Fireproof flame-retardant building insulation board and preparation method thereof
Through the synthesis of modified polystyrene and magnesium hydroxide and supercritical foaming technology, combined with the coating of thiophene and benzooxazole, a fire-resistant and flame-retardant building insulation board with excellent flame-retardant, anti-aging, antibacterial and electromagnetic shielding properties was prepared, which solved the problems of flammability and insufficient performance of existing building insulation boards.
Patent Information
- Application Number
- CN202411788722.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-06
- Publication Date
- 2025-02-28
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Existing building insulation boards are flammable, which makes it difficult to spread fires, causes economic losses, and lacks good flame retardant, anti-aging, antibacterial and electromagnetic shielding properties.
Modified polystyrene is prepared by reacting premodified polystyrene with 3-(3-bromopropyl)thiophene, and modified magnesium hydroxide is prepared by reacting premodified magnesium hydroxide with borate flame retardant monomer and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine. After mixing, it is supercritical foamed to obtain a polystyrene board. Then, the thiophene finishing solution and benzooxazole finishing solution are applied to the plate in turn to form a fire-resistant and flame-retardant building insulation board.
The prepared fire-resistant and flame-retardant building insulation board has excellent flame-retardant, anti-aging, antibacterial and electromagnetic shielding properties, which significantly improves the safety and performance of building insulation boards.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of thermal insulation boards, in particular to a fireproof and flame-retardant building thermal insulation board and a preparation method thereof. Background Art
[0002] In order to prevent the further aggravation of the energy crisis and environmental problems, the large-scale development of new energy-saving and environmentally friendly building materials has become the focus of global attention. Among them, the research and development and application of building exterior wall insulation materials are important measures to respond to the requirements of the social sustainable development strategy, which is conducive to achieving the goal of building a social ecological civilization. Conventional foam materials such as polystyrene foam boards have become the mainstream materials for current domestic and foreign building insulation systems due to their good antifreeze effect, high strength, low water absorption, light weight, and convenient construction. However, the board structure is loose, there are many gaps between the internal particles, the thermal conductivity is high, and it is very flammable.
[0003] At present, most of the exterior walls of high-rise buildings are made of flammable insulation materials. When a fire occurs, flammable materials further promote the spread of the fire, making it more difficult to evacuate personnel and put out fires, which will cause significant economic losses. Therefore, it is urgent to improve the fire retardant properties of building insulation boards. Summary of the invention
[0004] The object of the present invention is to provide a fire-retardant building insulation board and a preparation method thereof, so as to solve the problems existing in the prior art.
[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: A fireproof and flame-retardant building insulation board, wherein the fireproof and flame-retardant building insulation board is prepared by reacting pre-modified polystyrene and 3-(3-bromopropyl)thiophene to obtain modified polystyrene; reacting pre-modified magnesium hydroxide, a borate flame-retardant monomer, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine to obtain modified magnesium hydroxide; mixing the modified polystyrene and the modified magnesium hydroxide and then subjecting the mixture to supercritical foaming to obtain a polystyrene board; and coating the polystyrene board with a thiophene finishing liquid and a benzoxazole finishing liquid in sequence to obtain the fireproof and flame-retardant building insulation board; The pre-modified polystyrene is prepared by reacting polystyrene and dimethylallylamine; The borate flame retardant monomer is prepared by reacting pentaerythritol and boric acid; The pre-modified magnesium hydroxide is prepared by reacting magnesium hydroxide and 3-chloropropyltriethoxysilane; The thiophene finishing liquid is prepared by uniformly mixing thiophene, 3-thiopheneacetyl chloride, anhydrous ferric chloride and tetrahydrofuran; The benzoxazole finishing liquid is prepared by uniformly mixing 2-mercaptobenzoxazole, triethylamine and tetrahydrofuran.
[0006] A method for preparing a fireproof and flame-retardant building insulation board, the method for preparing the fireproof and flame-retardant building insulation board comprising the following preparation steps: (1) Place polystyrene in a plasticizer and stir at 180-182°C and 50-60 r / min for 10-12 min. Mix 0.06-0.08 times the mass of polystyrene with dimethylallylamine, diisopropyl peroxide, and acetone in a mass ratio of 1:(0.1-0.12):(3-4) and add to the plasticizer. Continue stirring and reacting for 8-10 min. Take out, dissolve with chloroform, precipitate with methanol, filter, and Wash with methanol 3 to 5 times, dry at 50 to 60°C for 8 to 10 hours under vacuum conditions to obtain pre-modified polystyrene; mix pre-modified polystyrene, 3-(3-bromopropyl)thiophene and toluene in a mass ratio of 1:(0.3 to 0.4):(9 to 11), stir at 50 to 60°C and 100 to 200 r / min for 4 to 5 hours, and dry at 50 to 60°C for 10 to 12 hours under vacuum conditions to obtain modified polystyrene; (2) Mix magnesium hydroxide and anhydrous ethanol in a mass ratio of 1:(65-75) and add silane hydrolyzate in an amount 18-20 times the mass of magnesium hydroxide, stir at 58-62°C and 400-600r / min for 3-4h, filter, wash with anhydrous ethanol 3-5 times, and dry at 75-85°C for 10-11h under vacuum to obtain pre-modified magnesium hydroxide; mix pre-modified magnesium hydroxide, borate flame retardant monomer, triethylamine, and N,N-dimethylformamide in a mixture of: The mass ratio is 1:(3-4):(0.03-0.05):(30-40), and the mixture is mixed evenly. 2-(allyloxy)-4,6-dichloro-1,3,5-triazine with a molar amount of 1.1-1.2 times of the borate flame retardant monomer is added. The mixture is stirred at 70-80°C and 300-500 r / min for 6-8 hours. The mixture is filtered, washed with anhydrous ethanol and deionized water for 3-5 times respectively, and dried at 50-60°C under vacuum conditions for 8-10 hours to obtain modified magnesium hydroxide. (3) Weigh 98-102 parts of modified polystyrene, 4-5 parts of modified magnesium hydroxide, and 0.6-1 part of diisopropyl peroxide by mass; place the modified polystyrene and modified magnesium hydroxide in an internal mixer, stir at 170-180°C and 30-40 r / min for 20-24 min, add diisopropyl peroxide and mix well, place on a flat tablet press, set the temperature of the flat tablet press to 158-162°C, the pressure to 15-16 MPa, and the time to 6-8 min; then place in a high-pressure foaming kettle, use carbon dioxide as a foaming agent for supercritical foaming, cool to room temperature, and obtain a polystyrene board; apply the thiophene finishing liquid on the polystyrene board, with a coating amount of 2.4-3 kg / m 2, dry at 68~70℃ for 6~8h, then apply benzoxazole finishing liquid, the coating amount is 1.6~2kg / m 2 , dried at 68~70℃ for 10~12h to obtain fire-retardant building insulation board.
[0007] As an optimization, the model of the polystyrene in step (1) is HIPS-622P.
[0008] As an optimization, the preparation method of the borate flame retardant monomer in step (2) is: add pentaerythritol and boric acid in a molar ratio of 1:(2.1-2.2) to benzene with a mass of 12-14 times that of pentaerythritol, stir at 76-78°C and 400-600r / min for 6-7h, and dry at 65-75°C under vacuum for 8-10h to obtain the borate flame retardant monomer; The reaction process is: .
[0009] As an optimization, the preparation method of the silane hydrolyzate in step (2) is as follows: 3-chloropropyltriethoxysilane and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(45~55), the pH value is adjusted to 4.8~5.2 with an oxalic acid aqueous solution with a molar concentration of 1~1.2 mol / L, and the mixture is stirred at 400~600 r / min for 16~20 min at room temperature to prepare a silane hydrolyzate.
[0010] As an optimization, the particle size of the magnesium hydroxide in step (2) is 3000 mesh.
[0011] As an optimization, the process parameters of the supercritical foaming in step (3) are as follows: the pressure of the high-pressure foaming reactor is set to 20-22 MPa, the temperature is set to 170-180°C, the pressure is released after 1.6-2 hours, and the pressure release time is 17-23 seconds.
[0012] As an optimization, the preparation method of the thiophene finishing liquid in step (3) is: thiophene, 3-thiopheneacetyl chloride, anhydrous ferric chloride, and tetrahydrofuran are uniformly mixed in a mass ratio of 1: (0.6~0.8): (0.03~0.04): (6~8) to prepare a thiophene finishing liquid.
[0013] As an optimization, the preparation method of the benzoxazole finishing solution in step (3) is: 2-mercaptobenzoxazole, triethylamine, and tetrahydrofuran are uniformly mixed in a mass ratio of 1:(0.03~0.05):(6~8) to prepare a benzoxazole finishing solution.
[0014] Compared with the prior art, the beneficial effects achieved by the present invention are: When preparing the fire-retardant building insulation board, the present invention reacts polystyrene and dimethylallylamine to obtain pre-modified polystyrene; reacts pre-modified polystyrene and 3-(3-bromopropyl)thiophene to obtain modified polystyrene; reacts pentaerythritol and boric acid to obtain borate flame retardant monomer; reacts magnesium hydroxide and 3-chloropropyltriethoxysilane to obtain pre-modified magnesium hydroxide; reacts pre-modified magnesium hydroxide, borate flame retardant monomer and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine to obtain modified magnesium hydroxide; supercritically foams the modified polystyrene and modified magnesium hydroxide after mixing to obtain a polystyrene board; and sequentially coats the polystyrene board with thiophene finishing liquid and benzoxazole finishing liquid to obtain the fire-retardant building insulation board. The fire-retardant building insulation board prepared by the present invention has excellent flame retardant, anti-aging, antibacterial and electromagnetic shielding properties.
[0015] First, dimethylallylamine is grafted onto the polystyrene molecular chain to obtain pre-modified polystyrene, and a tertiary amine structure is introduced into the side chain of the pre-modified polystyrene molecule; the tertiary amine structure introduced into the side chain of the pre-modified polystyrene molecule reacts with the bromine atom on 3-(3-bromopropyl)thiophene to obtain modified polystyrene, a quaternary ammonium salt structure is generated on the side chain of the modified polystyrene molecule, and a thiophene group is introduced at the same time; inside the building, if the air humidity is maintained at a high level for a long time, it is easy to cause the insulation board to get damp, especially in humid seasons and regions, the insulation board is more likely to mold; the quaternary ammonium salt structure has an antibacterial effect, which can improve the fire resistance. The antibacterial properties of fire-retardant building insulation boards; the thiophene groups introduced on the side chains of modified polystyrene molecules can undergo oxidative polymerization with thiophene and 3-thiopheneacetyl chloride in the thiophene finishing liquid to form a layer of polythiophene on the polystyrene board. Polythiophene is a conductive polymer material with good conductivity and electromagnetic wave absorption capacity, which gives the fire-retardant building insulation boards excellent electromagnetic shielding properties. The thiophene groups introduced on the side chains of polystyrene molecules form chemical bonds between the surface polythiophene and the polystyrene board, thereby improving the bonding strength of the polythiophene coating on the polystyrene board, preventing the polythiophene coating from peeling off, and improving the durability of the battery shielding performance.
[0016] Secondly, magnesium hydroxide and 3-chloropropyltriethoxysilane are reacted to obtain pre-modified magnesium hydroxide, and chlorine atoms are introduced on the surface of the pre-modified magnesium hydroxide; the pre-modified magnesium hydroxide, borate flame retardant monomer, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine are reacted to obtain modified magnesium hydroxide; the boric acid group on the borate flame retardant monomer and the chlorine atom on 2-(allyloxy)-4,6-dichloro-1,3,5-triazine undergo a substitution reaction, so that the borate flame retardant monomer and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine are polymerized and grown on the surface of the pre-modified magnesium hydroxide to obtain modified magnesium hydroxide, and organic boron, triazine structure and carbon-carbon double bonds are introduced into the modified magnesium hydroxide; organic boron has good smoke suppression, flame retardancy and non-toxicity, and the triazine structure will release non-combustible gas when heated, and these non-combustible gases dilute the concentration of combustible gas generated when the polymer is thermally decomposed and the oxygen concentration in the air, and at the same time, part of the heat is released in the non-combustible The gas is taken away when it is generated, and the organic boron and triazine structures are flame retardant synergistically, giving the fire-retardant building insulation board a more excellent flame retardant effect; magnesium hydroxide has an endothermic effect. When magnesium hydroxide is heated by a heat source, a dehydration reaction will occur to generate water vapor and magnesium oxide. This is an endothermic reaction that absorbs a large amount of heat. The generated magnesium oxide will also react with the carbide on the surface of the combustion product to generate a stable carbide layer. The carbide layer has good thermal insulation properties and can prevent the combustion product from contacting external oxygen; magnesium hydroxide, as an inorganic material, has poor dispersibility in polymer materials and is easy to agglomerate and produce defects. Surface modification of magnesium hydroxide can improve the compatibility of magnesium hydroxide with polystyrene, make magnesium hydroxide evenly dispersed in polystyrene, and give full play to the flame retardant properties of magnesium hydroxide; the carbon-carbon double bonds introduced on the modified magnesium hydroxide will cross-link with the modified polystyrene main chain under the action of the catalyst to form a cross-linked network structure, prevent the collapse of the bubbles formed after foaming, and enhance the stability of the bubbles.
[0017] Finally, thiophene finishing liquid and benzoxazole finishing liquid are coated on the polystyrene board in sequence to prepare the fire-retardant building insulation board. Thiophene and 3-thiopheneacetyl chloride in the thiophene finishing liquid are oxidatively polymerized on the polystyrene board to form a polythiophene coating, and an acyl chloride group is introduced; with the popularization of electronic, electrical and wireless communication equipment, the large amount of electromagnetic waves emitted by them makes people live in an environment shrouded in electromagnetic pollution. Electromagnetic radiation will directly threaten human health and affect various functions of the human body such as circulation, immunity, reproduction and metabolism; polythiophene is a conductive polymer material with good conductivity and electromagnetic wave absorption capacity, which gives the fire-retardant building insulation board excellent electromagnetic shielding performance; the introduced acyl chloride group undergoes a substitution reaction with the thiol group on 2-mercaptobenzoxazole in the benzoxazole finishing liquid to generate a mercaptoesterbenzoxazole structure on the surface of the fire-retardant building insulation board; the lone pair of electrons of the sulfur atom on the mercaptoesterbenzoxazole structure reduces the rigid structure of benzoxazole, improves the stability of benzoxazole, and at the same time enhances the ultraviolet absorption intensity, giving the fire-retardant building insulation board excellent anti-aging performance. DETAILED DESCRIPTION
[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.
[0019] Embodiment 1: A method for preparing a fireproof and flame-retardant building insulation board, the method for preparing the fireproof and flame-retardant building insulation board comprising the following preparation steps: (1) Place polystyrene in a plasticizer, stir at 180°C and 50 r / min for 12 min, mix 0.06 times the mass of polystyrene with dimethylallylamine, diisopropyl peroxide and acetone in a mass ratio of 1:0.1:3, add to the plasticizer, continue stirring and reacting for 10 min, take out, dissolve with chloroform, precipitate with methanol, filter, wash with methanol 3 times, and dry at 50°C for 10 h under vacuum conditions to obtain pre-modified polystyrene; mix pre-modified polystyrene, 3-(3-bromopropyl)thiophene and toluene in a mass ratio of 1:0.3:9, stir at 50°C and 100 r / min for 5 h, and dry at 50°C for 12 h under vacuum conditions to obtain modified polystyrene; (2) Add pentaerythritol and boric acid in a molar ratio of 1:2.1 to benzene (12 times the mass of pentaerythritol), stir at 76°C and 400 r / min for 7 h, and dry at 65°C for 10 h under vacuum to obtain a borate flame retardant monomer; mix 3-chloropropyltriethoxysilane and anhydrous ethanol in a mass ratio of 1:45, adjust the pH to 4.8 with an aqueous solution of oxalic acid with a molar concentration of 1 mol / L, stir at 400 r / min for 20 min at room temperature to prepare a silane hydrolyzate; mix magnesium hydroxide and anhydrous ethanol in a mass ratio of 1:65, add silane hydrolyzate (18 times the mass of magnesium hydroxide), and heat at 5 8°C, 400r / min stirring reaction for 4h, filtering, washing with anhydrous ethanol 3 times, and drying at 75°C for 11h under vacuum conditions to obtain pre-modified magnesium hydroxide; pre-modified magnesium hydroxide, borate flame retardant monomer, triethylamine, and N,N-dimethylformamide are mixed uniformly at a mass ratio of 1:3:0.03:30, 2-(allyloxy)-4,6-dichloro-1,3,5-triazine with a molar amount of 1.1 times that of borate flame retardant monomer is added, stirring at 70°C, 300r / min for 8h, filtering, washing with anhydrous ethanol and deionized water 3 times each, and drying at 50°C for 10h under vacuum conditions to obtain modified magnesium hydroxide; (3) Weigh 98 parts of modified polystyrene, 4 parts of modified magnesium hydroxide, and 0.6 parts of diisopropyl peroxide by mass; place the modified polystyrene and modified magnesium hydroxide in an internal mixer, stir at 170°C and 30 r / min for 24 min, add diisopropyl peroxide and mix well, place on a flat tablet press to make tablets, set the temperature of the flat tablet press to 158°C, the pressure to 15 MPa, and the time to 8 min; then place in a high-pressure foaming kettle, use carbon dioxide as a foaming agent for supercritical foaming, set the high-pressure foaming to 150°C, and press the tablets to 150°C. The pressure of the bubble kettle is 20MPa, the temperature is 170℃, the pressure is released after 2h, the pressure release time is 17s, and the polystyrene board is obtained by cooling to room temperature; thiophene, 3-thiopheneacetyl chloride, anhydrous ferric chloride, and tetrahydrofuran are mixed uniformly at a mass ratio of 1:0.6:0.03:6 to prepare a thiophene finishing liquid; 2-mercaptobenzoxazole, triethylamine, and tetrahydrofuran are mixed uniformly at a mass ratio of 1:0.03:6 to prepare a benzoxazole finishing liquid; the thiophene finishing liquid is coated on the polystyrene board, and the coating amount is 2.4kg / m 2 , dried at 68℃ for 8h, and then coated with benzoxazole finishing liquid, with a coating amount of 1.6kg / m 2 , dried at 68°C for 12h to obtain a fire-retardant building insulation board.
[0020] Embodiment 2:
[0021] A method for preparing a fireproof and flame-retardant building insulation board, the method for preparing the fireproof and flame-retardant building insulation board comprising the following preparation steps: (1) Place polystyrene in a plasticizer, stir at 181°C and 55 r / min for 11 min, mix 0.07 times the mass of polystyrene with dimethylallylamine, diisopropyl peroxide and acetone in a mass ratio of 1:0.11:3.5, add to the plasticizer, continue stirring and reacting for 9 min, take out, dissolve with chloroform, precipitate with methanol, filter, wash with methanol 4 times, and dry at 55°C for 9 h under vacuum conditions to obtain pre-modified polystyrene; mix pre-modified polystyrene, 3-(3-bromopropyl)thiophene and toluene in a mass ratio of 1:0.35:10, stir at 55°C and 150 r / min for 4.5 h, and dry at 55°C for 11 h under vacuum conditions to obtain modified polystyrene; (2) Add pentaerythritol and boric acid in a molar ratio of 1:2.15 to benzene (13 times the mass of pentaerythritol), stir at 77°C and 500 r / min for 6.5 h, and dry at 70°C under vacuum for 9 h to obtain a borate flame retardant monomer; mix 3-chloropropyltriethoxysilane and anhydrous ethanol in a mass ratio of 1:50, adjust the pH to 5.0 with an oxalic acid aqueous solution with a molar concentration of 1.1 mol / L, stir at 500 r / min for 18 min at room temperature to prepare a silane hydrolyzate; mix magnesium hydroxide and anhydrous ethanol in a mass ratio of 1:70, add silane hydrolyzate (19 times the mass of magnesium hydroxide), and heat at 60 ℃, 500r / min stirring reaction for 3.5h, filtered, washed with anhydrous ethanol 4 times, dried at 80℃ for 10.5h under vacuum conditions to obtain pre-modified magnesium hydroxide; pre-modified magnesium hydroxide, borate flame retardant monomer, triethylamine, N,N-dimethylformamide were mixed uniformly at a mass ratio of 1:3.5:0.04:35, 2-(allyloxy)-4,6-dichloro-1,3,5-triazine with a molar amount of 1.15 times that of borate flame retardant monomer was added, stirred at 75℃, 400r / min for 7h, filtered, washed with anhydrous ethanol and deionized water 4 times respectively, and dried at 55℃ for 9h under vacuum conditions to obtain modified magnesium hydroxide; (3) Weigh 100 parts of modified polystyrene, 4.5 parts of modified magnesium hydroxide, and 0.8 parts of diisopropyl peroxide by mass; place the modified polystyrene and modified magnesium hydroxide in an internal mixer, stir at 175°C and 35 r / min for 22 min, add diisopropyl peroxide and mix evenly, place on a flat tablet press to make tablets, set the temperature of the flat tablet press to 160°C, the pressure to 15.5 MPa, and the time to 7 min; then place in a high-pressure foaming kettle, use carbon dioxide as a foaming agent for supercritical foaming, set the high pressure to The pressure of the foaming kettle was 21 MPa and the temperature was 175°C. The pressure was released after 1.8 hours for 20 seconds. The polystyrene board was obtained by cooling to room temperature. Thiophene, 3-thiopheneacetyl chloride, anhydrous ferric chloride and tetrahydrofuran were mixed uniformly at a mass ratio of 1:0.7:0.035:7 to prepare a thiophene finishing liquid. 2-mercaptobenzoxazole, triethylamine and tetrahydrofuran were mixed uniformly at a mass ratio of 1:0.04:7 to prepare a benzoxazole finishing liquid. The thiophene finishing liquid was coated on the polystyrene board at a coating amount of 2.7 kg / m 2 , dried at 69℃ for 7h, and then coated with benzoxazole finishing liquid with a coating amount of 1.8kg / m 2 , dried at 69°C for 11h to obtain a fire-retardant building insulation board.
[0022] Embodiment 3: A method for preparing a fireproof and flame-retardant building insulation board, the method for preparing the fireproof and flame-retardant building insulation board comprising the following preparation steps: (1) Place polystyrene in a plasticizer, stir at 182°C and 60 r / min for 10 min, mix 0.08 times the mass of polystyrene with dimethylallylamine, diisopropyl peroxide and acetone in a mass ratio of 1:0.12:4, add to the plasticizer, continue stirring and reacting for 8 min, take out, dissolve with chloroform, precipitate with methanol, filter, wash with methanol 5 times, and dry at 60°C for 8 h under vacuum conditions to obtain pre-modified polystyrene; mix pre-modified polystyrene, 3-(3-bromopropyl)thiophene and toluene in a mass ratio of 1:0.4:11, stir at 60°C and 200 r / min for 4 h, and dry at 60°C for 10 h under vacuum conditions to obtain modified polystyrene; (2) Add pentaerythritol and boric acid in a molar ratio of 1:2.2 to benzene (14 times the mass of pentaerythritol), stir at 78°C and 600 r / min for 6 h, and dry at 75°C under vacuum for 8 h to obtain a borate flame retardant monomer; mix 3-chloropropyltriethoxysilane and anhydrous ethanol in a mass ratio of 1:55, adjust the pH to 5.2 with an oxalic acid aqueous solution with a molar concentration of 1.2 mol / L, stir at 600 r / min for 16 min at room temperature to prepare a silane hydrolyzate; mix magnesium hydroxide and anhydrous ethanol in a mass ratio of 1:75, add silane hydrolyzate (20 times the mass of magnesium hydroxide), and The pre-modified magnesium hydroxide was prepared by stirring at 62°C and 600 r / min for 3 h, filtering, washing with anhydrous ethanol for 5 times, and drying at 85°C for 10 h under vacuum conditions. The pre-modified magnesium hydroxide, borate flame retardant monomer, triethylamine, and N,N-dimethylformamide were uniformly mixed in a mass ratio of 1:4:0.05:40, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine with a molar amount of 1.2 times that of the borate flame retardant monomer was added. The pre-modified magnesium hydroxide was prepared by stirring at 80°C and 500 r / min for 6 h, filtering, washing with anhydrous ethanol and deionized water for 5 times respectively, and drying at 60°C for 8 h under vacuum conditions to obtain modified magnesium hydroxide. (3) Weigh 102 parts of modified polystyrene, 5 parts of modified magnesium hydroxide, and 1 part of diisopropyl peroxide by mass; place the modified polystyrene and modified magnesium hydroxide in an internal mixer, stir at 180°C and 40 r / min for 20 min, add diisopropyl peroxide and mix well, place on a flat tablet press, set the temperature of the flat tablet press to 162°C, the pressure to 16 MPa, and the time to 6 min; then place in a high-pressure foaming kettle, use carbon dioxide as a foaming agent for supercritical foaming, set the high-pressure foaming temperature to 162°C, the pressure to 16 MPa, and the time to 6 min. The pressure of the bubble kettle is 22MPa, the temperature is 180℃, the pressure is released after 1.6h, the pressure release time is 23s, and the polystyrene board is obtained by cooling to room temperature; thiophene, 3-thiopheneacetyl chloride, anhydrous ferric chloride, and tetrahydrofuran are mixed uniformly at a mass ratio of 1:0.8:0.04:8 to prepare a thiophene finishing liquid; 2-mercaptobenzoxazole, triethylamine, and tetrahydrofuran are mixed uniformly at a mass ratio of 1:0.05:8 to prepare a benzoxazole finishing liquid; the thiophene finishing liquid is coated on the polystyrene board, and the coating amount is 3kg / m 2 , dried at 70℃ for 6h, and then coated with benzoxazole finishing liquid, with a coating amount of 2kg / m 2 , and dried at 70°C for 10 hours to obtain a fire-retardant building insulation board.
[0023] Comparative Example 1: The preparation method of the fire-retardant building insulation board of Comparative Example 1 is different from that of Example 2 in that step (1) is not performed, and step (3) is modified as follows: 100 parts of polystyrene, 4.5 parts of modified magnesium hydroxide, and 0.8 parts of diisopropyl peroxide are weighed by mass; polystyrene and modified magnesium hydroxide are placed in an internal mixer, stirred at 175°C and 35r / min for 22min, diisopropyl peroxide is added and mixed evenly, and the mixture is placed on a flat tablet press for tableting, and the temperature of the flat tablet press is set to 160°C, the pressure is set to 15.5MPa, and the time is 7min; the mixture is placed in a high-pressure foaming kettle, and the mixture is stirred at 175°C and 35r / min for 22min. Carbon dioxide was used as a foaming agent for supercritical foaming. The pressure of the high-pressure foaming kettle was set to 21 MPa and the temperature was set to 175°C. The pressure was released after 1.8 hours. The pressure release time was 20 seconds. The polystyrene board was obtained by cooling to room temperature. Thiophene, 3-thiopheneacetyl chloride, anhydrous ferric chloride and tetrahydrofuran were mixed uniformly in a mass ratio of 1:0.7:0.035:7 to prepare a thiophene finishing liquid. 2-mercaptobenzoxazole, triethylamine and tetrahydrofuran were mixed uniformly in a mass ratio of 1:0.04:7 to prepare a benzoxazole finishing liquid. The thiophene finishing liquid was coated on the polystyrene board at a coating amount of 2.7 kg / m 2 , dried at 69℃ for 7h, and then coated with benzoxazole finishing liquid with a coating amount of 1.8kg / m 2 , and dried at 69° C. for 11 hours to obtain a fire-retardant building insulation board. The remaining steps are the same as those in Example 2.
[0024] Comparative Example 2: The preparation method of the fire-retardant building insulation board of Comparative Example 2 is different from that of Example 2 in that step (2) is not performed, and step (3) is modified as follows: 100 parts of modified polystyrene, 4.5 parts of magnesium hydroxide, and 0.8 parts of diisopropyl peroxide are weighed by mass; the modified polystyrene and magnesium hydroxide are placed in an internal mixer, stirred at 175°C and 35 r / min for 22 min, diisopropyl peroxide is added and mixed evenly, and the mixture is placed on a flat tablet press for tableting, and the temperature of the flat tablet press is set to 160°C, the pressure is set to 15.5 MPa, and the time is 7 min; the mixture is placed in a high-pressure foaming kettle, and the mixture is stirred at 175°C and 35 r / min for 22 min. Carbon dioxide was used as a foaming agent for supercritical foaming. The pressure of the high-pressure foaming kettle was set to 21 MPa and the temperature was set to 175°C. The pressure was released after 1.8 hours. The pressure release time was 20 seconds. The polystyrene board was obtained by cooling to room temperature. Thiophene, 3-thiopheneacetyl chloride, anhydrous ferric chloride and tetrahydrofuran were mixed uniformly in a mass ratio of 1:0.7:0.035:7 to prepare a thiophene finishing liquid. 2-mercaptobenzoxazole, triethylamine and tetrahydrofuran were mixed uniformly in a mass ratio of 1:0.04:7 to prepare a benzoxazole finishing liquid. The thiophene finishing liquid was coated on the polystyrene board at a coating amount of 2.7 kg / m 2 , dried at 69℃ for 7h, and then coated with benzoxazole finishing liquid with a coating amount of 1.8kg / m 2, and dried at 69° C. for 11 hours to obtain a fire-retardant building insulation board. The remaining steps are the same as those in Example 2.
[0025] Comparative Example 3: The preparation method of the fire-retardant building insulation board of Comparative Example 3 is different from that of Example 2 only in step (3). Step (3) is modified as follows: 100 parts of modified polystyrene, 4.5 parts of modified magnesium hydroxide, and 0.8 parts of diisopropyl peroxide are weighed by weight; the modified polystyrene and modified magnesium hydroxide are placed in an internal mixer, stirred at 175°C and 35 r / min for 22 min, diisopropyl peroxide is added and mixed evenly, and the mixture is placed on a flat tablet press for tableting, and the temperature of the flat tablet press is set to 160°C and the pressure is set to 200°C. The pressure was 15.5 MPa for 7 min; the pressure was placed in a high-pressure foaming kettle, and carbon dioxide was used as a foaming agent for supercritical foaming. The pressure of the high-pressure foaming kettle was set to 21 MPa and the temperature was 175 ° C. After 1.8 h, the pressure was released for 20 s, and the polystyrene board was obtained; 2-mercaptobenzoxazole, triethylamine, and tetrahydrofuran were mixed uniformly in a mass ratio of 1:0.04:7 to prepare a benzoxazole finishing liquid; the benzoxazole finishing liquid was coated on the polystyrene board at a coating amount of 1.8 kg / m 2 , and dried at 69° C. for 11 hours to obtain a fire-retardant building insulation board. The remaining steps are the same as those in Example 2.
[0026] Comparative Example 4: The preparation method of the fire-retardant building insulation board of Comparative Example 4 is different from that of Example 2 only in step (3). Step (3) is modified as follows: 100 parts of modified polystyrene, 4.5 parts of modified magnesium hydroxide, and 0.8 parts of diisopropyl peroxide are weighed by mass; the modified polystyrene and modified magnesium hydroxide are placed in an internal mixer, stirred at 175°C and 35 r / min for 22 min, diisopropyl peroxide is added and mixed evenly, and the mixture is placed on a flat tablet press for tableting, and the temperature of the flat tablet press is set to 160°C and the pressure is set to 15 .5MPa for 7min; then placed in a high-pressure foaming kettle, using carbon dioxide as a foaming agent for supercritical foaming, setting the pressure of the high-pressure foaming kettle to 21MPa, the temperature to 175℃, releasing the pressure after 1.8h, the pressure release time is 20s, and cooling to room temperature to obtain a polystyrene board; thiophene, 3-thiopheneacetyl chloride, anhydrous ferric chloride, and tetrahydrofuran are mixed uniformly in a mass ratio of 1:0.7:0.035:7 to prepare a thiophene finishing liquid; the thiophene finishing liquid is coated on the polystyrene board at a coating amount of 2.7kg / m 2 , and dried at 69° C. for 7 h to obtain a fire-retardant building insulation board. The remaining steps are the same as in Example 2.
[0027] Test Example 1 Flame retardant performance test Test method: The examples and comparative examples were prepared into standard specimens according to GB / T2406, and the limiting oxygen index of the standard specimens was tested. The results are shown in Table 1.
[0028]
[0029] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 1, it can be found that the fireproof and flame-retardant building insulation board prepared by the present invention has good flame-retardant properties.
[0030] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 2, indicating that magnesium hydroxide and 3-chloropropyltriethoxysilane are reacted to prepare pre-modified magnesium hydroxide, and chlorine atoms are introduced on the surface of the pre-modified magnesium hydroxide; the pre-modified magnesium hydroxide, borate flame retardant monomer, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine are reacted to prepare modified magnesium hydroxide; the boric acid group on the borate flame retardant monomer undergoes a substitution reaction with the chlorine atom on the 2-(allyloxy)-4,6-dichloro-1,3,5-triazine, so that the borate flame retardant monomer, 2-(allyloxy)-4,6-dichloro-1,3,5-triazine, (propyloxy)-4,6-dichloro-1,3,5-triazine is polymerized and grown on the surface of pre-modified magnesium hydroxide to obtain modified magnesium hydroxide, and organic boron and triazine structures are introduced into the modified magnesium hydroxide; organic boron has good smoke suppression, flame retardancy and non-toxicity, and the triazine structure releases non-combustible gas when heated. These non-combustible gases dilute the concentration of flammable gas generated when the polymer is thermally decomposed and the oxygen concentration in the air. At the same time, part of the heat is taken away when the non-combustible gas is generated. The organic boron and triazine structures synergistically flame retard, giving the fire-retardant building insulation board a more excellent flame retardant effect.
[0031] Test Example 2 Anti-aging performance test Test method: The embodiments and comparative examples were made into standard specimens according to GB8813, and the compressive strength of the standard specimens was tested by an electronic universal testing machine; the standard specimens were irradiated with a xenon arc lamp for 10 days, and the compressive strength of the standard specimens after ultraviolet aging treatment was tested, and the compressive strength change rate of the embodiments and comparative examples before and after ultraviolet aging treatment was calculated, and the compressive strength change rate = (original compressive strength of the specimen - compressive strength after ultraviolet aging treatment) / original compressive strength of the specimen × 100%. The results are shown in Table 2.
[0032]
[0033] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 2, it can be found that the fire-retardant building insulation board prepared by the present invention has good anti-aging performance.
[0034] By comparison, the compressive strength change rates of Examples 1 to 3 are less than those of Comparative Examples 3 to 4, and the compressive strength change rate of Comparative Example 3 is less than that of Comparative Example 4, indicating that the thiophene finishing liquid and the benzoxazole finishing liquid are sequentially coated on the polystyrene board to obtain a fire-retardant building insulation board. Thiophene and 3-thiopheneacetyl chloride in the thiophene finishing liquid are oxidatively polymerized on the polystyrene board to form a polythiophene coating, and an acyl chloride group is introduced; the introduced acyl chloride group undergoes a substitution reaction with the thiol group on 2-mercaptobenzoxazole in the benzoxazole finishing liquid to generate a mercaptoesterbenzoxazole structure on the surface of the fire-retardant building insulation board; the lone pair of electrons of the sulfur atom on the mercaptoesterbenzoxazole structure reduces the rigid structure of benzoxazole, improves the stability of benzoxazole, and enhances the ultraviolet absorption intensity, giving the fire-retardant building insulation board excellent anti-aging properties.
[0035] Test Example 3 Antibacterial performance test Test method: Cut the examples and comparative examples into 1 cm × 1 cm × 0.4 cm samples, wash them with ethanol and set aside; activate the E. coli strain and prepare it to a concentration of 2x10 4 cfu / ml bacterial suspension, then put the cut sample into the bacterial suspension, fix the conical flask containing the bacterial suspension and sample on an oscillating shaker, and shake at 300r / min for 2min at a temperature of 20℃. Take 1.0ml of the bacterial suspension and dilute it to 100 times, take 1.0ml of the sample solution after shaking, inoculate it on the agar base, and culture it at 37℃ for 48h under natural light. Count the colonies according to the method in GB15979-2003. Calculate the antibacterial rate according to the following formula: Antibacterial rate = (average colony count before sample shaking - average colony count after sample shaking) / average colony count before sample shaking x 100%. The results are shown in Table 3.
[0036]
[0037] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 3, it can be found that the fire-retardant building insulation board prepared by the present invention has good antibacterial performance.
[0038] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 1, indicating that dimethylallylamine is grafted onto a polystyrene molecular chain to obtain pre-modified polystyrene, and a tertiary amine structure is introduced into the side chain of the pre-modified polystyrene molecule; the tertiary amine structure introduced into the side chain of the pre-modified polystyrene molecule reacts with the bromine atom on 3-(3-bromopropyl)thiophene to obtain modified polystyrene, and a quaternary ammonium salt structure is generated on the side chain of the modified polystyrene molecule; inside a building, if the air humidity is maintained at a high level for a long time, it is easy to cause the insulation board to become damp, especially in humid seasons and regions, the insulation board is more likely to mold; the quaternary ammonium salt structure has an antibacterial effect and can improve the antibacterial properties of the fire-retardant building insulation board.
[0039] Test Example 4 Electromagnetic shielding performance test Test method: The examples and comparative examples were cut into samples with a size of 20 mm × 10 mm × 2.8 mm, and the electromagnetic shielding effectiveness values of the samples were measured using an Agilent N-5242A vector network tester in the frequency range of 8 to 12 GHz. The results are shown in Table 4.
[0040]
[0041] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 4, it can be found that the fire-retardant building insulation board prepared by the present invention has good electromagnetic shielding performance.
[0042] By comparison, the electromagnetic shielding effectiveness of Examples 1 to 3 is greater than that of Comparative Example 3, indicating that the thiophene finishing liquid and the benzoxazole finishing liquid are sequentially coated on the polystyrene board to obtain a fire-retardant building insulation board. Thiophene and 3-thiopheneacetyl chloride in the thiophene finishing liquid are oxidatively polymerized on the polystyrene board to form a polythiophene coating; with the popularization of electronic, electrical and wireless communication equipment, the large amount of electromagnetic waves emitted by them makes people live in an environment covered by electromagnetic pollution, and electromagnetic radiation will directly threaten human health and affect the body's own circulation, immunity, reproduction and metabolism and other functions; polythiophene is a conductive polymer material with good conductivity and electromagnetic wave absorption capacity, giving the fire-retardant building insulation board excellent electromagnetic shielding performance.
[0043] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A fire-retardant building insulation board, characterized in that: The fireproof and flame-retardant building insulation board is prepared by reacting pre-modified polystyrene and 3-(3-bromopropyl)thiophene to obtain modified polystyrene; reacting pre-modified magnesium hydroxide, borate flame-retardant monomer, and 2-(allyloxy)-4,6-dichloro-1,3,5-triazine to obtain modified magnesium hydroxide; mixing the modified polystyrene and the modified magnesium hydroxide and then performing supercritical foaming to obtain a polystyrene board; and coating the polystyrene board with a thiophene finishing liquid and a benzoxazole finishing liquid in sequence to obtain a fireproof and flame-retardant building insulation board. The pre-modified polystyrene is prepared by reacting polystyrene and dimethylallylamine; The borate flame retardant monomer is prepared by reacting pentaerythritol and boric acid; The pre-modified magnesium hydroxide is prepared by reacting magnesium hydroxide and 3-chloropropyltriethoxysilane; The thiophene finishing liquid is prepared by uniformly mixing thiophene, 3-thiopheneacetyl chloride, anhydrous ferric chloride and tetrahydrofuran; The benzoxazole finishing liquid is prepared by uniformly mixing 2-mercaptobenzoxazole, triethylamine and tetrahydrofuran.
2. A method for preparing a fire-retardant building insulation board, characterized in that: The method for preparing the fire-retardant building insulation board comprises the following preparation steps: (1) Place polystyrene in a plasticizer, stir at 180-182°C and 50-60 r / min for 10-12 min, add 0.06-0.08 times the mass of polystyrene dimethylallylamine, diisopropyl peroxide, and acetone in a mass ratio of 1:(0.1-0.12):(3-4) and mix evenly, add to the plasticizer, continue stirring and reacting for 8-10 min, take out, dissolve with chloroform, precipitate with methanol, filter, wash with methanol 3-5 times, and dry at 50-60°C under vacuum conditions for 8-10 h to obtain pre-modified polystyrene; Pre-modified polystyrene, 3-(3-bromopropyl)thiophene and toluene are uniformly mixed in a mass ratio of 1:(0.3-0.4):(9-11), stirred at 50-60°C and 100-200 r / min for 4-5 hours, and dried at 50-60°C for 10-12 hours under vacuum conditions to obtain modified polystyrene; (2) Mix magnesium hydroxide and anhydrous ethanol in a mass ratio of 1:(65-75) and add silane hydrolyzate in an amount 18-20 times the mass of magnesium hydroxide, stir at 58-62°C and 400-600 r / min for 3-4 hours, filter, wash with anhydrous ethanol 3-5 times, and dry at 75-85°C for 10-11 hours under vacuum conditions to obtain pre-modified magnesium hydroxide; Pre-modified magnesium hydroxide, borate flame retardant monomer, triethylamine, and N,N-dimethylformamide are mixed uniformly in a mass ratio of 1:(3-4):(0.03-0.05):(30-40), 2-(allyloxy)-4,6-dichloro-1,3,5-triazine in an amount of 1.1-1.2 times the molar amount of borate flame retardant monomer is added, the mixture is stirred at 70-80°C and 300-500 r / min for 6-8 hours, filtered, washed with anhydrous ethanol and deionized water for 3-5 times respectively, and dried at 50-60°C under vacuum conditions for 8-10 hours to obtain modified magnesium hydroxide; (3) Weigh 98-102 parts of modified polystyrene, 4-5 parts of modified magnesium hydroxide, and 0.6-1 part of diisopropyl peroxide by mass; place the modified polystyrene and modified magnesium hydroxide in an internal mixer, stir at 170-180°C and 30-40 r / min for 20-24 min, add diisopropyl peroxide and mix well, place on a flat tablet press, set the temperature of the flat tablet press to 158-162°C, the pressure to 15-16 MPa, and the time to 6-8 min; then place in a high-pressure foaming kettle, use carbon dioxide as a foaming agent for supercritical foaming, cool to room temperature, and obtain a polystyrene board; apply the thiophene finishing liquid on the polystyrene board, with a coating amount of 2.4-3 kg / m 2 , dry at 68~70℃ for 6~8h, then apply benzoxazole finishing liquid, the coating amount is 1.6~2kg / m 2 , dried at 68~70℃ for 10~12h to obtain fire-retardant building insulation board.
3. The method for preparing a fire-retardant building insulation board according to claim 2, characterized in that: The model of the polystyrene in step (1) is HIPS-622P.
4. The method for preparing a fire-retardant building insulation board according to claim 2, characterized in that: The preparation method of the borate flame retardant monomer in step (2) is as follows: pentaerythritol and boric acid are added in a molar ratio of 1:(2.1-2.2) to benzene with a mass of 12-14 times that of pentaerythritol, and the mixture is stirred at 76-78°C and 400-600 r / min for 6-7 hours, and dried at 65-75°C under vacuum conditions for 8-10 hours to obtain the borate flame retardant monomer.
5. The method for preparing a fire-retardant building insulation board according to claim 2, characterized in that: The preparation method of the silane hydrolyzate in step (2) is as follows: 3-chloropropyltriethoxysilane and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(45-55), the pH value is adjusted to 4.8-5.2 with an aqueous solution of oxalic acid having a molar concentration of 1-1.2 mol / L, and the mixture is stirred at 400-600 r / min for 16-20 min at room temperature to prepare a silane hydrolyzate.
6. The method for preparing a fire-retardant building insulation board according to claim 2, characterized in that: The particle size of the magnesium hydroxide in step (2) is 3000 mesh.
7. The method for preparing a fire-retardant building insulation board according to claim 2, characterized in that: The process parameters of the supercritical foaming in step (3) are as follows: the pressure of the high-pressure foaming reactor is set to 20-22 MPa, the temperature is set to 170-180°C, the pressure is released after 1.6-2 hours, and the pressure release time is 17-23 seconds.
8. The method for preparing a fire-retardant building insulation board according to claim 2, characterized in that: The preparation method of the thiophene finishing liquid in step (3) is: thiophene, 3-thiopheneacetyl chloride, anhydrous ferric chloride, and tetrahydrofuran are uniformly mixed in a mass ratio of 1: (0.6-0.8): (0.03-0.04): (6-8) to prepare a thiophene finishing liquid.
9. The method for preparing a fire-retardant building insulation board according to claim 2, characterized in that: The preparation method of the benzoxazole finishing liquid in step (3) is: 2-mercaptobenzoxazole, triethylamine, and tetrahydrofuran are uniformly mixed in a mass ratio of 1:(0.03-0.05):(6-8) to prepare the benzoxazole finishing liquid.