CN116496753A - High-performance organic silicon sealant and preparation method thereof - Google Patents
High-performance organic silicon sealant and preparation method thereof Download PDFInfo
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- CN116496753A CN116496753A CN202310782008.7A CN202310782008A CN116496753A CN 116496753 A CN116496753 A CN 116496753A CN 202310782008 A CN202310782008 A CN 202310782008A CN 116496753 A CN116496753 A CN 116496753A
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- component
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- linking agent
- montmorillonite
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- 239000000565 sealant Substances 0.000 title claims abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 23
- 239000010703 silicon Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 63
- 239000010452 phosphate Substances 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 60
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 54
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 45
- 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 claims abstract description 40
- 239000003063 flame retardant Substances 0.000 claims abstract description 39
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 26
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 25
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011246 composite particle Substances 0.000 claims abstract description 24
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940083037 simethicone Drugs 0.000 claims abstract description 24
- 238000009830 intercalation Methods 0.000 claims abstract description 20
- 230000002687 intercalation Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 229920002545 silicone oil Polymers 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 64
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 35
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 claims description 22
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- IPGANOYOHAODGA-UHFFFAOYSA-N dilithium;dimagnesium;dioxido(oxo)silane Chemical compound [Li+].[Li+].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IPGANOYOHAODGA-UHFFFAOYSA-N 0.000 claims description 13
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 239000001110 calcium chloride Substances 0.000 claims description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 11
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 229940117955 isoamyl acetate Drugs 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 239000004590 silicone sealant Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- JDSVPBCKKXDLRS-UHFFFAOYSA-K aluminum;phosphate;trihydrate Chemical compound O.O.O.[Al+3].[O-]P([O-])([O-])=O JDSVPBCKKXDLRS-UHFFFAOYSA-K 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- WVPKAWVFTPWPDB-UHFFFAOYSA-N dichlorophosphinic acid Chemical class OP(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000011521 glass Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 230000008093 supporting effect Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention relates to the technical field of organic silicon sealants and discloses a high-performance organic silicon sealant and a preparation method thereof; the method comprises the following steps: uniformly stirring alpha, omega-dihydroxyl polydimethylsiloxane, simethicone and nano calcium carbonate, dispersing in vacuum, adding hollow composite particles, and dispersing in vacuum to obtain a component A; uniformly stirring dimethyl silicone oil and flame-retardant intercalation modified montmorillonite, dispersing in vacuum, adding gamma-aminopropyl triethoxysilane, a phosphate cross-linking agent and an organotin catalyst, and dispersing in vacuum to obtain a component B; and uniformly mixing the component A and the component B in vacuum to obtain the organosilicon sealant.
Description
Technical Field
The invention relates to the technical field of organic silicon sealants, in particular to a high-performance organic silicon sealant and a preparation method thereof.
Background
The silicone sealant, as a common organic silicone sealant, has the advantages of excellent weather resistance, aging resistance, high temperature resistance, low temperature resistance and the like, and is widely applied to the fields of automobile manufacturing and the like, including automobile panels, structural members, power transmission systems, shock absorption, braking systems and the like. However, the organic silicon sealant has the defect of inflammability, so that the organic silicon sealant cannot effectively resist flame in the running and using processes of an automobile if the organic silicon sealant is burnt, a common method is to add a flame retardant additive into the organic silicon sealant by a physical blending method, but the added flame retardant additive cannot be organically combined with reinforcing fillers, cross-linking agents and other additives in the organic silicon sealant, so that the compatibility is poor, and the mechanical property and the processing property of the organic silicon sealant are reduced.
Therefore, the invention of the high-performance organic silicon sealant has important significance.
Disclosure of Invention
The invention aims to provide a high-performance organic silicon sealant and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of high-performance organic silicon sealant comprises the following steps:
s1: adding a phosphate cross-linking agent into an ethanol solution, and regulating the pH to 2-5 to obtain a cross-linking agent solution; adding phosphate modified montmorillonite into ethanol solution, heating to 80-85 ℃ and reacting for 1-2h to obtain montmorillonite solution; adding the cross-linking agent solution into the montmorillonite solution, adjusting the pH value to 2-5, heating to 80-85 ℃ for reaction for 8-10h, washing, filtering, drying, grinding and sieving to obtain the flame-retardant intercalation modified montmorillonite;
s2: uniformly stirring alpha, omega-dihydroxyl polydimethylsiloxane, simethicone and nano calcium carbonate, dispersing in vacuum, adding hollow composite particles, and dispersing in vacuum to obtain a component A; uniformly stirring dimethyl silicone oil and flame-retardant intercalation modified montmorillonite, dispersing in vacuum, adding gamma-aminopropyl triethoxysilane, a phosphate cross-linking agent and an organotin catalyst, and dispersing in vacuum to obtain a component B; uniformly mixing the component A and the component B in vacuum to obtain the organosilicon sealant;
further, the phosphate cross-linking agent is prepared according to the following method:
uniformly stirring pentaerythritol and phosphorus oxychloride, adding calcium chloride, heating to 110-115 ℃ under nitrogen atmosphere, reacting for 6-8h, filtering, washing and drying to obtain dichlorophosphate; stirring the dichlorophosphate, acetonitrile and triethylamine uniformly, adding gamma-aminopropyl triethoxysilane, heating to 65-70 ℃ under nitrogen atmosphere for reaction for 24-36h, washing, filtering, concentrating under reduced pressure, and drying to obtain a phosphate cross-linking agent;
further, the hollow composite particles are prepared as follows:
adding lithium magnesium silicate into deionized water to form a dispersion, regulating the pH to 9.5-10, adding 3- (trimethoxysilyl) propyl methacrylate and isoamyl acetate to react for 8-10h at room temperature, purging with nitrogen for 30-45min, adding potassium persulfate to heat to 70-75 ℃ to react for 12-16h, centrifuging, washing and drying to obtain the hollow composite particles.
Further, in the dichlorophosphate, pentaerythritol: the mass ratio of the phosphorus oxychloride is 1 (6-8); the addition amount of the calcium chloride is 0.7-0.8% of the mass of the pentaerythritol; in the phosphate cross-linking agent, the dichlorophosphate: triethylamine: the mass ratio of the gamma-aminopropyl triethoxysilane is (4-6): 3-4): 6-8.
Further, the phosphate modified montmorillonite is prepared according to the following method:
adjusting pH of 5-6wt% nanometer montmorillonite water solution to 2-2.5, adding aluminum hydroxide-phosphoric acid solution, stirring for 30-45min, adding ammonium hydroxide solution under stirring until pH is 4.7-4.9, filtering, washing, and drying to obtain phosphate modified montmorillonite.
Further, the aluminum hydroxide-phosphoric acid solution is composed of aluminum hydroxide and an aqueous phosphoric acid solution; nano montmorillonite: aluminum hydroxide: the mass ratio of the phosphoric acid aqueous solution is 10 (2-3) to 8.1-12.1.
Further, the lithium magnesium silicate: 3- (trimethoxysilyl) propyl methacrylate: the mass ratio of the isoamyl acetate is 0.2 (0.2-0.4) to 1; the addition amount of the potassium persulfate is 5-6% of the mass of the lithium magnesium silicate.
Further, the phosphate cross-linking agent: the mass ratio of the phosphate modified montmorillonite is (1.5-2) 1.
Further, in the component A, the raw materials comprise, by mass, 150-200 parts of alpha, omega-dihydroxypolydimethylsiloxane, 80-100 parts of simethicone, 200-250 parts of nano calcium carbonate and 20-40 parts of hollow composite particles; in the component B, the raw materials account for 60-80 parts of simethicone, 25-40 parts of flame-retardant intercalation modified montmorillonite, 10-15 parts of gamma-aminopropyl triethoxysilane, 10-20 parts of phosphate cross-linking agent and 0.1-0.5 part of organotin catalyst according to mass fraction; component A: the mass ratio of the component B is (13-15): 1.
Further, the organotin catalyst is SDL101.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes nano montmorillonite as a carrier, and evenly deposits phosphate on the surface of the nano montmorillonite; and then, taking the phosphate grafted by the silane coupling agent as an intercalation modifier to further intercalate and modify the nano montmorillonite to prepare the flame-retardant intercalation modified montmorillonite. The difference with the traditional flame retardant modifier is that the traditional flame retardant modifier can generate a compact carbon layer to isolate air and other combustion-supporting gases when being heated, decomposed and combusted, and prevent heat transfer so as to achieve the aim of flame retardance. The Na+ cations contained in the components of the flame-retardant intercalation modified montmorillonite and the phosphate loaded on the surface form low-melting-point phosphate when the flame-retardant intercalation modified montmorillonite is heated to about 500 ℃, transient liquid phases are formed in the heating process, a solution precipitation matrix is added to promote the growth of phosphate particles, the phosphate particles in the transient liquid phases are continuously aggregated in the process of increasing the temperature, when the temperature is increased to about 600 ℃, the phosphate particle aggregate is broken, the system energy is reduced, meanwhile, a layer of phosphate coating is formed on the surface of the nano-montmorillonite due to the diffusion of the heat stirring effect, and Mg2+ in the nano-montmorillonite reacts with part of phosphate to form magnesium phosphate along with the temperature further increased to about 900 ℃, so that a structural ceramic network taking the nano-montmorillonite as a skeleton and the phosphate as the nano-coating is generated. The three-dimensional nano-structure ceramic network provides firm supporting effect for the carbon layer formed in the N, P element combustion process, and effectively improves the flame retardant property of the organosilicon sealant.
According to the invention, the dichlorophosphate reacts with the KH550 silane coupling agent, the P-containing flame-retardant structure is successfully introduced into the cross-linking agent, and the P-containing flame-retardant organosilicon sealant is successfully prepared through the cross-linking effect. The modified montmorillonite has the same intercalation structure as nano montmorillonite, greatly improves the dispersion performance and compatibility of the modified montmorillonite in the organosilicon sealant, and solves the problem of reduced mechanical property after the traditional flame retardant auxiliary agent is added. Meanwhile, the interfacial force of the intercalated modified nano montmorillonite is enhanced, and a large number of freely moving molecular chains in the sealant can be fixed in the montmorillonite sheets through intercalation, so that the mechanical property of the sealant is greatly enhanced.
According to the invention, the hollow composite particles are prepared from the lithium magnesium silicate and the polymer by an emulsion polymerization method, a large amount of siloxane structures in the polymer greatly enhance the dispersion performance in the resealing glue, and organic silicon substrates generate irregular residues to adhere in a network structure of the hollow composite particles in the thermal decomposition process at 500-700 ℃, so that the connection strength between networks is enhanced, the hollow structure is kept unchanged all the time, and the excellent shape stability of the organic silicon sealant in the ablation process is improved. When the temperature is further increased to 900 ℃, the magnesium lithium silicate is fused, decomposed and adhered to the nano montmorillonite framework to further strengthen the ceramic network and the supporting strength, and further improve the flame retardant property.
Description of the embodiments
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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.
It should be noted that the manufacturers of all the raw materials according to the present invention include, without any particular limitation: the specification of the nano montmorillonite is CEC=100 meq/100g, the specification of the alpha, omega-dihydroxyl polydimethylsiloxane is 20000 mPas, and the viscosity of the simethicone is 350 mPas.
Example 1: a preparation method of high-performance organosilicon sealant comprises the following steps: s1: uniformly stirring 10g of pentaerythritol and 60g of phosphorus oxychloride, adding 0.07g of calcium chloride, heating to 110 ℃ under nitrogen atmosphere for reaction for 6 hours, filtering, washing and drying to obtain dichlorophosphate; uniformly stirring 4g of dichlorophosphate, 100mL of acetonitrile and 3g of triethylamine, adding 6g of gamma-aminopropyl triethoxysilane, heating to 65 ℃ under nitrogen atmosphere for reaction for 24 hours, washing, filtering, concentrating under reduced pressure, and drying to obtain a phosphate cross-linking agent;
s2: adding 10g of nano montmorillonite into 190g of water, uniformly stirring, and regulating the pH value to 2 to obtain a nano montmorillonite aqueous solution with the concentration of 5 wt%; adding 2g of aluminum hydroxide into 8.1g of 85wt% phosphoric acid aqueous solution, stirring for 30min, adding ammonium hydroxide solution until the pH is 4.7 under stirring, filtering, washing and drying to obtain phosphate modified montmorillonite;
s3: 15g of phosphate cross-linking agent is added into 100mL of ethanol solution, and the pH is adjusted to 3, so as to obtain a cross-linking agent solution; adding 10g of phosphate modified montmorillonite into 100mL of ethanol solution, heating to 80 ℃ for reaction for 1h to obtain montmorillonite solution; adding the cross-linking agent solution into the montmorillonite solution, adjusting the pH value to 2, heating to 80 ℃ for reaction for 8 hours, washing, filtering, drying, grinding and sieving to obtain the flame-retardant intercalation modified montmorillonite;
s4: adding 2g of lithium magnesium silicate into 50mL of ionized water to form a dispersion, adjusting the pH to 9.5, adding 2g of 3- (trimethoxysilyl) propyl methacrylate and 10g of isoamyl acetate to react for 8 hours at room temperature, purging with nitrogen for 30 minutes, adding 0.1g of potassium persulfate to heat to 70 ℃ to react for 12 hours, centrifuging, washing and drying to obtain hollow composite particles;
s5: uniformly stirring 150g of alpha, omega-dihydroxypolydimethylsiloxane, 80g of simethicone and 200g of nano calcium carbonate, dispersing in vacuum for 20min, adding 20g of hollow composite particles, and dispersing in vacuum for 10min to obtain a component A; uniformly stirring 60g of simethicone and 25g of flame-retardant intercalated modified montmorillonite, dispersing in vacuum for 25min, adding 10g of gamma-aminopropyl triethoxysilane, 10g of phosphate cross-linking agent and 0.1g of organotin catalyst, and dispersing in vacuum for 5min to obtain a component B; and uniformly mixing 150g of the component A and 10g of the component B in vacuum to obtain the organosilicon sealant.
Example 2: a preparation method of high-performance organosilicon sealant comprises the following steps: s1: uniformly stirring 10g of pentaerythritol and 60g of phosphorus oxychloride, adding 0.07g of calcium chloride, heating to 110 ℃ under nitrogen atmosphere for reaction for 6 hours, filtering, washing and drying to obtain dichlorophosphate; uniformly stirring 4g of dichlorophosphate, 100mL of acetonitrile and 3g of triethylamine, adding 6g of gamma-aminopropyl triethoxysilane, heating to 65 ℃ under nitrogen atmosphere for reaction for 24 hours, washing, filtering, concentrating under reduced pressure, and drying to obtain a phosphate cross-linking agent;
s2: adding 10g of nano montmorillonite into 190g of water, uniformly stirring, and regulating the pH value to 2 to obtain a nano montmorillonite aqueous solution with the concentration of 5 wt%; adding 2g of aluminum hydroxide into 8.1g of 85wt% phosphoric acid aqueous solution, stirring for 30min, adding ammonium hydroxide solution until the pH is 4.7 under stirring, filtering, washing and drying to obtain phosphate modified montmorillonite;
s3: 15g of phosphate cross-linking agent is added into 100mL of ethanol solution, and the pH is adjusted to 3, so as to obtain a cross-linking agent solution; adding 10g of phosphate modified montmorillonite into 100mL of ethanol solution, heating to 80 ℃ for reaction for 1h to obtain montmorillonite solution; adding the cross-linking agent solution into the montmorillonite solution, adjusting the pH value to 2, heating to 80 ℃ for reaction for 8 hours, washing, filtering, drying, grinding and sieving to obtain the flame-retardant intercalation modified montmorillonite;
s4: adding 2g of lithium magnesium silicate into 50mL of ionized water to form a dispersion, adjusting the pH to 9.5, adding 2g of 3- (trimethoxysilyl) propyl methacrylate and 10g of isoamyl acetate to react for 8 hours at room temperature, purging with nitrogen for 30 minutes, adding 0.1g of potassium persulfate to heat to 70 ℃ to react for 12 hours, centrifuging, washing and drying to obtain hollow composite particles;
s5: uniformly stirring 150g of alpha, omega-dihydroxypolydimethylsiloxane, 80g of simethicone and 200g of nano calcium carbonate, dispersing in vacuum for 20min, adding 40g of hollow composite particles, and dispersing in vacuum for 10min to obtain a component A; uniformly stirring 60g of simethicone and 40g of flame-retardant intercalated modified montmorillonite, dispersing in vacuum for 25min, adding 10g of gamma-aminopropyl triethoxysilane, 20g of phosphate cross-linking agent and 0.1g of organotin catalyst, and dispersing in vacuum for 5min to obtain a component B; and (3) uniformly mixing 130g of the component A and 10g of the component B in vacuum to obtain the organosilicon sealant.
Example 3: a preparation method of high-performance organosilicon sealant comprises the following steps: s1: uniformly stirring 10g of pentaerythritol and 60g of phosphorus oxychloride, adding 0.07g of calcium chloride, heating to 110 ℃ under nitrogen atmosphere for reaction for 6 hours, filtering, washing and drying to obtain dichlorophosphate; uniformly stirring 4g of dichlorophosphate, 100mL of acetonitrile and 3g of triethylamine, adding 6g of gamma-aminopropyl triethoxysilane, heating to 65 ℃ under nitrogen atmosphere for reaction for 24 hours, washing, filtering, concentrating under reduced pressure, and drying to obtain a phosphate cross-linking agent;
s2: adding 10g of nano montmorillonite into 190g of water, uniformly stirring, and regulating the pH value to 2 to obtain a nano montmorillonite aqueous solution with the concentration of 5 wt%; adding 2g of aluminum hydroxide into 8.1g of 85wt% phosphoric acid aqueous solution, stirring for 30min, adding ammonium hydroxide solution until the pH is 4.7 under stirring, filtering, washing and drying to obtain phosphate modified montmorillonite;
s3: 15g of phosphate cross-linking agent is added into 100mL of ethanol solution, and the pH is adjusted to 3, so as to obtain a cross-linking agent solution; adding 10g of phosphate modified montmorillonite into 100mL of ethanol solution, heating to 80 ℃ for reaction for 1h to obtain montmorillonite solution; adding the cross-linking agent solution into the montmorillonite solution, adjusting the pH value to 2, heating to 80 ℃ for reaction for 8 hours, washing, filtering, drying, grinding and sieving to obtain the flame-retardant intercalation modified montmorillonite;
s4: adding 2g of lithium magnesium silicate into 50mL of ionized water to form a dispersion, adjusting the pH to 9.5, adding 2g of 3- (trimethoxysilyl) propyl methacrylate and 10g of isoamyl acetate to react for 8 hours at room temperature, purging with nitrogen for 30 minutes, adding 0.1g of potassium persulfate to heat to 70 ℃ to react for 12 hours, centrifuging, washing and drying to obtain hollow composite particles;
s5: uniformly stirring 150g of alpha, omega-dihydroxypolydimethylsiloxane, 80g of simethicone and 200g of nano calcium carbonate, dispersing in vacuum for 20min, adding 30g of hollow composite particles, and dispersing in vacuum for 10min to obtain a component A; uniformly stirring 60g of simethicone and 35g of flame-retardant intercalated modified montmorillonite, dispersing in vacuum for 25min, adding 10g of gamma-aminopropyl triethoxysilane, 15g of phosphate cross-linking agent and 0.1g of organotin catalyst, and dispersing in vacuum for 5min to obtain a component B; and (3) uniformly mixing 140g of the component A and 10g of the component B in vacuum to obtain the organosilicon sealant.
Comparative example 1: a preparation method of high-performance organosilicon sealant comprises the following steps: s1: uniformly stirring 150g of alpha, omega-dihydroxypolydimethylsiloxane, 80g of simethicone and 200g of nano calcium carbonate, dispersing in vacuum for 20min, adding 20g of hollow glass microspheres, and dispersing in vacuum for 10min to obtain a component A; uniformly stirring 60g of simethicone and 25g of organic montmorillonite, dispersing in vacuum for 25min, adding 10g of gamma-aminopropyl triethoxysilane, 10g of cross-linking agent, 5g of DOPO and 0.1g of organotin catalyst, and dispersing in vacuum for 5min to obtain a component B; and uniformly mixing 150g of the component A and 10g of the component B in vacuum to obtain the organosilicon sealant. Wherein, the organic montmorillonite is prepared by the reaction of montmorillonite and hexadecyl trimethyl ammonium bromide.
Comparative example 2: a preparation method of high-performance organosilicon sealant comprises the following steps: s1: uniformly stirring 10g of pentaerythritol and 60g of phosphorus oxychloride, adding 0.07g of calcium chloride, heating to 110 ℃ under nitrogen atmosphere for reaction for 6 hours, filtering, washing and drying to obtain dichlorophosphate; uniformly stirring 4g of dichlorophosphate, 100mL of acetonitrile and 3g of triethylamine, adding 6g of gamma-aminopropyl triethoxysilane, heating to 65 ℃ under nitrogen atmosphere for reaction for 24 hours, washing, filtering, concentrating under reduced pressure, and drying to obtain a phosphate cross-linking agent;
s2: adding 10g of nano montmorillonite into 190g of water, uniformly stirring, and regulating the pH value to 2 to obtain a nano montmorillonite aqueous solution with the concentration of 5 wt%; adding 2g of aluminum hydroxide into 8.1g of 85wt% phosphoric acid aqueous solution, stirring for 30min, adding ammonium hydroxide solution until the pH is 4.7 under stirring, filtering, washing and drying to obtain phosphate modified montmorillonite;
s3: 15g of phosphate cross-linking agent is added into 100mL of ethanol solution, and the pH is adjusted to 3, so as to obtain a cross-linking agent solution; adding 10g of phosphate modified montmorillonite into 100mL of ethanol solution, heating to 80 ℃ for reaction for 1h to obtain montmorillonite solution; adding the cross-linking agent solution into the montmorillonite solution, adjusting the pH value to 2, heating to 80 ℃ for reaction for 8 hours, washing, filtering, drying, grinding and sieving to obtain the flame-retardant intercalation modified montmorillonite;
s4: uniformly stirring 150g of alpha, omega-dihydroxypolydimethylsiloxane, 80g of simethicone and 200g of nano calcium carbonate, dispersing in vacuum for 20min, adding 20g of hollow glass beads, and dispersing in vacuum for 10min to obtain a component A; uniformly stirring 60g of simethicone and 25g of flame-retardant intercalated modified montmorillonite, dispersing in vacuum for 25min, adding 10g of gamma-aminopropyl triethoxysilane, 10g of phosphate cross-linking agent and 0.1g of organotin catalyst, and dispersing in vacuum for 5min to obtain a component B; and uniformly mixing 150g of the component A and 10g of the component B in vacuum to obtain the organosilicon sealant.
Comparative example 3: a preparation method of high-performance organosilicon sealant comprises the following steps: s1: uniformly stirring 10g of pentaerythritol and 60g of phosphorus oxychloride, adding 0.07g of calcium chloride, heating to 110 ℃ under nitrogen atmosphere for reaction for 6 hours, filtering, washing and drying to obtain dichlorophosphate; uniformly stirring 4g of dichlorophosphate, 100mL of acetonitrile and 3g of triethylamine, adding 6g of gamma-aminopropyl triethoxysilane, heating to 65 ℃ under nitrogen atmosphere for reaction for 24 hours, washing, filtering, concentrating under reduced pressure, and drying to obtain a phosphate cross-linking agent;
s2: adding 10g of nano montmorillonite into 190g of water, uniformly stirring, and regulating the pH value to 2 to obtain a nano montmorillonite aqueous solution with the concentration of 5 wt%; adding 2g of aluminum hydroxide into 8.1g of 85wt% phosphoric acid aqueous solution, stirring for 30min, adding ammonium hydroxide solution until the pH is 4.7 under stirring, filtering, washing and drying to obtain phosphate modified montmorillonite;
s4: adding 2g of lithium magnesium silicate into 50mL of ionized water to form a dispersion, adjusting the pH to 9.5, adding 2g of 3- (trimethoxysilyl) propyl methacrylate and 10g of isoamyl acetate to react for 8 hours at room temperature, purging with nitrogen for 30 minutes, adding 0.1g of potassium persulfate to heat to 70 ℃ to react for 12 hours, centrifuging, washing and drying to obtain hollow composite particles;
s5: uniformly stirring 150g of alpha, omega-dihydroxypolydimethylsiloxane, 80g of simethicone and 200g of nano calcium carbonate, dispersing in vacuum for 20min, adding 20g of hollow composite particles, and dispersing in vacuum for 10min to obtain a component A; uniformly stirring 60g of simethicone and 25g of phosphate modified montmorillonite, dispersing in vacuum for 25min, adding 10g of gamma-aminopropyl triethoxysilane, 10g of phosphate cross-linking agent and 0.1g of organotin catalyst, and dispersing in vacuum for 5min to obtain a component B; and uniformly mixing 150g of the component A and 10g of the component B in vacuum to obtain the organosilicon sealant.
Comparative example 4: a preparation method of high-performance organosilicon sealant comprises the following steps: s1: uniformly stirring 10g of pentaerythritol and 60g of phosphorus oxychloride, adding 0.07g of calcium chloride, heating to 110 ℃ under nitrogen atmosphere for reaction for 6 hours, filtering, washing and drying to obtain dichlorophosphate; uniformly stirring 4g of dichlorophosphate, 100mL of acetonitrile and 3g of triethylamine, adding 6g of gamma-aminopropyl triethoxysilane, heating to 65 ℃ under nitrogen atmosphere for reaction for 24 hours, washing, filtering, concentrating under reduced pressure, and drying to obtain a phosphate cross-linking agent;
s2: 15g of phosphate cross-linking agent is added into 100mL of ethanol solution, and the pH is adjusted to 3, so as to obtain a cross-linking agent solution; adding 10g of nano montmorillonite into 100mL of ethanol solution, heating to 80 ℃ for reaction for 1h to obtain montmorillonite solution; adding the cross-linking agent solution into the montmorillonite solution, adjusting the pH value to 2, heating to 80 ℃ for reaction for 8 hours, washing, filtering, drying, grinding and sieving to obtain the flame-retardant intercalation modified montmorillonite;
s3: adding 2g of lithium magnesium silicate into 50mL of ionized water to form a dispersion, adjusting the pH to 9.5, adding 2g of 3- (trimethoxysilyl) propyl methacrylate and 10g of isoamyl acetate to react for 8 hours at room temperature, purging with nitrogen for 30 minutes, adding 0.1g of potassium persulfate to heat to 70 ℃ to react for 12 hours, centrifuging, washing and drying to obtain hollow composite particles;
s4: uniformly stirring 150g of alpha, omega-dihydroxypolydimethylsiloxane, 80g of simethicone and 200g of nano calcium carbonate, dispersing in vacuum for 20min, adding 20g of hollow composite particles, and dispersing in vacuum for 10min to obtain a component A; uniformly stirring 60g of simethicone and 25g of flame-retardant intercalated modified montmorillonite, dispersing in vacuum for 25min, adding 10g of gamma-aminopropyl triethoxysilane, 10g of phosphate cross-linking agent and 0.1g of organotin catalyst, and dispersing in vacuum for 5min to obtain a component B; and uniformly mixing 150g of the component A and 10g of the component B in vacuum to obtain the organosilicon sealant.
Comparative example 5: a preparation method of high-performance organosilicon sealant comprises the following steps: s1: uniformly stirring 10g of pentaerythritol and 60g of phosphorus oxychloride, adding 0.07g of calcium chloride, heating to 110 ℃ under nitrogen atmosphere for reaction for 6 hours, filtering, washing and drying to obtain dichlorophosphate; uniformly stirring 4g of dichlorophosphate, 100mL of acetonitrile and 3g of triethylamine, adding 6g of gamma-aminopropyl triethoxysilane, heating to 65 ℃ under nitrogen atmosphere for reaction for 24 hours, washing, filtering, concentrating under reduced pressure, and drying to obtain a phosphate cross-linking agent;
s2: 15g of phosphate cross-linking agent is added into 100mL of ethanol solution, and the pH is adjusted to 3, so as to obtain a cross-linking agent solution; adding 10g of nano montmorillonite into 100mL of ethanol solution, heating to 80 ℃ for reaction for 1h to obtain montmorillonite solution; adding the cross-linking agent solution into the montmorillonite solution, adjusting the pH value to 2, heating to 80 ℃ for reaction for 8 hours, washing, filtering, drying, grinding and sieving to obtain the flame-retardant intercalation modified montmorillonite;
s3: uniformly stirring 150g of alpha, omega-dihydroxypolydimethylsiloxane, 80g of simethicone and 200g of nano calcium carbonate, dispersing in vacuum for 20min, adding 20g of hollow glass beads, and dispersing in vacuum for 10min to obtain a component A; uniformly stirring 60g of simethicone and 25g of flame-retardant intercalated modified montmorillonite, dispersing in vacuum for 25min, adding 10g of gamma-aminopropyl triethoxysilane, 10g of phosphate cross-linking agent and 0.1g of organotin catalyst, and dispersing in vacuum for 5min to obtain a component B; and uniformly mixing 150g of the component A and 10g of the component B in vacuum to obtain the organosilicon sealant.
And (3) testing: mechanical property test: the silicone sealants prepared in examples 1 to 3 and comparative examples 1 to 5 were cured for 7d according to GB/T528-1998 standard at 25℃and 50% relative humidity, cut into standard dumbbell-shaped test pieces, and tested for tensile strength and elongation at break using a universal tester.
Flame retardant performance test: the limiting oxygen index test was performed on samples of dimensions 100mm by 6mm by 2mm according to GB/T10707-2008.
The vertical burning test was performed on samples 120mm by 12mm by 3mm in size according to UL 94-2009 standard.
TABLE 1 Silicone sealant Performance test
| Tensile Strength/MPa | Elongation at break/% | UL-94 | Oxygen index/% | |
| Example 1 | 0.96 | 383 | V-0 | 33.2 |
| Example 2 | 1.22 | 374 | V-0 | 34.4 |
| Example 3 | 1.18 | 392 | V-0 | 33.9 |
| Comparative example 1 | 0.42 | 302 | V-2 | 26.4 |
| Comparative example 2 | 0.78 | 360 | V-0 | 31.2 |
| Comparative example 3 | 0.88 | 378 | V-0 | 32.2 |
| Comparative example 4 | 0.95 | 381 | V-0 | 31.5 |
| Comparative example 5 | 0.93 | 380 | V-1 | 28.8 |
Conclusion: the organosilicon sealant prepared in the examples 1-3 has excellent mechanical properties and flame retardant properties.
In comparative example 1, organic montmorillonite was added instead of modified nano montmorillonite, hollow glass microspheres were substituted for hollow composite particles, and DOPO flame retardant was directly added, resulting in reduced compatibility, reduced molecular segment fixation, and reduced mechanical properties and flame retardant properties.
In comparative example 2, no hollow composite particles were added, and the absence of reinforcing filler resulted in a decrease in mechanical properties; resulting in a reduced skeletal support and a reduced flame retardant performance.
In comparative example 3, no intercalation modification is performed on the nano montmorillonite, which results in weakening of the fixing effect of the free moving molecular chain segments in the sealant, resulting in reduction of mechanical properties, reduction of components of the flame retardant, and reduction of flame retardant properties.
In comparative example 4, the nano montmorillonite surface is not silicate loaded, so that the ceramic coating is slowly formed, the skeleton supporting effect is weakened, and the mechanical property and the flame retardant property are reduced.
In comparative example 5, the nano montmorillonite surface was not silicate loaded, and hollow glass beads were used to substitute for hollow composite particles, so that a ceramic coating could not be formed, the skeleton supporting effect was weakened, and the mechanical properties and flame retardant properties were reduced.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of high-performance organic silicon sealant is characterized by comprising the following steps: the method comprises the following steps:
s1: adding a phosphate cross-linking agent into an ethanol solution, and regulating the pH to 2-5 to obtain a cross-linking agent solution; adding phosphate modified montmorillonite into ethanol solution, heating to 80-85 ℃ and reacting for 1-2h to obtain montmorillonite solution; adding the cross-linking agent solution into the montmorillonite solution, adjusting the pH value to 2-5, heating to 80-85 ℃ for reaction for 8-10h, washing, filtering, drying, grinding and sieving to obtain the flame-retardant intercalation modified montmorillonite;
s2: uniformly stirring alpha, omega-dihydroxyl polydimethylsiloxane, simethicone and nano calcium carbonate, dispersing in vacuum, adding hollow composite particles, and dispersing in vacuum to obtain a component A; uniformly stirring dimethyl silicone oil and flame-retardant intercalation modified montmorillonite, dispersing in vacuum, adding gamma-aminopropyl triethoxysilane, a phosphate cross-linking agent and an organotin catalyst, and dispersing in vacuum to obtain a component B; uniformly mixing the component A and the component B in vacuum to obtain the organosilicon sealant;
the phosphate cross-linking agent is prepared by the following steps:
uniformly stirring pentaerythritol and phosphorus oxychloride, adding calcium chloride, heating to 110-115 ℃ under nitrogen atmosphere, reacting for 6-8h, filtering, washing and drying to obtain dichlorophosphate; stirring the dichlorophosphate, acetonitrile and triethylamine uniformly, adding gamma-aminopropyl triethoxysilane, heating to 65-70 ℃ under nitrogen atmosphere for reaction for 24-36h, washing, filtering, concentrating under reduced pressure, and drying to obtain a phosphate cross-linking agent;
the hollow composite particles are prepared according to the following method:
adding lithium magnesium silicate into deionized water to form a dispersion, regulating the pH to 9.5-10, adding 3- (trimethoxysilyl) propyl methacrylate and isoamyl acetate to react for 8-10h at room temperature, purging with nitrogen for 30-45min, adding potassium persulfate to heat to 70-75 ℃ to react for 12-16h, centrifuging, washing and drying to obtain the hollow composite particles.
2. The method for preparing the high-performance organic silicon sealant according to claim 1, which is characterized in that: in dichlorophosphate esters, pentaerythritol: the mass ratio of the phosphorus oxychloride is 1 (6-8); the addition amount of the calcium chloride is 0.7-0.8% of the mass of the pentaerythritol; in the phosphate cross-linking agent, the dichlorophosphate: triethylamine: the mass ratio of the gamma-aminopropyl triethoxysilane is (4-6): 3-4): 6-8.
3. The method for preparing the high-performance organic silicon sealant according to claim 1, which is characterized in that: in the step S1, the phosphate modified montmorillonite is prepared according to the following method:
adjusting pH of 5-6wt% nanometer montmorillonite water solution to 2-2.5, adding aluminum hydroxide-phosphoric acid solution, stirring for 30-45min, adding ammonium hydroxide solution under stirring until pH is 4.7-4.9, filtering, washing, and drying to obtain phosphate modified montmorillonite.
4. A method for preparing a high performance silicone sealant according to claim 3, wherein: the aluminum hydroxide-phosphoric acid solution consists of aluminum hydroxide and phosphoric acid aqueous solution; nano montmorillonite: aluminum hydroxide: the mass ratio of the phosphoric acid aqueous solution is 10 (2-3) to 8.1-12.1.
5. The method for preparing the high-performance organic silicon sealant according to claim 1, which is characterized in that: lithium magnesium silicate: 3- (trimethoxysilyl) propyl methacrylate: the mass ratio of the isoamyl acetate is 0.2 (0.2-0.4) to 1; the addition amount of the potassium persulfate is 5-6% of the mass of the lithium magnesium silicate.
6. The method for preparing the high-performance organic silicon sealant according to claim 1, which is characterized in that: in step S1, phosphate cross-linking agent: the mass ratio of the phosphate modified montmorillonite is (1.5-2) 1.
7. The method for preparing the high-performance organic silicon sealant according to claim 1, which is characterized in that: in the component A, the raw materials account for 150-200 parts of alpha, omega-dihydroxy polydimethylsiloxane, 80-100 parts of simethicone, 200-250 parts of nano calcium carbonate and 20-40 parts of hollow composite particles in parts by weight; in the component B, the raw materials account for 60-80 parts of simethicone, 25-40 parts of flame-retardant intercalation modified montmorillonite, 10-15 parts of gamma-aminopropyl triethoxysilane, 10-20 parts of phosphate cross-linking agent and 0.1-0.5 part of organotin catalyst according to mass fraction; component A: the mass ratio of the component B is (13-15): 1.
8. The silicone sealant according to any one of claims 1 to 7, wherein the silicone sealant is prepared by a method for preparing a high-performance silicone sealant.
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