CN117004084A - Anti-dripping flame retardant, and preparation method and application thereof - Google Patents
Anti-dripping flame retardant, and preparation method and application thereof Download PDFInfo
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- CN117004084A CN117004084A CN202311038947.7A CN202311038947A CN117004084A CN 117004084 A CN117004084 A CN 117004084A CN 202311038947 A CN202311038947 A CN 202311038947A CN 117004084 A CN117004084 A CN 117004084A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- 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 82
- 238000002360 preparation method Methods 0.000 title abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 37
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 229920002379 silicone rubber Polymers 0.000 claims description 27
- 150000000703 Cerium Chemical class 0.000 claims description 24
- 239000004945 silicone rubber Substances 0.000 claims description 24
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 17
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 5
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 nitrogen-containing compound Chemical class 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- UMXXGDJOCQSQBV-UHFFFAOYSA-N n-ethyl-n-(triethoxysilylmethyl)ethanamine Chemical compound CCO[Si](OCC)(OCC)CN(CC)CC UMXXGDJOCQSQBV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
Abstract
The invention provides a molten drop-resistant flame retardant, a preparation method and application thereof, wherein the molten drop-resistant flame retardant comprises an in-situ composite material of cerium oxide and carbon nanotubes.
Description
Technical Field
The invention belongs to the technical field of anti-dripping flame retardants, and particularly relates to an anti-dripping flame retardant, a preparation method and application thereof.
Background
Room temperature vulcanized silicone Rubber (RTV) belongs to one of silicone rubbers, can be cured at room temperature, is convenient to use, has the advantages of excellent high and low temperature resistance, weather resistance, aging resistance, ozone resistance, hydrophobicity, innocuity, excellent electrical insulation, outstanding surface activity and the like, and is widely applied to building sealants, waterproof coatings, insulating sealants and the like. However, room temperature vulcanized silicone rubber is a flammable material, and is accompanied by serious dripping during combustion, which is extremely liable to cause the spread of fire and secondary fire, so that improvement of flame retardance and dripping resistance of room temperature vulcanized silicone rubber is required.
CN106633917a discloses a flame retardant silicone rubber material cooperated with a nano flame retardant and a nitrogen-phosphorus intumescent flame retardant and a preparation method thereof, wherein the material comprises the following components in percentage by weight: 68.0 to 82.0 percent of silicon rubber, 0.5 to 5.0 percent of nano flame retardant, 18.0 to 25.0 percent of nitrogen-phosphorus intumescent flame retardant and 0.5 to 2.5 percent of vulcanizing agent. According to the technical scheme, the nano flame retardant is uniformly dispersed in the silicone rubber matrix, so that the combustion performance of the silicone rubber can be remarkably reduced, the mechanical performance of the silicone rubber can be improved, the nitrogen-phosphorus flame retardant can endow the silicone rubber with excellent flame retardant performance, and the synergistic flame retardant effect of the nitrogen-phosphorus flame retardant and the silicone rubber is remarkable.
CN115491038A discloses a halogen-free platinum flame retardant for silicone rubber and a preparation method thereof, wherein the halogen-free platinum flame retardant for silicone rubber comprises the following components: 55-75 parts of silicon rubber, 5-10 parts of platinum catalyst, 3-5 parts of nitrogen-containing compound, 0.5-1 part of phosphorus-containing compound, 12-30 parts of inorganic powder, 0-5 parts of alkynol compound and 0.3-0.5 part of coupling agent. According to the technical scheme, the specific platinum catalyst, the nitrogen-containing compound, the phosphorus-containing compound and the inorganic powder are selected to be compounded, so that the flame retardant property of the silicone rubber product is greatly improved, but the cost of the platinum catalyst is higher, and the cost of the halogen-free platinum flame retardant for the silicone rubber is increased.
CN115044208A discloses a method for preparing a water-resistant double-metal hydroxide flame-retardant silicone rubber, which enhances thermal stability by loading layered metal hydroxide on melamine polyphosphate, and utilizing its excellent gas-phase flame-retardant ability and layered metal hydroxide catalytic char-forming ability; meanwhile, in order to improve the compatibility and dispersibility of the flame retardant and the rubber, polydimethylsiloxane is used for carrying out second hydrophobic modification on the flame retardant; the high-efficiency halogen-free intumescent flame retardant obtained by modification effectively improves the water resistance and the thermal stability of the silicone rubber material, but the preparation steps of the water-resistant bimetal hydroxide flame-retardant silicone rubber are complicated.
Therefore, it is necessary to develop a flame retardant which has good stability, simple preparation process, flame retardance, smoke suppression and melt drip resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a melt-drip-resistant flame retardant, and a preparation method and application thereof. The anti-dripping flame retardant comprises an in-situ composite material of cerium oxide and carbon nano tubes, wherein the cerium oxide and the carbon nano tubes have a synergistic effect, can obviously improve the flame retardant effect, and simultaneously has an obvious anti-dripping effect.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a melt drop resistant flame retardant comprising an in situ composite of ceria and carbon nanotubes.
According to the invention, the ceria can improve the thermal stability and the char formation effect of the polymer material, improve the flame retardant property of the polymer material, and the ceria and the carbon nano tube have synergistic effect, and the in-situ composite material of the ceria and the carbon nano tube can form a three-dimensional network structure in a polymer material system, so that the anti-dripping property of the polymer material is improved, and a stable and firm char layer can be formed to isolate oxygen when the polymer material is combusted, thereby improving the flame retardant property.
Preferably, the ceria is nano ceria.
In a second aspect, the present invention provides a method for preparing the anti-dripping flame retardant according to the first aspect, the method comprising the steps of: and mixing cerium salt, water, a precipitator and the carbon nano tube, and reacting to obtain the anti-dripping flame retardant.
Preferably, the mixing includes mixing cerium salt with water to obtain cerium salt solution, dropping aqueous solution of precipitant, adjusting pH to 8-12 (e.g., 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5 or 12, etc.), and adding carbon nanotube for mixing.
Preferably, the reaction is carried out in a hydrothermal kettle.
Preferably, the cerium salt comprises a trivalent cerium salt.
Preferably, the trivalent cerium salt includes any one or a combination of at least two of cerium nitrate, cerium chloride, or cerium sulfate.
Preferably, the precipitant comprises any one or a combination of at least two of ammonia water, sodium hydroxide, potassium hydroxide or sodium carbonate.
Preferably, the temperature of the mixing is 25-50deg.C, such as 30deg.C, 32deg.C, 35deg.C, 38deg.C, 40deg.C, 42 deg.C, 45deg.C, 48deg.C or 49deg.C, etc.
Preferably, the temperature of the reaction is 110-300 ℃, e.g., 115 ℃, 120 ℃, 150 ℃, 200 ℃, 220 ℃, 250 ℃, 270 ℃, 280 ℃, 290 ℃, or the like.
Preferably, the reaction time is 6-48h, e.g. 8h, 10h, 12h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 47h, etc.
Preferably, the concentration of cerium salt in the cerium salt solution is 0.1 to 10.0mol/L, for example 0.2mol/L, 0.5mol/L, 1.0mol/L, 2.0mol/L, 4.0mol/L, 5.0mol/L, 7.0mol/L, 9.0mol/L, 9.5mol/L, or the like.
In the invention, the concentration of cerium salt in the cerium salt solution is 0.1-10.0mol/L, and if the concentration of cerium salt is too high, a large amount of agglomeration is generated in the prepared cerium dioxide; if the concentration of cerium salt is too small, the yield of nano cerium dioxide is small, the production cost is greatly increased, and the discharge amount of wastewater is greatly increased.
Preferably, the concentration of the precipitant in the aqueous solution of the precipitant is 0.1 to 5.0mol/L, for example 0.2mol/L, 0.5mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4.0mol/L, 4.5mol/L or the like.
Preferably, the dropping speed is 1-50mL/min, such as 2mL/min, 5mL/min, 10mL/min, 15mL/min, 20mL/min, 25mL/min, 30mL/min, 35mL/min, 40mL/min or 45mL/min, etc.
Preferably, the concentration of the carbon nanotubes in the mixed solution obtained by mixing the cerium salt, water, the precipitant and the carbon nanotubes is 1.0-100.0g/L, for example, 2.0g/L, 5.0g/L, 10.0g/L, 30.0g/L, 50.0g/L, 70.0g/L, 90.0g/L, 95.0g/L, etc.
In the invention, the concentration of the carbon nano tube in the mixed solution of cerium salt, water, precipitant and carbon nano tube is 1.0-100.0g/L, if the concentration of the carbon nano tube is too large, the concentration of the reactant in the mixed solution is too large, and the viscosity of the mixed solution is too large, so that normal reaction cannot be performed; if the concentration of the carbon nanotubes is too small, the production cost is greatly increased, and the discharge amount of wastewater is greatly increased.
In a third aspect, the invention provides a flame-retardant room temperature vulcanized silicone rubber, wherein the preparation raw materials of the flame-retardant room temperature vulcanized silicone rubber comprise the anti-dripping flame retardant in the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the anti-dripping flame retardant comprises an in-situ composite material of cerium oxide and carbon nano tubes, wherein the cerium oxide and the carbon nano tubes have a synergistic effect, can obviously improve the flame retardant effect, and simultaneously has obvious anti-dripping and smoke suppression effects. Preferably, the limiting oxygen index of the flame-retardant room temperature vulcanized silicone rubber prepared by the anti-dripping flame retardant is 26.9-29.1%, the UL94 vertical burning grade is V-0, and the flame-retardant effect is good.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a molten drop resistant flame retardant and a preparation method thereof, wherein the molten drop resistant flame retardant is an in-situ composite material of nano cerium dioxide and carbon nano tubes, and the preparation method is as follows:
mixing water and cerium nitrate to prepare 0.1mol/L cerium nitrate solution, adding 1000mL of 0.1mol/L cerium nitrate solution into a stirring kettle, controlling the temperature of the stirring kettle to be 25 ℃ under continuous stirring, then dropwise adding 0.1mol/L sodium hydroxide solution at a speed of 1.0mL/min until the pH value is 9.0, and stopping dropwise adding the sodium hydroxide solution. After the reaction is finished, adding 1g of carbon nano tube, stirring uniformly, transferring the mixture into a hydrothermal kettle, adjusting the rotating speed of the hydrothermal kettle to be 10r/min, reacting for 6 hours at 160 ℃, and after the reaction is finished, centrifugally separating and washing to obtain the anti-dripping flame retardant.
Example 2
The embodiment provides a molten drop resistant flame retardant and a preparation method thereof, wherein the molten drop resistant flame retardant is an in-situ composite material of nano cerium dioxide and carbon nano tubes, and the preparation method is as follows:
mixing water and cerium chloride to prepare 10mol/L cerium chloride solution, adding 1000mL of 10mol/L cerium chloride solution into a stirring kettle, controlling the temperature of the stirring kettle to be 50 ℃ under continuous stirring, then dropwise adding 5mol/L ammonia water solution at the speed of 50mL/min until the pH is 12, and stopping dropwise adding the ammonia water solution. After the reaction is completed, adding 100g of carbon nano tube, uniformly stirring, transferring into a hydrothermal kettle, regulating the rotating speed of the hydrothermal kettle to 1000r/min, and reacting for 48 hours at 200 ℃. After the reaction is completed, centrifugally separating and washing to obtain the anti-dripping flame retardant.
Example 3
The embodiment provides a molten drop resistant flame retardant and a preparation method thereof, wherein the molten drop resistant flame retardant is an in-situ composite material of nano cerium dioxide and carbon nano tubes, and the preparation method is as follows:
mixing water and cerium sulfate to prepare 5mol/L cerium sulfate solution, adding 1000mL of the 5mol/L cerium sulfate solution into a stirring kettle, controlling the temperature of the stirring kettle to be 30 ℃ under continuous stirring, then dropwise adding 3mol/L sodium carbonate solution at the speed of 30mL/min until the pH value is 11, and stopping dropwise adding the sodium carbonate solution. After the reaction is completed, 50g of carbon nano tube is added, stirred uniformly, then transferred into a hydrothermal kettle, the rotating speed of the hydrothermal kettle is adjusted to be 500r/min, and the reaction is carried out for 36 hours at the temperature of 300 ℃. After the reaction is completed, centrifugal separation and washing are carried out to obtain the in-situ composite nano cerium dioxide/carbon nano tube anti-dripping flame retardant.
Example 4
This example provides a melt drop-resistant flame retardant and a method for preparing the same, which are different from example 1 only in that the concentration of the cerium nitrate solution is adjusted to 12mol/L, and other conditions are the same as example 1.
Example 5
This example provides a melt drop-resistant flame retardant and a method for producing the same, which are different from example 1 only in that the amount of carbon nanotubes added was adjusted to 110g, and the other conditions were the same as in example 1.
Comparative example 1
The comparative example provides a molten drop-resistant flame retardant which is nano cerium dioxide and the preparation method thereof is as follows:
mixing water and cerium nitrate to prepare 0.1mol/L cerium nitrate solution, adding 1000mL of 0.1mol/L cerium nitrate solution into a stirring kettle, controlling the temperature of the stirring kettle to be 25 ℃ under continuous stirring, then dropwise adding 0.1mol/L sodium hydroxide solution at a speed of 1.0mL/min until the pH value is 9.0, and stopping dropwise adding the sodium hydroxide solution. After the reaction is completed, transferring the mixture into a hydrothermal kettle, adjusting the rotating speed of the hydrothermal kettle to be 10r/min, reacting for 6 hours at 160 ℃, and after the reaction is completed, centrifugally separating and washing to obtain the anti-dripping flame retardant.
Comparative example 2
The comparative example provides a melt drop resistant flame retardant which is a carbon nanotube.
Comparative example 3
The comparative example provides a melt-drop-resistant flame retardant which is a mixture of nano cerium oxide and carbon nanotubes in a mass ratio of 17:1, wherein the mass ratio of the nano cerium oxide to the carbon nanotubes in the mixture is the same as that of the nano cerium oxide to the carbon nanotubes in the in-situ composite material in example 1.
The anti-dripping flame retardants provided in the above examples and comparative examples were subjected to the following performance test.
100g of hydroxyl-terminated polydimethylsiloxane (viscosity: 10000cs,25 ℃ C.), 30g of anti-dripping flame retardant, 0.3g of dibutyltin dilaurate and 0.5g of diethylaminomethyl triethoxysilane were melt-mixed to prepare flame-retardant room temperature vulcanized silicone rubber and subjected to the following performance test.
(1) Limiting oxygen index: the limiting oxygen index was obtained by testing according to GB/T2406-1993 oxygen index method of Plastic Combustion Performance test method.
(2) UL94 vertical burn rating: the test was performed in accordance with ANST/UL94-1985 to obtain a UL94 vertical burn rating.
The test results are shown in Table 1.
TABLE 1
In Table 1 "-" represents that this result was not measured.
As shown in the test results of Table 1, the limiting oxygen index of the flame-retardant room temperature vulcanized silicone rubber prepared by the anti-dripping flame retardant provided in examples 1-3 is 26.9-29.1%, the UL94 vertical burning grade is V-0, and the flame-retardant effect is good.
Compared with the example 1, if the concentration of the cerium nitrate solution is too high (example 4), a large amount of nano cerium dioxide in the product is agglomerated, so that the particle size of the product is too high, the limiting oxygen index of the prepared flame-retardant room temperature vulcanized silicone rubber is reduced, the UL94 vertical burning grade is V-2, the flame-retardant effect is reduced, and the performance of the anti-dripping flame retardant prepared by adopting the cerium salt solution with specific concentration is better.
When the concentration of the carbon nanotubes was too high (example 5) as compared with example 1, the viscosity of the mixed solution was too high, the fluidity was no longer exhibited, the reaction was not performed, and the anti-dripping flame retardant was not produced, which proved that the anti-dripping flame retardant could be produced by using the carbon nanotubes of a specific concentration.
Compared with example 1, when nano cerium oxide was used as the anti-dripping flame retardant (comparative example 1), the limiting oxygen index was lowered, the UL94 vertical burning grade was V-2, and the flame retardant effect was lowered.
Compared with example 1, when carbon nanotubes were used as the anti-dripping flame retardant (comparative example 2), the limiting oxygen index was lowered, the UL94 vertical burning rating was V-1, and the flame retardant effect was lowered.
Compared with example 1, if a mixture of nano cerium oxide and carbon nanotubes is used as the anti-dripping flame retardant (comparative example 3), the limiting oxygen index is lowered, the UL94 vertical burning grade is V-1, and the flame retardant effect is lowered.
The applicant states that the invention is illustrated by the above examples as to a melt drop resistant flame retardant and a method of making and using the same, but the invention is not limited to, i.e. it is not meant that the invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A molten drop resistant flame retardant, characterized in that the molten drop resistant flame retardant comprises an in situ composite of ceria and carbon nanotubes.
2. The anti-drip flame retardant of claim 1, wherein said ceria is nano ceria.
3. A method of preparing the anti-drip flame retardant according to claim 1 or 2, comprising the steps of: and mixing cerium salt, water, a precipitator and the carbon nano tube, and reacting to obtain the anti-dripping flame retardant.
4. The method of claim 3, wherein the mixing comprises mixing cerium salt with water to obtain cerium salt solution, dropping aqueous solution of precipitant, adjusting pH to 8-12, and adding carbon nanotubes.
5. The process according to claim 3 or 4, wherein the reaction is carried out in a hydrothermal kettle;
preferably, the cerium salt comprises a trivalent cerium salt;
preferably, the trivalent cerium salt includes any one or a combination of at least two of cerium nitrate, cerium chloride, or cerium sulfate.
6. The method of any one of claims 3 to 5, wherein the precipitant comprises any one or a combination of at least two of ammonia water, sodium hydroxide, potassium hydroxide, or sodium carbonate.
7. The method of any one of claims 3-6, wherein the temperature of mixing is 25-50 ℃;
preferably, the temperature of the reaction is 110-300 ℃;
preferably, the reaction time is from 6 to 48 hours.
8. The method according to any one of claims 4 to 7, wherein the concentration of cerium salt in the cerium salt solution is 0.1 to 10.0mol/L;
preferably, the concentration of the precipitant in the aqueous solution of the precipitant is 0.1-5.0mol/L;
preferably, the dropping speed is 1-50mL/min.
9. The method according to any one of claims 3 to 8, wherein the concentration of the carbon nanotubes in the mixed solution obtained by mixing the cerium salt, water, the precipitant and the carbon nanotubes is 1.0 to 100.0g/L.
10. A flame retardant room temperature vulcanized silicone rubber, characterized in that the raw materials for preparing the flame retardant room temperature vulcanized silicone rubber comprise the anti-dripping flame retardant as defined in claim 1 or 2.
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| CN202311038947.7A CN117004084A (en) | 2023-08-17 | 2023-08-17 | Anti-dripping flame retardant, and preparation method and application thereof |
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| CN202311038947.7A CN117004084A (en) | 2023-08-17 | 2023-08-17 | Anti-dripping flame retardant, and preparation method and application thereof |
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