CN117165092A - Flame-retardant foaming silica gel material and preparation method thereof - Google Patents
Flame-retardant foaming silica gel material and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000741 silica gel Substances 0.000 title claims abstract description 53
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 48
- 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 46
- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 238000005187 foaming Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052582 BN Inorganic materials 0.000 claims abstract description 80
- -1 methyl hydrogen Chemical compound 0.000 claims abstract description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 229920002545 silicone oil Polymers 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000004088 foaming agent Substances 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 20
- 229920001661 Chitosan Polymers 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 15
- 229920001690 polydopamine Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- IUTYMBRQELGIRS-UHFFFAOYSA-N boric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OB(O)O.NC1=NC(N)=NC(N)=N1 IUTYMBRQELGIRS-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 3
- 239000000523 sample Substances 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011231 conductive filler Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 229920002379 silicone rubber Polymers 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- DDCDEKHXBABHHI-UHFFFAOYSA-N acetylene cyclohexanol Chemical compound C1(CCCCC1)O.C#C DDCDEKHXBABHHI-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 239000004945 silicone rubber Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 102000048470 Dixin Human genes 0.000 description 1
- 108700037673 Dixin Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 239000011738 major mineral Substances 0.000 description 1
- 235000011963 major mineral Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 239000002210 silicon-based material Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant foaming silica gel material and a preparation method thereof. The flame-retardant foaming silica gel material comprises liquid base gel, methyl hydrogen-containing silicone oil, heat conducting filler, foaming agent, platinum catalyst, inhibitor and functional boron nitride. The invention fully stirs the liquid base adhesive, methyl hydrogen silicone oil, heat conductive filler, foaming agent, inhibitor and functional boron nitride, adds platinum catalyst, stirs them evenly rapidly, moves to the mould to be vulcanized to obtain the flame-retardant foaming silica gel material. Compared with the prior art, the flame-retardant foamed silica gel material prepared by the invention has the advantages of high stability and good flame-retardant effect.
Description
Technical Field
The invention relates to the technical field of silica gel materials, in particular to a flame-retardant foaming silica gel material and a preparation method thereof.
Background
Silicone rubber is always a large class of products in the organic silicon materials with the largest yield and the widest application, and has the characteristics of excellent heat resistance, cold resistance, dielectric property, ozone resistance, aging resistance and the like. Has become the first choice material in the fields of military aerospace, medical treatment, automobiles, construction and the like.
The foaming silica gel is a porous high polymer elastic material formed by the silicone rubber after the foaming process, has the advantages of light weight and good heat insulation performance besides the excellent performance of the silicone rubber, and has the advantages of high and low temperature resistance, weather resistance, environmental protection and the like which are not available in other foam materials; can be made into flexible silicone rubber products such as human body, insoles, shoulder pads, patches, anti-slip pads, etc., and the foaming silicone rubber can be used for a long time at the temperature of-65 ℃ to 200 ℃ and maintain the soft and elastic performance. However, a large number of hydrocarbon groups exist on the side chain of the organic silicon, combustion can occur under the conditions of high temperature or fire, however, the hole structure in the foamed silica gel enables the silica gel material to have higher air flow conductivity, combustion is more facilitated, the higher the foaming ratio is, the greater the flame-retardant difficulty is, and therefore flame-retardant components are often added into the foamed silica gel material to synthesize the flame-retardant foamed silica gel material so as to improve the flame-retardant effect of the foamed silica gel.
CN114381123a discloses a preparation method of a ceramic flame-retardant foamed silica gel material, through preparation of vinyl silicone resin, preparation of base material, preparation of a component a and preparation of a component B flame-retardant organic silicon foam material, finally, the component a and the component B are mixed for use, so that the foamed silica gel material is passively combusted to form porous ceramic, the porous ceramic has heat preservation performance to avoid further diffusion of fire, but the porous ceramic also has a pore structure to enable the silica gel material to have higher air circulation, and air combustion can be facilitated.
CN115926428A discloses a dual-component inert gas room temperature foaming sealing silica gel and a preparation method thereof, wherein the-NCO group reactivity of two modified silicone oils is lower than that of a common small molecular monomer, sufficient operation time is provided for A, B dual-component mixture, but white carbon black is adopted for reinforcement, the tackifying effect of the white carbon black on silica gel materials is obvious but the silica gel is not easy to mix, and the addition of the carbon black can influence the production of other colors of the foamed silica gel.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is to provide a flame-retardant foamed silica gel material, which improves the flame-retardant effect of the silica gel material.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the flame-retardant foaming silica gel material comprises the following components: platinum catalyst, inhibitor, functional boron nitride, foaming agent, heat conducting filler, methyl hydrogen silicone oil and liquid base adhesive.
Preferably, the flame-retardant foaming silica gel material comprises the following components: 0.1-1wt% of platinum catalyst, 0.5-5wt% of inhibitor, 2-15wt% of functionalized boron nitride, 1-10wt% of foaming agent, 3-20wt% of heat conducting filler, 5-60wt% of methyl hydrogen silicone oil and the balance of liquid base adhesive.
Preferably, the preparation method of the functionalized boron nitride comprises the following steps: in terms of the weight portions of the components,
uniformly mixing 1-5 parts of hexagonal boron nitride and 0.1-0.15 part of glycine, fully grinding for 3-4 hours at the ball milling speed of 600-850r/min, and placing in air; adding water, maintaining at room temperature for 1-3 hr, performing ultrasonic treatment at 20-40KHz and 20-35deg.C for 2-8min, centrifuging, collecting precipitate, repeating ultrasonic treatment for 2-4 times, and drying at 55-85deg.C in vacuum oven for 20-28 hr; obtaining the hydroxylated boron nitride;
dispersing 1-5 parts of hydroxylated boron nitride in isopropanol, mechanically stirring for 2-8h, and moving the solution to ultrasonic at 20-45KHz and 25-65 ℃ for 4-8h to obtain hydroxylated boron nitride dispersoid; dissolving 2-7 parts of ferric nitrate nonahydrate in ethanol, adding a hydroxylated boron nitride dispersoid, stirring for 1-4 hours, adding 2-8 parts of urea, and reacting for 0.5-2 hours at room temperature; filtering to obtain filter residue, washing with ethanol for 1-4 times, placing the filter residue into a ceramic cup of a muffle furnace, and maintaining at 180-220deg.C for 1-2 hr; obtaining the functionalized boron nitride.
Preferably, the production method of the functionalized boron nitride comprises the following steps: in terms of the weight portions of the components,
uniformly mixing 1-5 parts of hexagonal boron nitride and 1-5 parts of melamine borate, fully grinding for 3-4 hours at the ball milling speed of 600-850r/min, and placing in air; adding water, maintaining at room temperature for 1-3 hr, performing ultrasonic treatment at 20-40KHz and 20-35deg.C for 2-8min, centrifuging, collecting precipitate, repeating ultrasonic treatment for 2-4 times, and drying at 55-85deg.C in vacuum oven for 20-28 hr; obtaining melamine borate-boron nitride;
dispersing 1-5 parts of melamine borate-boron nitride in isopropanol, mechanically stirring for 2-8h, and moving the solution to be subjected to ultrasonic treatment at 20-45KHz and 25-65 ℃ for 4-8h to obtain melamine borate-boron nitride dispersoids; 2-7 parts of ferric nitrate nonahydrate is dissolved in ethanol, added into melamine borate-boron nitride dispersoid, stirred for 1-4 hours, added with 2-8 parts of urea and reacted for 0.5-2 hours at room temperature; filtering to obtain filter residue, washing with ethanol for 1-4 times, placing the filter residue into a ceramic cup of a muffle furnace, and maintaining at 180-220deg.C for 1-2 hr; obtaining the functionalized boron nitride.
Preferably, the production method of the functionalized boron nitride comprises the following steps: in terms of the weight portions of the components,
mixing 1-5 parts of hexagonal boron nitride and 30-65 parts of Tris buffer solution, performing ultrasonic treatment for 20-45min by using a probe, and adding NaOH aqueous solution until the pH is 7-9; adding 0.1-4 parts of dopamine hydrochloride, standing at room temperature for 14-20h, centrifuging at 4000-6000rpm for 2-14min, and washing until the pH of the supernatant is neutral; finally drying in a vacuum oven at 60-95 ℃ for 20-32h; obtaining polydopamine modified boron nitride;
dispersing 1-5 parts of polydopamine modified boron nitride in isopropanol, mechanically stirring for 2-8h, and moving the mixture to ultrasonic at 20-45KHz and 25-65 ℃ for 4-8h to obtain polydopamine modified boron nitride dispersoid; 2-7 parts of ferric nitrate nonahydrate is dissolved in ethanol, added into polydopamine modified boron nitride dispersoid, stirred for 1-4 hours, added with 2-8 parts of urea, and reacted for 0.5-2 hours at room temperature; filtering to obtain filter residue, washing with ethanol for 1-4 times, placing the filter residue into a ceramic cup of a muffle furnace, and maintaining at 180-220deg.C for 1-2 hr; obtaining the functionalized boron nitride.
Preferably, the production method of the functionalized boron nitride comprises the following steps: in terms of the weight portions of the components,
dissolving 1-5 parts of chitosan in 20-26 parts of dilute hydrochloric acid, adding water to adjust the pH to 2-5, adding 1-5 parts of hexagonal boron nitride, performing ultrasonic treatment for 10-28min, centrifuging, and washing until the pH of the supernatant is neutral; drying in a vacuum oven at 60-95 ℃ for 20-32h to obtain chitosan modified boron nitride;
dispersing 1-5 parts of chitosan modified boron nitride in isopropanol, mechanically stirring for 2-8h, and moving the solution to ultrasonic at 20-45KHz and 25-65 ℃ for 4-8h to obtain a chitosan modified boron nitride dispersion; dissolving 2-7 parts of ferric nitrate nonahydrate in ethanol, adding the ferric nitrate nonahydrate into the chitosan modified boron nitride dispersoid, stirring for 1-4 hours, adding 2-8 parts of urea, and reacting for 0.5-2 hours at room temperature; filtering to obtain filter residue, washing with ethanol for 1-4 times, placing the filter residue into a ceramic cup of a muffle furnace, and maintaining at 180-220deg.C for 1-2 hr; obtaining the functionalized boron nitride.
Preferably, the inhibitor is any one of alkynol compound, nitrile compound, vinyl siloxane or organic peroxide.
Preferably, the heat conducting filler is any one of aluminum oxide, magnesium oxide and silicon carbide.
Preferably, the foaming agent is any one of azodiisobutyronitrile, azodiisoheptonitrile and hydroxyl-containing organosilicon compound.
The preparation method of the flame-retardant foaming silica gel material comprises the following steps: fully stirring the liquid base adhesive, methyl hydrogen-containing silicone oil, the heat-conducting filler, the foaming agent, the inhibitor and the functional boron nitride, then adding the platinum catalyst, rapidly and uniformly stirring, and moving into a mould to be vulcanized for 1-30min at the temperature of 100-130 ℃ and the pressure of 6-9MPa to obtain the flame-retardant foaming silica gel material.
Hexagonal boron nitride is one of the most rapid two-dimensional layered materials developed at present, and has excellent thermal performance, mechanical property and chemical stability, adjacent boron atoms and nitrogen atoms are connected through covalent bonds to form a layered structure, layers are combined through weak intermolecular force Van der Waals force, and the poor dispersibility in a silica gel material is caused by the weak intermolecular force between the layers, but meanwhile, massive hexagonal boron nitride crystals can be peeled into hexagonal boron nitride nano-sheets.
The layered structure of hexagonal boron nitride may act as a fire barrier during combustion. The hexagonal boron nitride nanosheets can be modified in situ through ferric oxide nanoparticles, so that free radicals can be effectively captured; the in-situ modified hexagonal boron nitride nano-sheets of the ferric oxide nano-particles are uniformly mixed into the addition-cured silicon rubber, and the interlayer blocking effect and the free radical quenching effect are combined, so that the heat stability and the flame retardance of the flame-retardant foaming silica gel material can be improved.
By modifying the hexagonal boron nitride, hydroxylated hexagonal boron nitride, boric acid cyanuric acid-boron nitride, polydopamine modified boron nitride and chitosan modified boron nitride can be more uniformly dispersed into the flame-retardant foaming silica gel material, so that the flame retardance of the flame-retardant foaming silica gel can be improved.
The invention has the beneficial effects that:
1. compared with the prior art, the method has the advantages that the boron nitride is directly used for directly playing a role in flame retardance in the flame retardance foaming silica gel material, free radicals can be effectively captured through the in-situ modification of the hexagonal boron nitride nano-sheets by the ferric oxide nano-particles, the in-situ modification of the hexagonal boron nitride nano-sheets by the ferric oxide nano-particles is uniformly mixed into the addition-cured silicone rubber, the interlayer blocking effect and the free radical quenching effect are combined, and the flame retardance effect of the flame retardance foaming silica gel material can be improved.
2. Compared with the prior art, the method has the advantages that the hexagonal boron nitride is further modified to obtain hydroxylated hexagonal boron nitride, melamine-boron borate-boron nitride, polydopamine modified boron nitride and chitosan modified boron nitride respectively, so that the dispersion performance of the hexagonal boron nitride in the flame-retardant foaming silica gel material is further improved, and the flame-retardant effect of the flame-retardant foaming silica gel is further improved.
Detailed Description
Parameters of specific chemicals are used, sources.
Hexagonal boron nitride: model: BN; particle size: 12500 mesh; CAS:10043-11-5.
Melamine borate: purchased from sienna dada chemical technology limited.
Chitosan: CAS:9012-76-4, product number: 101, jiangsu Yanke biology strength provider.
Dilute hydrochloric acid: the concentration of hydrochloric acid used in the invention is 2mol/L.
Tris buffer solution: pH 9.00,0.05mol/L.
Iron oxide, in powder form, particle size: 800 mesh; CAS:99, a step of; the major mineral product strength suppliers of the Shijia.
Vinyl silicone oil double-end-capped polydimethylsiloxane, CAS (CAS) 68083-19-2, model: QL-2311VDV, jining green alliance chemical technology Co., ltd.
Methyl hydrogen silicone oil: CAS:63148-57-2, viscosity 5cs-300cs, content 0.1-1.6; shenzhen Ji Peng silicon fluorine materials Co., ltd.
Platinum catalyst, karstedt catalyst, platinum content 3000ppm, wohan Kelmike biomedical technology Co.
Acetylene cyclohexanol: CAS:78-27-3; model: 100236; the dixin chemical industry limited company in Zhongshan.
Example 1
A flame-retardant foaming silica gel material is prepared by uniformly stirring 56g of liquid-based rubber vinyl silicone oil double-end-capped polydimethylsiloxane, 28g of methyl hydrogen-containing silicone oil, 10g of heat-conducting filler alumina, 3g of foaming agent azo diisobutyronitrile, 0.5g of inhibitor acetylene cyclohexanol, 2.3g of functionalized boron nitride and 0.2g of platinum catalyst, and then transferring the mixture into a mold to be vulcanized for 10min at 120 ℃ and 8 MPa.
The preparation method of the functionalized boron nitride comprises the following steps:
1) 2g of hexagonal boron nitride and 0.1g of glycine were uniformly mixed, and a mixture having a diameter of 5mm (number: 30 And 3mm (number: 15 Zirconia balls with different sizes are fully ground for 2 hours at the ball milling speed of 700r/min through an omnidirectional planetary ball mill, and are placed in the air for 15 minutes; then adding 5mL of distilled water, and reacting for 2h at 25 ℃; subsequently, ultrasonic treatment is carried out for 6min at 20KHz and 25 ℃; centrifuging at 1500rpm for 7min; washing the precipitate with deionized water until the pH of the supernatant is neutral; finally, drying the product in a vacuum oven at 80 ℃ for 24 hours to obtain hydroxylated boron nitride;
2) 2g of the hydroxylated boron nitride in the step 1) is weighed and dispersed in 375mL of isopropanol, and is mechanically stirred for 6 hours at 5000rpm, and simultaneously, the hydroxylated boron nitride dispersion is obtained by ultrasonic waves for 6 hours at 20KHz and 25 ℃; 2.54g of ferric nitrate nonahydrate is dissolved in 200mL of ethanol, added into the hydroxylated boron nitride dispersoid, mechanically stirred for 3 hours at 7000rpm, added with 3g of urea and reacted for 1 hour at 25 ℃; filtering to obtain filter residue, washing with ethanol for 3 times, placing the filter residue into a ceramic cup of a muffle furnace, heating from 25deg.C to 200deg.C at a heating rate of 5deg.C/min, maintaining at 200deg.C for 60min, and naturally cooling to room temperature to obtain functionalized boron nitride.
Example 2
A flame-retardant foaming silica gel material is prepared by uniformly stirring 56g of liquid-based rubber vinyl silicone oil double-end-capped polydimethylsiloxane, 28g of methyl hydrogen-containing silicone oil, 10g of heat-conducting filler alumina, 3g of foaming agent azo diisobutyronitrile, 0.5g of inhibitor acetylene cyclohexanol, 2.3g of functionalized boron nitride and 0.2g of platinum catalyst, and then transferring the mixture into a mold to be vulcanized for 10min at 120 ℃ and 8 MPa.
The preparation method of the functionalized boron nitride comprises the following steps:
1) 2g of hexagonal boron nitride and 2g of melamine borate were uniformly mixed, and a mixture having a diameter of 5mm (number: 30 And 3mm (number: 15 Zirconia balls with different sizes are fully ground for 2 hours at the ball milling speed of 700r/min through an omnidirectional planetary ball mill, and are placed in the air for 15 minutes; then adding 5mL of distilled water, and reacting for 2h at 25 ℃; subsequently, ultrasonic treatment is carried out for 6min at 20KHz and 25 ℃; centrifuging at 1500rpm for 7min; washing the precipitate with deionized water until the pH of the supernatant is neutral; finally, drying the product in a vacuum oven at 80 ℃ for 24 hours to obtain melamine borate-boron nitride;
2) 2g of melamine borate-boron nitride in 1) is weighed and dispersed in 375mL of isopropanol, and is mechanically stirred for 6 hours at 5000rpm, and simultaneously, ultrasonic waves are carried out for 6 hours at 20KHz and 25 ℃ to obtain melamine borate-boron nitride dispersoids; 2.54g of ferric nitrate nonahydrate is dissolved in 200mL of ethanol, added into melamine borate-boron nitride dispersoid, mechanically stirred for 3h at 7000rpm, added with 3g of urea and reacted for 1h at 25 ℃; filtering to obtain filter residue, washing with ethanol for 3 times, placing the filter residue into a ceramic cup of a muffle furnace, heating from 25deg.C to 200deg.C at a heating rate of 5deg.C/min, maintaining at 200deg.C for 60min, and naturally cooling to room temperature to obtain functionalized boron nitride.
Example 3
A flame-retardant foaming silica gel material is prepared by uniformly stirring 56g of liquid-based rubber vinyl silicone oil double-end-capped polydimethylsiloxane, 28g of methyl hydrogen-containing silicone oil, 10g of heat-conducting filler alumina, 3g of foaming agent azo diisobutyronitrile, 0.5g of inhibitor acetylene cyclohexanol, 2.3g of functionalized boron nitride and 0.2g of platinum catalyst, and then transferring the mixture into a mold to be vulcanized for 10min at 120 ℃ and 8 MPa.
The preparation method of the functionalized boron nitride comprises the following steps:
1) 2g of hexagonal boron nitride and 35mL of LTris buffer were added to a flask containing 200mL of deionized water and sonicated with a probe for 30min; then adding NaOH aqueous solution with the concentration of 0.85mol/L until the pH value is 8.5; adding 1g of dopamine hydrochloride into a flask, continuously reacting for 16 hours at 25 ℃, centrifuging for 7 minutes at 5000rpm, taking precipitate, washing with deionized water until the pH value of the supernatant becomes neutral; finally, drying the product in a vacuum oven at 80 ℃ for 24 hours to obtain polydopamine modified boron nitride;
2) 2g of polydopamine modified boron nitride in the step 1) is weighed and dispersed in 375mL of isopropanol, and is mechanically stirred for 6 hours at 5000rpm, and simultaneously, ultrasonic waves are carried out for 6 hours at 20KHz and 25 ℃ to obtain polydopamine modified boron nitride dispersion; 2.54g of ferric nitrate nonahydrate is dissolved in 200mL of ethanol, added into the polydopamine modified boron nitride dispersoid, mechanically stirred for 3 hours at 7000rpm, added with 3g of urea and reacted for 1 hour at 25 ℃; filtering to obtain filter residue, washing with ethanol for 3 times, placing the filter residue into a ceramic cup of a muffle furnace, heating from 25deg.C to 200deg.C at a heating rate of 5deg.C/min, maintaining at 200deg.C for 60min, and naturally cooling to room temperature to obtain functionalized boron nitride.
Example 4
A flame-retardant foaming silica gel material is prepared by uniformly stirring 56g of liquid-based rubber vinyl silicone oil double-end-capped polydimethylsiloxane, 28g of methyl hydrogen-containing silicone oil, 10g of heat-conducting filler alumina, 3g of foaming agent azo diisobutyronitrile, 0.5g of inhibitor acetylene cyclohexanol, 2.3g of functionalized boron nitride and 0.2g of platinum catalyst, and then transferring the mixture into a mold to be vulcanized for 10min at 120 ℃ and 8 MPa.
The preparation method of the functionalized boron nitride comprises the following steps:
1) 2g of chitosan is dissolved in 20mL of dilute hydrochloric acid solution with the concentration of 2mol/L, and deionized water is added to adjust the pH to 4.5; adding 2g of hexagonal boron nitride, and processing for 20min at 20KHz and 45 ℃ by using a cell pulverizer; centrifuging, taking supernatant, washing with deionized water until the pH of the product is neutral; finally, drying the product in a vacuum oven at 80 ℃ for 24 hours to obtain chitosan modified boron nitride;
2) 2g of chitosan modified boron nitride in the step 1) is weighed and dispersed in 375mL of isopropanol, and is mechanically stirred for 6 hours at 5000rpm, and simultaneously, ultrasonic waves are carried out for 6 hours at 20KHz and 25 ℃ to obtain chitosan modified boron nitride dispersoids; 2.54g of ferric nitrate nonahydrate is dissolved in 200mL of ethanol, added into chitosan modified boron nitride dispersoid, mechanically stirred for 3h at 7000rpm, added with 3g of urea and reacted for 1h at 25 ℃; filtering to obtain filter residue, washing with ethanol for 3 times, placing the filter residue into a ceramic cup of a muffle furnace, heating from 25deg.C to 200deg.C at a heating rate of 5deg.C/min, maintaining at 200deg.C for 60min, and naturally cooling to room temperature to obtain functionalized boron nitride.
Comparative example 1
A flame-retardant foaming silica gel material is prepared from 56g of liquid-based rubber vinyl silicone oil double-end-capped polydimethylsiloxane, 28g of methyl hydrogen-containing silicone oil, 10g of heat-conducting filler alumina, 3g of foaming agent azodiisobutyronitrile, 0.5g of inhibitor acetylene cyclohexanol, 1.15g of ferric oxide, 1.15g of hexagonal boron nitride and 0.2g of platinum catalyst by stirring uniformly, and vulcanizing at 120 ℃ and 8MPa for 10 min.
Test example 1
As can be seen from examples 1-4 and comparative example 1, the flame-retardant foamed silica gel material prepared by the method provided by the invention has the advantages that melamine borate-boron nitride is obtained by modifying boron nitride with melamine borate, and the melamine borate-boron nitride is used as a flame retardant in the foamed silica gel material, so that the flame-retardant effect is best, and the tensile strength is better. The reason is that the melamine borate is a boron-nitrogen co-effective flame retardant, which has both solid-phase flame retardance of boron and gas-phase flame retardance of nitrogen.
Claims (10)
1. The flame-retardant foaming silica gel material is characterized by comprising the following components: liquid base adhesive, methyl hydrogen-containing silicone oil, heat conducting filler, foaming agent, platinum catalyst, inhibitor and functional boron nitride.
2. The flame retardant foamed silica gel material of claim 1 wherein: comprises the following components in percentage by weight: 0.1-1wt% of platinum catalyst, 0.5-5wt% of inhibitor, 2-15wt% of functionalized boron nitride, 1-10wt% of foaming agent, 3-20wt% of heat conducting filler, 5-60wt% of methyl hydrogen silicone oil and the balance of liquid base adhesive.
3. The flame-retardant foamed silica gel material according to claim 1 or 2, wherein the preparation method of the functionalized boron nitride comprises the following steps: in terms of the weight portions of the components,
uniformly mixing 1-5 parts of hexagonal boron nitride and 0.1-0.15 part of glycine, fully grinding for 3-4 hours at the ball milling speed of 600-850r/min, and placing in air; adding water, maintaining at room temperature for 1-3 hr, performing ultrasonic treatment at 20-40KHz and 20-35deg.C for 2-8min, centrifuging, collecting precipitate, repeating ultrasonic treatment for 2-4 times, and drying at 55-85deg.C in vacuum oven for 20-28 hr; obtaining the hydroxylated boron nitride;
dispersing 1-5 parts of hydroxylated boron nitride in isopropanol, mechanically stirring for 2-8h, and moving the solution to ultrasonic at 20-45KHz and 25-65 ℃ for 4-8h to obtain hydroxylated boron nitride dispersoid; dissolving 2-7 parts of ferric nitrate nonahydrate in ethanol, adding the ferric nitrate nonahydrate into the hydroxylated boron nitride dispersoid, stirring for 1-4 hours, adding 2-8 parts of urea, and reacting for 0.5-2 hours at room temperature; filtering to obtain filter residue, washing with ethanol for 1-4 times, placing the filter residue into a ceramic cup of a muffle furnace, and maintaining at 180-220deg.C for 1-2 hr; obtaining the functionalized boron nitride.
4. The flame-retardant foamed silica gel material according to claim 1 or 2, wherein the production method of the functionalized boron nitride comprises the following steps: in terms of the weight portions of the components,
uniformly mixing 1-5 parts of hexagonal boron nitride and 1-5 parts of melamine borate, fully grinding for 3-4 hours at the ball milling speed of 600-850r/min, and placing in air; adding water, maintaining at room temperature for 1-3 hr, performing ultrasonic treatment at 20-40KHz and 20-35deg.C for 2-8min, centrifuging, collecting precipitate, repeating ultrasonic treatment for 2-4 times, and drying at 55-85deg.C in vacuum oven for 20-28 hr; obtaining melamine borate-boron nitride;
dispersing 1-5 parts of melamine borate-boron nitride in isopropanol, mechanically stirring for 2-8h, and moving the solution to be subjected to ultrasonic treatment at 20-45KHz and 25-65 ℃ for 4-8h to obtain melamine borate-boron nitride dispersoids; 2-7 parts of ferric nitrate nonahydrate is dissolved in ethanol, added into melamine borate-boron nitride dispersoid, stirred for 1-4 hours, added with 2-8 parts of urea and reacted for 0.5-2 hours at room temperature; filtering to obtain filter residue, washing with ethanol for 1-4 times, placing the filter residue into a ceramic cup of a muffle furnace, and maintaining at 180-220deg.C for 1-2 hr; obtaining the functionalized boron nitride.
5. The flame-retardant foamed silica gel material according to claim 1 or 2, wherein the production method of the functionalized boron nitride comprises the following steps: in terms of the weight portions of the components,
mixing 1-5 parts of hexagonal boron nitride and 30-65 parts of Tris buffer solution, performing ultrasonic treatment for 20-45min by using a probe, and adding NaOH aqueous solution until the pH is 7-9; adding 0.1-4 parts of dopamine hydrochloride, standing at room temperature for 14-20h, centrifuging at 4000-6000rpm for 2-14min, and washing until the pH of the supernatant is neutral; finally drying in a vacuum oven at 60-95 ℃ for 20-32h; obtaining polydopamine modified boron nitride;
dispersing 1-5 parts of polydopamine modified boron nitride in isopropanol, mechanically stirring for 2-8h, and moving the mixture to ultrasonic at 20-45KHz and 25-65 ℃ for 4-8h to obtain polydopamine modified boron nitride dispersoid; 2-7 parts of ferric nitrate nonahydrate is dissolved in ethanol, added into polydopamine modified boron nitride dispersoid, stirred for 1-4 hours, added with 2-8 parts of urea, and reacted for 0.5-2 hours at room temperature; filtering to obtain filter residue, washing with ethanol for 1-4 times, placing the filter residue into a ceramic cup of a muffle furnace, and maintaining at 180-220deg.C for 1-2 hr; obtaining the functionalized boron nitride.
6. The flame-retardant foamed silica gel material according to claim 1 or 2, wherein the production method of the functionalized boron nitride is as follows: in terms of the weight portions of the components,
dissolving 1-5 parts of chitosan in 20-26 parts of dilute hydrochloric acid, adding water to adjust the pH to 2-5, adding 1-5 parts of hexagonal boron nitride, performing ultrasonic treatment for 10-28min, centrifuging, and washing until the pH of the supernatant is neutral; drying in a vacuum oven at 60-95 ℃ for 20-32h to obtain chitosan modified boron nitride;
dispersing 1-5 parts of chitosan modified boron nitride in isopropanol, mechanically stirring for 2-8h, and moving the solution to ultrasonic at 20-45KHz and 25-65 ℃ for 4-8h to obtain a chitosan modified boron nitride dispersion; dissolving 2-7 parts of ferric nitrate nonahydrate in ethanol, adding the ferric nitrate nonahydrate into the chitosan modified boron nitride dispersoid, stirring for 1-4 hours, adding 2-8 parts of urea, and reacting for 0.5-2 hours at room temperature; filtering to obtain filter residue, washing with ethanol for 1-4 times, placing the filter residue into a ceramic cup of a muffle furnace, and maintaining at 180-220deg.C for 1-2 hr; obtaining the functionalized boron nitride.
7. The flame retardant foamed silica gel material according to claim 1 or 2, wherein: the inhibitor is any one of alkynol compounds, nitrile compounds, vinyl siloxane or organic peroxides.
8. The flame retardant foamed silica gel material according to claim 1 or 2, wherein: the heat conducting filler is any one of aluminum oxide, magnesium oxide and silicon carbide.
9. The flame retardant foamed silica gel material according to claim 1 or 2, wherein: the foaming agent is any one of azodiisobutyronitrile, azodiisoheptonitrile and hydroxyl-containing organosilicon compound.
10. The method for preparing a flame retardant foamed silica gel material according to any one of claims 2 to 9, comprising the steps of: fully stirring the liquid base adhesive, methyl hydrogen-containing silicone oil, the heat-conducting filler, the foaming agent, the inhibitor and the functional boron nitride, then adding the platinum catalyst, rapidly and uniformly stirring, and moving into a mould to be vulcanized for 1-30min at the temperature of 100-130 ℃ and the pressure of 6-9MPa to obtain the flame-retardant foaming silica gel material.
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