CN112048152A - Flame-retardant sealing material and preparation method thereof - Google Patents
Flame-retardant sealing material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a flame-retardant sealing material, which is an epoxy resin material containing a flame retardant; the flame retardant is metal-organic framework material organic magnesium aluminum, and the preparation method comprises the following steps: s1, dissolving magnesium nitrate, aluminum nitrate and terephthalic acid in a solvent to obtain a first solution; s2, adding the polystyrene microspheres into a container, and spraying a pore-foaming agent to obtain porous polystyrene beads; s3, transferring the first solution into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, adding porous polystyrene beads, performing ultrasonic treatment until the porous polystyrene beads are uniformly dispersed, and then dropwise adding ammonia water to adjust the pH value; and S4, placing the hydrothermal synthesis kettle in a muffle furnace for reaction, washing, filtering and calcining to obtain the metal-organic framework material loaded with the organic magnesium and aluminum. According to the invention, through the research on the flame retardant, the better mechanical property and adhesion of the epoxy resin sealing material are ensured, and meanwhile, the sealing material has higher flame retardance, better hydrophobicity, dispersibility, compatibility and mechanical property.
Description
Technical Field
The invention relates to the technical field of sealing materials, in particular to a flame-retardant sealing material and a preparation method thereof.
Background
During the construction of a building, a large number of building pipelines, such as air-conditioning pipelines, smoke-exhaust-preventing pipelines, water supply and drainage pipelines, heating and power pipelines, ventilating pipelines, gas pipelines, oil pipes and other process pipelines, transversely penetrate between a floor slab and bodies. The pipelines pass through holes formed in walls and floors, or gaps between floors and walls and between walls are all paths for fire propagation. In addition, some gaps are reserved for ensuring the normal use of fire doors, fire windows, fire valves and fire-proof rolling shutters in buildings. Without effective blocking of these holes or gaps, in the event of a fire, these holes or gaps would create a smoky effect and a difference in fire pressure across the holes or gaps, causing the fire to spread gradually in adjacent rooms, compromising the life and property of other fire zones.
At present, the fireproof sealing material is generally adopted at home and abroad to block openings or holes formed when various penetrations penetrate through walls or floors, the volume of the fireproof sealing material expands firstly and then hardens under the action of high temperature and flame to form a hard microporous fire-retardant carbon layer, the heat-insulating layer has good heat-insulating property and plays roles in fire-retardant smoke blocking and heat insulation, and meanwhile, the expanded fire-retardant carbon layer can completely fill the holes left after the ablation of combustible materials such as cable insulating skins and the like, so that the fireproof plugging is thoroughly and effectively achieved.
The existing fireproof sealing material has poor flame retardant effect, the raw materials are not uniformly mixed, so that the material has low structural stability and poor fireproof flame retardance, and the mechanical property of the sealant is often greatly reduced by adopting a filled inorganic flame retardant or an intumescent flame retardant, so that the hot point of the current research is how to effectively improve the flame retardant property of the sealant and not obviously reduce other properties.
Disclosure of Invention
The invention aims to provide a flame-retardant sealing material and a preparation method thereof, wherein the synthesized flame retardant metal-organic framework material organic magnesium aluminum has excellent thermal stability, does not generate corrosive gas, is non-volatile, has the advantages of no toxicity, smoke suppression and the like, but generally needs larger filling amount, the flame-retardant and smoke suppression effect is better when the adding amount is larger, and moderate flame retardance can be obtained only when the adding amount is high.
The technical scheme of the invention is realized as follows:
the invention provides a flame-retardant sealing material, which is an epoxy resin material containing a flame retardant;
the flame retardant is a metal-organic framework material organic magnesium aluminum, and the preparation method comprises the following steps:
s1, dissolving magnesium nitrate, aluminum nitrate and terephthalic acid in a first solvent to obtain a first solution;
s2, adding the polystyrene microspheres into a container, and spraying a certain amount of n-octanol and polyvinyl acetate solution to form holes to obtain porous polystyrene beads;
s3, transferring the first solution into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, adding the porous polystyrene beads obtained in the step S2, performing ultrasonic treatment until the beads are uniformly dispersed, and then dropwise adding ammonia water to adjust the pH value to 7.5-8.5;
s4, placing the hydrothermal synthesis kettle in a muffle furnace for reaction, naturally cooling to room temperature, washing and filtering reaction liquid by deionized water, and calcining the obtained beads in the muffle furnace to obtain the metal-organic framework material loaded with the organic magnesium and aluminum.
Preferably, the epoxy resin is a bisphenol a type epoxy resin.
As a further improvement of the invention, the mass ratio of the aluminum nitrate, the magnesium nitrate, the terephthalic acid and the first solvent in the step S1 is 1:1 (0.5-1.5): 100; the first solvent is one or a mixture of deionized water, ethanol, methanol and tetrahydrofuran.
As a further improvement of the invention, in step S2, the mass fraction of n-octanol in the solution of n-octanol and polyvinyl acetate is 30-50 wt%, the mass fraction of polyvinyl acetate solution is 5-15 wt%, and the mass ratio of the polystyrene microsphere to the sprayed solution of n-octanol and polyvinyl acetate is 100: (2-10).
As a further improvement of the invention, the reaction temperature of the step S4 is 180-200 ℃, and the reaction time is 48-60 h; the calcination temperature is 400-420 ℃, and the calcination time is 48-60 h.
As a further improvement of the invention, the flame retardant further comprises chloroplatinic acid.
As a further improvement of the invention, the mass ratio of the organic magnesium aluminum and the chloroplatinic acid of the metal-organic framework material is 100: (1-5).
As a further improvement of the invention, the paint also comprises a plasticizer, a filler and an adhesion promoter.
As a further improvement of the present invention, the plasticizer is selected from one or more of di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate, diethyl phthalate, butylbenzyl phthalate, tetraisooctyl pyromellitate, acetyl tributyl citrate, trioctyl phosphate and diphenyloctyl phosphate; the filler is one or more of calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, talcum powder, kaolin, mica powder and wollastonite; the adhesion promoter is polyamide resin and/or polyurethane resin.
As a further improvement of the invention, the content of the epoxy resin is 12-37 wt%, the content of the plasticizer is 12-50 wt%, the content of the filler is 20-70 wt%, the content of the adhesion promoter is 0.5-5 wt%, and the content of the flame retardant is 2-7 wt% based on the total weight of the composition.
The invention further provides a preparation method of the flame-retardant sealing material, which comprises the following steps:
s1, heating and melting epoxy resin, adding a plasticizer, and uniformly mixing to obtain a first component;
s2, uniformly mixing the flame retardant and the filler to obtain a second component;
s3, mixing the first component obtained in the step S1 with the second component obtained in the step S2, adding an adhesion promoter, and uniformly mixing to obtain a mixed material;
and S4, rolling and forming the mixed material obtained in the step S3, and cooling to obtain the flame-retardant sealing material.
The action mechanism of the flame retardant metal-organic framework material organic magnesium aluminum is as follows: on one hand, the crystal water is released when being heated, and the crystal water is evaporated into water vapor at high temperature and absorbs a large amount of heat, so that the surface temperature of the material is reduced, and the thermal decomposition and combustion rate of the polymer are also obviously reduced; on the other hand, the concentration of the combustible gas is diluted to a certain extent by a large amount of water vapor generated by evaporation; meanwhile, the aluminum oxide and the magnesium oxide generated by thermal decomposition have larger surface area, and can absorb smoke and combustible micromolecules, thereby playing a role in flame retardance.
The mechanism is that in the thermal degradation process of 400-500 ℃, chloroplatinic acid initiates the degradation of side chain methyl of bisphenol A epoxy resin and couples with free radicals to cause the generation of crosslinking points, and the free radical reaction is that C-CH is catalyzed by platinum3Bonds are homolytic to a methyl group and an alkyl radical initiated, the former getting a hydrogen atom from the other methyl group to form methane and releasing a methylene radical to link to the oxyalkylene chain, and eventually this oversized radical chain attacks the adjacent polymer chain and initiates crosslinking reactions of the polymer matrix, thereby inhibiting the formation of degradation-promoting transition complexes (low molar mass cyclic polysiloxanes).
The invention has the following beneficial effects:
the preparation method has the advantages of mild conditions, low energy consumption, simple preparation method and easily obtained raw materials. The method realizes the large-scale loading of the organic magnesium and the aluminum in the pore channels inside the porous polystyrene carrier, and the organic magnesium and the aluminum have high loading rate. In the pretreatment process of the polystyrene carrier, a high-efficiency pore-forming agent is adopted to form pores, so that the chelation of metal atoms in the organic magnesium and aluminum and the carrier is facilitated, the interaction force of the organic magnesium and aluminum and the inner wall of a pore channel of the carrier is enhanced, and the stable loading of the organic magnesium and the aluminum is realized. In addition, the uniform dispersion of organic magnesium and aluminum in the inner pore channels of the carrier is realized, and the organic framework composite material with microporous-mesoporous-macroporous multilevel pore channels is prepared.
The organic magnesium-aluminum of the flame retardant metal-organic framework material synthesized by the invention has excellent thermal stability, does not generate corrosive gas, is not volatile, has the advantages of no toxicity, smoke suppression and the like, but generally needs larger filling amount, the more the addition amount is, the better the flame retardant and smoke suppression effect is, and the moderate flame retardance can be obtained only by high addition amount.
According to the invention, through the research on the flame retardant, the better mechanical property and adhesion of the epoxy resin sealing material are ensured, and meanwhile, the sealing material has higher flame retardance, better hydrophobicity, dispersibility, compatibility and mechanical property.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
N-octanol, CAS number 111-87-5; polyvinyl acetate, CAS No. 9003-20-7; polystyrene, CAS number 9003-53-6; polystyrene microspheres were purchased from Thermo Fisher corporation.
Di-n-octyl phthalate, CAS number 117-84-0; diisodecyl phthalate having CAS number 26761-40-0; dibutyl phthalate, CAS number 84-74-2; diethyl phthalate, CAS number 84-66-2;
polyamide resin, CAS No. 63428-84-2; polyurethane resin, CAS No. 9009-54-5;
kaolin, CAS number 1332-58-7; mica powder, CAS number 12001-26-2; calcium carbonate, CAS number 471-34-1.
Example 1
The raw materials comprise (by weight percent): the content of bisphenol a type epoxy resin was 37% by weight, the content of di-n-octyl phthalate was 12% by weight, the content of calcium carbonate was 48.5% by weight, the content of polyamide resin was 0.5% by weight, and the content of flame retardant was 2% by weight.
The flame retardant is metal-organic framework material organic magnesium aluminum, and the preparation method comprises the following steps:
s1, dissolving 1mol of magnesium nitrate, 1mol of aluminum nitrate and 0.5mol of terephthalic acid in 100mL of deionized water to obtain a first solution;
s2, adding 100g of polystyrene microspheres into a container, and spraying 2g of a solution containing 30 wt% of n-octanol and 5 wt% of polyvinyl acetate to form holes so as to obtain porous polystyrene beads;
s3, transferring the first solution into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, adding the porous polystyrene beads obtained in the step S2, performing ultrasonic treatment until the porous polystyrene beads are uniformly dispersed, and then dropwise adding ammonia water to adjust the pH value to 7.5;
s4, placing the hydrothermal synthesis kettle in a muffle furnace for reaction at the temperature of 180 ℃ for 48 hours, naturally cooling to room temperature, washing and filtering reaction liquid by deionized water, and calcining the obtained beads in the muffle furnace at the temperature of 400 ℃ for 48 hours to obtain the metal-organic framework material loaded with the organic magnesium and aluminum.
The preparation method of the flame-retardant sealing material comprises the following steps:
s1, heating and melting bisphenol A epoxy resin, adding di-n-octyl phthalate, and uniformly mixing to obtain a first component;
s2, uniformly mixing the flame retardant and calcium carbonate to obtain a second component;
s3, mixing the first component obtained in the step S1 with the second component obtained in the step S2, adding polyamide resin, and uniformly mixing to obtain a mixed material;
and S4, rolling and forming the mixed material obtained in the step S3, and cooling to obtain the flame-retardant sealing material.
Example 2
The raw materials comprise (by weight percent): the content of bisphenol a type epoxy resin was 12% by weight, the content of di-n-octyl phthalate was 50% by weight, the content of calcium carbonate was 26% by weight, the content of polyamide resin was 5% by weight, and the content of flame retardant was 7% by weight.
The flame retardant is metal-organic framework material organic magnesium aluminum, and the preparation method comprises the following steps:
s1, dissolving 1mol of magnesium nitrate, 1mol of aluminum nitrate and 1.5mol of terephthalic acid in 100mL of ethanol water solution (ethanol content is 50 wt%) to obtain a first solution;
s2, adding 100g of polystyrene microspheres into a container, and spraying 10g of a solution containing 50 wt% of n-octanol and 15 wt% of polyvinyl acetate to form holes so as to obtain porous polystyrene beads;
s3, transferring the first solution into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, adding the porous polystyrene beads obtained in the step S2, performing ultrasonic treatment until the porous polystyrene beads are uniformly dispersed, and then dropwise adding ammonia water to adjust the pH value to 8;
s4, placing the hydrothermal synthesis kettle in a muffle furnace for reaction at the reaction temperature of 200 ℃ for 60 hours, naturally cooling to room temperature, washing and filtering reaction liquid by deionized water, and calcining the obtained beads in the muffle furnace at the calcination temperature of 420 ℃ for 60 hours to obtain the metal-organic framework material loaded with the organic magnesium and aluminum.
The preparation method of the flame-retardant sealing material comprises the following steps:
s1, heating and melting bisphenol A epoxy resin, adding di-n-octyl phthalate, and uniformly mixing to obtain a first component;
s2, uniformly mixing the flame retardant and calcium carbonate to obtain a second component;
s3, mixing the first component obtained in the step S1 with the second component obtained in the step S2, adding polyamide resin, and uniformly mixing to obtain a mixed material;
and S4, rolling and forming the mixed material obtained in the step S3, and cooling to obtain the flame-retardant sealing material.
Example 3
The raw materials comprise (by weight percent): the content of bisphenol a type epoxy resin was 20 wt%, the content of diisodecyl phthalate was 50 wt%, the content of calcium carbonate was 20 wt%, the content of polyurethane resin was 5 wt%, and the content of flame retardant was 5 wt%.
The flame retardant is metal-organic framework material organic magnesium aluminum, and the preparation method comprises the following steps:
s1, dissolving 1mol of magnesium nitrate, 1mol of aluminum nitrate and 1mol of terephthalic acid in 100mL of methanol-ethanol-water solution (the methanol content is 15 wt%, and the ethanol content is 25 wt%) to obtain a first solution;
s2, adding 100g of polystyrene microspheres into a container, and spraying 6g of a solution containing 40 wt% of n-octanol and 10 wt% of polyvinyl acetate to form holes so as to obtain porous polystyrene beads;
s3, transferring the first solution into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, adding the porous polystyrene beads obtained in the step S2, performing ultrasonic treatment until the porous polystyrene beads are uniformly dispersed, and then dropwise adding ammonia water to adjust the pH value;
s4, placing the hydrothermal synthesis kettle in a muffle furnace for reaction at 190 ℃ for 52 hours, naturally cooling to room temperature, washing and filtering reaction liquid by deionized water, and calcining the obtained beads in the muffle furnace at 410 ℃ for 52 hours to obtain the metal-organic framework material loaded with the organic magnesium and aluminum.
The preparation method of the flame-retardant sealing material comprises the following steps:
s1, heating and melting bisphenol A epoxy resin, adding diisodecyl phthalate, and uniformly mixing to obtain a first component;
s2, uniformly mixing the flame retardant and calcium carbonate to obtain a second component;
s3, mixing the first component obtained in the step S1 with the second component obtained in the step S2, adding polyurethane resin, and uniformly mixing to obtain a mixed material;
and S4, rolling and forming the mixed material obtained in the step S3, and cooling to obtain the flame-retardant sealing material.
Example 4
The raw materials comprise (by weight percent): the content of bisphenol a type epoxy resin was 12 wt%, the content of dibutyl phthalate was 12 wt%, the content of mica powder was 70 wt%, the content of polyurethane resin was 3 wt%, and the content of flame retardant was 3 wt%.
The flame retardant is metal-organic framework material organic magnesium aluminum, and the preparation method comprises the following steps:
s1, dissolving 1mol of magnesium nitrate, 1mol of aluminum nitrate and 1mol of terephthalic acid in 100mL of methanol-ethanol-water solution (the methanol content is 15 wt%, and the ethanol content is 25 wt%) to obtain a first solution;
s2, adding 100g of polystyrene microspheres into a container, and spraying 6g of a solution containing 40 wt% of n-octanol and 10 wt% of polyvinyl acetate to form holes so as to obtain porous polystyrene beads;
s3, transferring the first solution into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, adding the porous polystyrene beads obtained in the step S2, performing ultrasonic treatment until the porous polystyrene beads are uniformly dispersed, and then dropwise adding ammonia water to adjust the pH value;
s4, placing the hydrothermal synthesis kettle in a muffle furnace for reaction at 190 ℃ for 52 hours, naturally cooling to room temperature, washing and filtering reaction liquid by deionized water, and calcining the obtained beads in the muffle furnace at 410 ℃ for 52 hours to obtain the metal-organic framework material loaded with the organic magnesium and aluminum.
The preparation method of the flame-retardant sealing material comprises the following steps:
s1, heating and melting bisphenol A epoxy resin, adding dibutyl phthalate, and uniformly mixing to obtain a first component;
s2, uniformly mixing the flame retardant and the mica powder to obtain a second component;
s3, mixing the first component obtained in the step S1 with the second component obtained in the step S2, adding polyurethane resin, and uniformly mixing to obtain a mixed material;
and S4, rolling and forming the mixed material obtained in the step S3, and cooling to obtain the flame-retardant sealing material.
Example 5
The raw materials comprise (by weight percent): the content of bisphenol a type epoxy resin was 27% by weight, the content of diethyl phthalate was 20% by weight, the content of kaolin was 50% by weight, the content of polyurethane resin was 1% by weight, and the content of flame retardant was 2% by weight.
The flame retardant is a mixture of metal-organic framework material organic magnesium aluminum and chloroplatinic acid, and the mass ratio of the metal-organic framework material organic magnesium aluminum to the chloroplatinic acid is 100: 3, the preparation method of the metal-organic framework material organic magnesium aluminum comprises the following steps:
s1, dissolving 1mol of magnesium nitrate, 1mol of aluminum nitrate and 1mol of terephthalic acid in 100mL of methanol-ethanol-water solution (the methanol content is 15 wt%, and the ethanol content is 25 wt%) to obtain a first solution;
s2, adding 100g of polystyrene microspheres into a container, and spraying 6g of a solution containing 40 wt% of n-octanol and 10 wt% of polyvinyl acetate to form holes so as to obtain porous polystyrene beads;
s3, transferring the first solution into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, adding the porous polystyrene beads obtained in the step S2, performing ultrasonic treatment until the porous polystyrene beads are uniformly dispersed, and then dropwise adding ammonia water to adjust the pH value to 8.5;
s4, placing the hydrothermal synthesis kettle in a muffle furnace for reaction at 190 ℃ for 52 hours, naturally cooling to room temperature, washing and filtering reaction liquid by deionized water, and calcining the obtained beads in the muffle furnace at 410 ℃ for 52 hours to obtain the metal-organic framework material loaded with the organic magnesium and aluminum.
The preparation method of the flame-retardant sealing material comprises the following steps:
s1, heating and melting bisphenol A epoxy resin, adding diethyl phthalate, and uniformly mixing to obtain a first component;
s2, uniformly mixing the flame retardant and kaolin to obtain a second component;
s3, mixing the first component obtained in the step S1 with the second component obtained in the step S2, adding polyurethane resin, and uniformly mixing to obtain a mixed material;
and S4, rolling and forming the mixed material obtained in the step S3, and cooling to obtain the flame-retardant sealing material.
Comparative example 1
Compared with example 5, the flame retardant is all the metal-organic framework material organic magnesium aluminum, and other conditions are not changed.
The raw materials comprise (by weight percent): the content of bisphenol a type epoxy resin was 27% by weight, the content of diethyl phthalate was 20% by weight, the content of kaolin was 50% by weight, the content of polyurethane resin was 1% by weight, and the content of flame retardant was 2% by weight.
The flame retardant is metal-organic framework material organic magnesium aluminum, and the preparation method comprises the following steps:
s1, dissolving 1mol of magnesium nitrate, 1mol of aluminum nitrate and 1mol of terephthalic acid in 100mL of methanol-ethanol-water solution (the methanol content is 15 wt%, and the ethanol content is 25 wt%) to obtain a first solution;
s2, adding 100g of polystyrene microspheres into a container, and spraying 6g of a solution containing 40 wt% of n-octanol and 10 wt% of polyvinyl acetate to form holes so as to obtain porous polystyrene beads;
s3, transferring the first solution into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, adding the porous polystyrene beads obtained in the step S2, performing ultrasonic treatment until the porous polystyrene beads are uniformly dispersed, and then dropwise adding ammonia water to adjust the pH value to 8.5;
s4, placing the hydrothermal synthesis kettle in a muffle furnace for reaction at 190 ℃ for 52 hours, naturally cooling to room temperature, washing and filtering reaction liquid by deionized water, and calcining the obtained beads in the muffle furnace at 410 ℃ for 52 hours to obtain the metal-organic framework material loaded with the organic magnesium and aluminum.
The preparation method of the flame-retardant sealing material comprises the following steps:
s1, heating and melting bisphenol A epoxy resin, adding diethyl phthalate, and uniformly mixing to obtain a first component;
s2, uniformly mixing the flame retardant and kaolin to obtain a second component;
s3, mixing the first component obtained in the step S1 with the second component obtained in the step S2, adding polyurethane resin, and uniformly mixing to obtain a mixed material;
and S4, rolling and forming the mixed material obtained in the step S3, and cooling to obtain the flame-retardant sealing material.
Comparative example 2
Compared with example 5, the flame retardant is all chloroplatinic acid, and other conditions are not changed.
The raw materials comprise (by weight percent): the content of bisphenol a type epoxy resin was 27% by weight, the content of diethyl phthalate was 20% by weight, the content of kaolin was 50% by weight, the content of polyurethane resin was 1% by weight, and the content of flame retardant was 2% by weight.
The flame retardant is chloroplatinic acid.
The preparation method of the flame-retardant sealing material comprises the following steps:
s1, heating and melting bisphenol A epoxy resin, adding diethyl phthalate, and uniformly mixing to obtain a first component;
s2, uniformly mixing the flame retardant and kaolin to obtain a second component;
s3, mixing the first component obtained in the step S1 with the second component obtained in the step S2, adding polyurethane resin, and uniformly mixing to obtain a mixed material;
and S4, rolling and forming the mixed material obtained in the step S3, and cooling to obtain the flame-retardant sealing material.
Test example 1
The flame-retardant sealing materials obtained in examples 1 to 5 and comparative examples 1 to 2 and commercially available flame-retardant sealing materials were subjected to a limiting oxygen index test as follows:
the test index is the limiting oxygen index percent, and the sample is tested according to the experimental standard GB/T2406.2-2009. The shape of the sample is I, the length is 100mm, the width is 10mm, and the thickness is 4 mm; ignition method a, 15 samples of the same formulation were tested and averaged.
The results are shown in Table 1.
TABLE 1
| Group of | Limiting oxygen fingerNumber (%) |
| Example 1 | 24.5 |
| Example 2 | 26.7 |
| Example 3 | 25.9 |
| Example 4 | 27.2 |
| Example 5 | 37.7 |
| Comparative example 1 | 22.1 |
| Comparative example 2 | 18.7 |
| Is commercially available | 20.5 |
Test example 2
The flame retardant sealing materials obtained in examples 1 to 5 and comparative examples 1 to 2 and commercially available flame retardant sealing materials were subjected to a vertical burning test as follows:
according to test method B of GB/T2408 + 2008 'determination of Plastic Combustion Performance': carrying out a vertical combustion test, carrying out a UL-94 vertical combustion test on the test samples by adopting an CZF-5 horizontal vertical combustor, testing 5 test samples by using the same formula, and averaging; t is t1Refers to the first afterflame time of the sample in seconds(s); t is t2Refers to the second afterflame time of the sample in seconds(s); t is tfRefers to the total afterflame time in seconds(s).
The results are shown in Table 2.
TABLE 2
The test data for comparative examples 1-5 can also be visualized as: the flame-retardant sealing material has good flame retardant property, wherein the flame retardant property in the embodiment 5 is the best, and the flame retardant in the embodiment 5 is a mixture of metal-organic framework materials, namely organic magnesium aluminum and chloroplatinic acid.
Compared with the embodiment 5, the comparative examples 1 and 2 are respectively not added with chloroplatinic acid or metal-organic framework material organic magnesium aluminum, on one hand, the synthesized flame retardant metal-organic framework material organic magnesium aluminum releases crystal water when heated, and the crystal water is evaporated into water vapor at high temperature and absorbs a large amount of heat, so that the surface temperature of the material is reduced, and the thermal decomposition and combustion rate of the polymer are obviously reduced; on the other hand, the concentration of the combustible gas is diluted to a certain extent by a large amount of water vapor generated by evaporation; meanwhile, the aluminum oxide and the magnesium oxide generated by thermal decomposition have larger surface area, and can absorb smoke and combustible micromolecules, thereby playing a role in flame retardance. The mechanism is that in the thermal degradation process of 400-500 ℃, chloroplatinic acid initiates the degradation of side chain methyl of bisphenol A epoxy resin and couples with free radicals to cause the generation of crosslinking points, and the free radical reaction is that C-CH is catalyzed by platinum3Initiated by homolytic cleavage of the bond into a methyl group which derives a hydrogen atom from the other methyl group to form methane and releases a methylene radical to link to the oxyalkylene chain, and an alkyl radical which, ultimately, attacks the adjacent polymer chain and initiates the polymer matrixA crosslinking reaction, thereby suppressing the formation of a transition complex (cyclic polysiloxane of low molar mass) that promotes degradation. Therefore, the chloroplatinic acid and the organic magnesium-aluminum of the metal-organic framework material have synergistic effect in the aspect of improving the flame retardant property.
Test example 3
The flame retardant sealing materials prepared in examples 1 to 5 and comparative examples 1 to 2 and commercially available flame retardant sealing materials were subjected to mechanical property tests as follows:
the mechanical property test method is carried out according to GB/T1040.3-2006 third part for testing plastic tensile property, the sample adopts a type 2 sample, the length is 150mm, the width is 15mm, the distance between clamps is 100mm, the tensile speed is 100mm/min, 5 longitudinal samples and 5 transverse samples are tested by the same formula, and an average value is taken.
The results are shown in Table 3.
TABLE 3
The test data for comparative example 5, comparative examples 1, 2 and common bisphenol a type epoxy resin can also be seen visually: the invention further improves the dispersibility and compatibility of the flame retardant in an epoxy resin system by preparing the organic magnesium-aluminum of the metal-organic framework material, forms a flexible chain between the flame retardant containing the organic chain structure and the epoxy resin, increases the interface combination effect of the flame retardant and the epoxy resin, enhances the stability of the flame retardant, further improves the flame retardant property of the epoxy resin and also improves the mechanical property of the epoxy resin.
Compared with the prior art, the preparation method has the advantages of mild conditions, low energy consumption, simple preparation method and easily obtained raw materials. The method realizes the large-scale loading of the organic magnesium and the aluminum in the pore channels inside the porous polystyrene carrier, and the organic magnesium and the aluminum have high loading rate. In the pretreatment process of the polystyrene carrier, a high-efficiency pore-forming agent is adopted to form pores, so that the chelation of metal atoms in the organic magnesium and aluminum and the carrier is facilitated, the interaction force of the organic magnesium and aluminum and the inner wall of a pore channel of the carrier is enhanced, and the stable loading of the organic magnesium and the aluminum is realized. In addition, the uniform dispersion of organic magnesium and aluminum in the inner pore channels of the carrier is realized, and the organic framework composite material with microporous-mesoporous-macroporous multilevel pore channels is prepared.
The organic magnesium-aluminum of the flame retardant metal-organic framework material synthesized by the invention has excellent thermal stability, does not generate corrosive gas, is not volatile, has the advantages of no toxicity, smoke suppression and the like, but generally needs larger filling amount, the more the addition amount is, the better the flame retardant and smoke suppression effect is, and the moderate flame retardance can be obtained only by high addition amount.
According to the invention, through the research on the flame retardant, the better mechanical property and adhesion of the epoxy resin sealing material are ensured, and meanwhile, the sealing material has higher flame retardance, better hydrophobicity, dispersibility, compatibility and mechanical property.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A flame-retardant sealing material is characterized in that it is an epoxy resin material containing a flame retardant;
the flame retardant is a metal-organic framework material organic magnesium aluminum, and the preparation method comprises the following steps:
s1, dissolving magnesium nitrate, aluminum nitrate and terephthalic acid in a first solvent to obtain a first solution;
s2, adding the polystyrene microspheres into a container, and spraying a certain amount of n-octanol and polyvinyl acetate solution to form holes to obtain porous polystyrene beads;
s3, transferring the first solution into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, adding the porous polystyrene beads obtained in the step S2, performing ultrasonic treatment until the beads are uniformly dispersed, and then dropwise adding ammonia water to adjust the pH value to 7.5-8.5;
s4, placing the hydrothermal synthesis kettle in a muffle furnace for reaction, naturally cooling to room temperature, washing and filtering reaction liquid by deionized water, and calcining the obtained beads in the muffle furnace to obtain the metal-organic framework material loaded with the organic magnesium and aluminum.
2. The flame-retardant sealing material according to claim 1, wherein the ratio of the amounts of the aluminum nitrate, the magnesium nitrate, the terephthalic acid and the first solvent in step S1 is 1:1 (0.5-1.5): 100; the first solvent is one or a mixture of deionized water, ethanol, methanol and tetrahydrofuran.
3. The flame retardant sealing material according to claim 1, wherein in step S2, the mass fraction of n-octanol in the solution of n-octanol and polyvinyl acetate is 30 to 50 wt%, the mass fraction of polyvinyl acetate solution is 5 to 15 wt%, and the mass ratio of the polystyrene microspheres to the sprayed solution of n-octanol and polyvinyl acetate is 100: (2-10).
4. The flame retardant sealing material as claimed in claim 1, wherein the reaction temperature of step S4 is 180-200 ℃ and the reaction time is 48-60 h; the calcination temperature is 400-420 ℃, and the calcination time is 48-60 h.
5. The flame-retardant sealing material according to claim 1, wherein the flame retardant further comprises chloroplatinic acid.
6. The flame retardant sealing material of claim 4 wherein the metal-organic framework material comprises the following components in a mass ratio of the organic magnesium aluminum to the chloroplatinic acid of 100: (1-5).
7. The flame retardant sealing material of claim 1 further comprising a plasticizer, a filler and an adhesion promoter.
8. A flame retardant sealant according to claim 7 wherein said plasticizer is selected from one or more of di-n-octyl phthalate, diisodecyl phthalate, dibutyl phthalate, diethyl phthalate, butylbenzyl phthalate, tetraisooctyl pyromellitate, tributyl acetylcitrate, tributyl citrate, trioctyl phosphate and diphenyloctyl phosphate; the filler is one or more of calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, talcum powder, kaolin, mica powder and wollastonite; the adhesion promoter is polyamide resin and/or polyurethane resin.
9. The flame retardant sealant according to claim 7, wherein the epoxy resin is contained in an amount of 12 to 37 wt%, the plasticizer is contained in an amount of 12 to 50 wt%, the filler is contained in an amount of 20 to 70 wt%, the adhesion promoter is contained in an amount of 0.5 to 5 wt%, and the flame retardant is contained in an amount of 2 to 7 wt%, based on the total weight of the composition.
10. A method for preparing a flame retardant sealing material according to any of claims 1 to 9, comprising the steps of:
s1, heating and melting epoxy resin, adding a plasticizer, and uniformly mixing to obtain a first component;
s2, uniformly mixing the flame retardant and the filler to obtain a second component;
s3, mixing the first component obtained in the step S1 with the second component obtained in the step S2, adding an adhesion promoter, and uniformly mixing to obtain a mixed material;
and S4, rolling and forming the mixed material obtained in the step S3, and cooling to obtain the flame-retardant sealing material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116041719A (en) * | 2022-12-23 | 2023-05-02 | 北京航天新立科技有限公司 | Halogen-free flame retardant, flame-retardant modified epoxy resin and preparation methods thereof |
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2020
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041719A (en) * | 2022-12-23 | 2023-05-02 | 北京航天新立科技有限公司 | Halogen-free flame retardant, flame-retardant modified epoxy resin and preparation methods thereof |
| CN116041719B (en) * | 2022-12-23 | 2024-04-30 | 北京航天新立科技有限公司 | Halogen-free flame retardant, flame-retardant modified epoxy resin and preparation methods thereof |
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