achieve the purposes of flame retardance and smoke suppression, is safe and environment-friendly, and can reduce environmental pollution.
3. The preparation process of the invention has simple operation, green, low production cost, simple process, high benefit, strong controllability, no pollution of three wastes, less equipment investment and convenient use of products.
Drawings
FIG. 1 is a schematic structural diagram of a smoke suppression and attenuation hybrid material of the present invention.
Figure 2 shows XRD patterns of smoke suppressants of different structures in examples of the present invention.
Fig. 3 is an SEM image of smoke suppressants of different structures in the examples of the present invention. Wherein a and d are smoke suppressants taking alumina nano particles as carriers, b and e are smoke suppressants taking alumina nano sheets as carriers, and c and f are smoke suppressants taking alumina nano microspheres as carriers.
FIG. 4 is a graph showing the cone calorimeter curves of various amounts of addition versus material in examples of the present invention. Wherein a is the heat release rate curve of the composite materials with different addition amounts, b is the total heat release rate curve of the composite materials with different addition amounts, c is the smoke release rate curve of the composite materials with different addition amounts, and d is the total smoke release curve of the composite materials with different addition amounts.
FIG. 5 shows the smoke density and smoke toxicity curves of the composite materials with different structures according to the embodiment of the invention, wherein a is the smoke density curve of TPU and the composite materials thereof, b is the highest smoke density of all materials, and c is CO 2 And the yield d is the CO yield, and the excellent smoke and toxicity inhibition effect of the smoke inhibitor on the material is shown.
FIG. 6 is a thermogravimetric curve of a composite material of different structure in an embodiment of the present invention. a is the thermal weight loss curve of the sample under nitrogen, and b is the differential thermal weight curve of the sample under nitrogen.
FIG. 7 is a graph showing a combustion test of a steady-state tube furnace for a composite material with different structures in an embodiment of the present invention, a is the transmittance of the composite material, b is the total shading rate of the composite material, c is the CO of the composite material 2 Concentration d is total CO of the composite material 2 Yield, e, is the CO concentration of the composite and e is the total CO yield of the composite.
Detailed Description
For further explanation of the technical solution of the present invention, preferred embodiments of the present invention are described below with reference to examples, however, it should be understood that these descriptions are only for further explanation of features and advantages of the present invention, and are not limiting of the claims of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: preparation of alumina nanoparticles
(1) Dissolving aluminum nitrate in deionized water, stirring for 1h to form a uniform solution, slowly dropwise adding ammonia water under the condition of continuous stirring to fully precipitate, and obtaining a suspension with a pH value of about 9 after fully precipitation.
(2) The suspension was filtered to give a white precipitate, which was washed 3 times with deionized water, and the precipitate obtained was collected and dried in a forced air oven for 12h at 100 ℃.
(3) And calcining the dried sample in a muffle furnace for 4 hours, wherein the temperature of the muffle furnace is 600 ℃, and obtaining the white alumina nano particles.
Example 2: preparation of alumina nanosheets
(1) Aluminum isopropoxide was added to a mixture of absolute ethanol and deionized water, stirred at 80 ℃ for 1 hour, and the mixed solution was transferred to a teflon lined stainless steel autoclave and hydrothermally treated at 200 ℃ for 24 hours.
(2) Filtering the product obtained by the hydrothermal reaction, filtering the obtained precipitate, washing the precipitate with deionized water and ethanol for 3 times respectively, collecting the obtained precipitate, and drying the precipitate in a blast oven for 12 hours at 100 ℃.
(3) And calcining the dried sample in a muffle furnace for 4 hours, wherein the temperature of the muffle furnace is 600 ℃, and obtaining the white alumina nano-sheet.
Example 3: preparation of alumina nano microsphere
(1) Aluminum nitrate was dissolved in isopropanol and stirred for 1h to form a homogeneous solution, glycerin was slowly added dropwise under constant stirring to mix thoroughly, the mixed solution was transferred to a stainless steel autoclave with teflon liner and hydrothermally treated at 180 ℃ for 16h.
(2) The suspension was filtered to give a white precipitate, which was washed 3 times with ethanol, and the precipitate obtained was collected and dried in a forced air oven for 12h at 60 ℃.
(3) The dried sample was dispersed in a mixed solution of water and ethanol at a ratio of 1:1, and stirred under gentle stirring. The stirring time was 16h and the stirring rate was 300rpm.
(4) The above mixed solution was centrifuged, washed 3 times with ethanol, and the obtained precipitate was collected and dried in a forced air oven for 12 hours at 60 ℃.
(5) And calcining the dried sample in a muffle furnace for 4 hours, wherein the temperature of the muffle furnace is 500 ℃, and obtaining the white alumina nano-microsphere.
Example 4: preparation of efficient smoke-suppressing and toxicity-reducing agent
(1) Different Al to be prepared 2 O 3 The carrier was uniformly dispersed in n-hexane, and the gas in the pore canal of the carrier was removed, and the stirring time was 1h and the stirring rate was 300rpm.
(2) Slowly dripping the nickel nitrate aqueous solution into the mixed suspension, and finishing the surface loading of the active component after the dripping is finished.
(3) And continuously stirring the mixed solution for 60min, uniformly mixing, and drying in a forced air oven for 12h at the temperature of 100 ℃.
(4) And calcining the dried sample in a muffle furnace for 8 hours, wherein the temperature of the muffle furnace is 700 ℃, and obtaining the efficient smoke suppression and attenuation hybrid material.
Example 5: preparation of flame-retardant TPU composite materials with different smoke suppressant addition amounts
(1) Drying TPU master batches in an oven for 6 hours, and removing water for standby;
(2) Dissolving the dried TPU master batch in N, N-Dimethylformamide (DMF), adding a smoke suppressant into the mixed solution under the stirring condition, stirring to mix uniformly, pouring the mixed solution into water to wash out the excessive DMF solution, and drying the precipitate in an air blast bellows at 80 ℃ for a certain time to obtain the TPU composite material.
(4) According to the addition amounts (0, 1, 2 and 3 wt%) of different smoke suppressants, the prepared composite material is named TPU and 1wt% NiO/Al 2 O 3 -P/TPU、2wt％NiO/Al 2 O 3 P/TPU and 3wt% NiO/Al 2 O 3 -P/TPU。
FIG. 4 is a graph showing the flammability of flame retardant TPU composites of samples with varying smoke suppressant addition, with severe burning of the samples after ignition, accompanied by a large amount of smoke, due to the high flammability of TPUIs released. As can be seen from the graph, the addition of the smoke suppressant has less influence on heat release, but greatly reduces the total smoke of the composite material, and the smoke suppression effect is better along with the higher addition, so that 3wt% of NiO/Al is selected 2 O 3 The P/TPU material is subjected to intensive research analysis.
Example 6: preparation of flame-retardant TPU composite material added with smoke suppressants with different structures
(1) Drying TPU master batches in an oven for 6 hours, and removing water for standby;
(2) Dissolving the dried TPU master batch in N, N-Dimethylformamide (DMF), adding a smoke suppressant into the mixed solution under the stirring condition, stirring to mix uniformly, pouring the mixed solution into water to wash out the excessive DMF solution, and drying the precipitate in an air blast bellows at 80 ℃ for a certain time to obtain the TPU composite material.
(4) Smoke suppressants (NiO, al) according to different structures 2 O 3 、NiO/Al 2 O 3 -P、NiO/Al 2 O 3 -S、NiO/Al 2 O 3 M) in an amount of 3% by weight, the composite material obtained was designated NiO/TPU and Al 2 O 3 /TPU、NiO/Al 2 O 3 -P/TPU、NiO/Al 2 O 3 S/TPU and NiO/Al 2 O 3 -M/TPU。
Fig. 5 shows the smoke density and smoke toxicity curves of the composite materials with different structures in the embodiment of the invention, which shows the excellent smoke and toxicity inhibition effect of the smoke suppressant on the materials, the sheet smoke suppressant has the best effect, and the smoke suppressant reaches 48%, and the toxicity is obviously reduced compared with the pure TPU. Figure 6 shows the steady state tube furnace combustion process for the sample TPU and composite. Because of the high flammability of TPU, the sample burns vigorously after ignition, accompanied by the release of a large amount of smoke. Compared with the prior art, the addition of the high-efficiency smoke suppressant can reduce the total smoke amount and the smoke toxicity of the composite material, wherein NiO/Al 2 O 3 The total smoke amount of the S/TPU is reduced by 28.5 percent, the CO amount is reduced by 65.7 percent, the toxicity is greatly reduced, and the excellent smoke suppression and toxicity reduction performances are shown.
Fig. 2 shows smoke suppression according to various embodiments of the present inventionXRD patterns of the agent, al being present in all smoke suppressant components 2 O 3 Characteristic peaks, and characteristic peaks of the AlNi alloy appear in part of the samples.
Fig. 3 is an SEM picture of smoke suppressants of different structures in the examples of the present invention, and the smoke suppressants prepared have different structures and sizes. The size of the granular smoke suppressant is in the range of 50-100 nm; the size of the flaky smoke suppressant is 5-30 mu m, and the size of the microspherical smoke suppressant is 200-500 nm.
FIG. 4 is a graph showing the combustion performance of the flame retardant TPU composite materials with different addition amounts of smoke suppressant, showing the influence of the addition amounts of different smoke suppressants on the combustion process of the TPU material, wherein the smoke suppression effect of 3wt% of the addition amount is the best, and the smoke suppression effect of 40% is achieved.
Fig. 5 shows the smoke density and smoke toxicity curves of the composite materials with different structures in the embodiment of the invention, which shows the excellent smoke and toxicity inhibition effect of the smoke suppressant on the materials, the sheet smoke suppressant has the best effect, and the smoke suppressant reaches 48%, and the toxicity is obviously reduced compared with the pure TPU.
FIG. 6 is a thermal weight curve of a composite material of different structure in an embodiment of the invention, the addition of smoke suppressant advances the decomposition of TPU, and increases carbon residue from 4.87wt% to 9.41wt%, smoke suppressant can increase the carbon layer formed by combustion and suppress heat and mass transfer processes.
FIG. 7 is a graph showing the combustion test of a steady-state tube furnace of a composite material with different structures in an embodiment of the invention, wherein the addition of a smoke suppressant significantly reduces the total smoke and the smoke toxicity of the composite material, and the CO yield, CO 2 The yield is increased.
Claims (9)
1. A preparation method of a high-efficiency smoke suppression and attenuation hybrid material is characterized by comprising the following steps:
the method adopts alumina with different structures as a carrier and nickel oxide with a load active component as a high-efficiency smoke suppression and toxicity reduction hybrid material, and specifically comprises the following steps:
step 1: firstly, synthesizing alumina nano particles, alumina nano sheets and alumina nano microspheres as carriers of smoke suppression and attenuation hybrid materials;
step 2: then uniformly dispersing the alumina carrier into normal hexane, dripping completely dissolved nickel nitrate aqueous solution into the system under the stirring condition, and continuously stirring and mixing for a certain time after the dripping is finished to finish the loading of active components;
step 3: and (2) drying the mixed solution obtained in the step (2) in a blast oven, and calcining at a high temperature in a muffle furnace after drying to obtain the high-efficiency smoke-suppressing and toxicity-reducing hybrid material.
2. The method of manufacturing according to claim 1, characterized in that:
in the step 1, the alumina nano-particles are prepared by a coprecipitation method, and the size of the alumina nano-particles is in the range of 50-100 nm; the alumina nano-sheet is prepared by a hydrothermal method, and the size of the alumina nano-sheet is in the range of 5-30 mu m; the alumina nanometer microsphere is prepared by a template method, and the size of the alumina nanometer microsphere is in the range of 200-500 nm.
3. The method of manufacturing according to claim 1, characterized in that:
in the efficient smoke suppression and attenuation hybrid material, the active center nickel oxide accounts for 10 weight percent of the total mass.
4. The method of manufacturing according to claim 1, characterized in that:
in the step 2, the concentration of the nickel nitrate aqueous solution is 0.1mol/L, the mixing and stirring speed is 300rpm, and the stirring time is 30-60min.
5. The method of manufacturing according to claim 1, characterized in that:
in the step 3, the drying temperature is 80-120 ℃ and the drying time is 6-12h.
6. The method of manufacturing according to claim 1, characterized in that:
in the step 3, the calcination temperature is 400-600 ℃ and the calcination time is 6-10h.
7. The application of the efficient smoke suppression and attenuation hybrid material prepared by the preparation method according to any one of claims 1 to 6 is characterized in that: the smoke suppression and attenuation hybrid material is used as an additive to be added into thermoplastic polyurethane, so that the flame retardance and smoke suppression performance of the composite material are improved.
8. The use according to claim 7, characterized in that:
when the smoke suppression and attenuation hybrid material is used as an additive to be added into thermoplastic polyurethane, a solvent method is adopted to construct a composite material.
9. The use according to claim 7, characterized in that:
the addition amount of the smoke suppression and attenuation hybrid material is 1-3wt% of the total mass of the composite material.
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