CN111995790A - High-flame-retardant polyurethane external wall thermal insulation material for building and preparation method thereof - Google Patents
High-flame-retardant polyurethane external wall thermal insulation material for building and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high flame-retardant polyurethane external wall heat-insulating material for buildings and a preparation method thereof, wherein the heat-insulating material is prepared from the following raw materials in parts by weight: 100-120 parts of polyether polyol, 80-100 parts of triisocyanate, 10-15 parts of expanded perlite, 20-30 parts of foaming agent, 10-20 parts of flame retardant, 10-15 parts of light stabilizer and 3-5 parts of catalyst; the flame retardant can generate oxyacid of phosphorus, the oxyacid of phosphorus can catalyze hydroxyl-containing compounds to dehydrate into carbon, a coke layer is further generated on the surface of the heat preservation material, the coke layer can isolate oxygen and insulate heat, so that flame is extinguished, the light stabilizer can generate nitroxide free radicals after being illuminated, the nitroxide free radicals can capture free radicals generated by the material and inactivate the free radicals to generate ester, and the ester can react with peroxy radicals to regenerate the nitroxide free radicals, so that light energy is consumed.
Description
Technical Field
The invention belongs to the technical field of preparation of heat insulation materials, and particularly relates to a high-flame-retardant polyurethane exterior wall heat insulation material for a building and a preparation method thereof.
Background
Along with the global energy shortage, all countries pay attention to energy conservation, in the building field, along with the continuous development of real estate, the problem of energy shortage is increasingly prominent, in the building energy conservation field, one of the important ways for reducing the building heating energy consumption is to reduce the heat loss of the building peripheral structure to the maximum extent, the wall body is the main body of the building peripheral structure, and the polyurethane thermal insulation material also becomes the current common thermal insulation material.
The flame retardance of the existing polyurethane heat-insulating material is poor, open flame cannot be quickly extinguished when combustion occurs, and in the long-time use process, flame-retardant substances in the heat-insulating material are easy to separate out, so that the flame retardance of the heat-insulating material is reduced or even the flame retardance is lost, the heat-insulating material can be illuminated when the heat-insulating material is used, and the heat-insulating material can generate photochemical reaction in the long-time illumination process, so that the self performance is reduced, and the heat-insulating capacity is reduced.
Disclosure of Invention
The invention aims to provide a high-flame-retardant polyurethane external wall thermal insulation material for buildings and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the flame retardance of the existing polyurethane heat-insulating material is poor, open flame cannot be quickly extinguished when combustion occurs, and in the long-time use process, flame-retardant substances in the heat-insulating material are easy to separate out, so that the flame retardance of the heat-insulating material is reduced or even the flame retardance is lost, the heat-insulating material can be illuminated when the heat-insulating material is used, and the heat-insulating material can generate photochemical reaction in the long-time illumination process, so that the self performance is reduced, and the heat-insulating capacity is reduced.
The purpose of the invention can be realized by the following technical scheme:
a high flame-retardant polyurethane exterior wall thermal insulation material for buildings is prepared from the following raw materials in parts by weight: 100-120 parts of polyether polyol, 80-100 parts of triisocyanate, 10-15 parts of expanded perlite, 20-30 parts of foaming agent, 10-20 parts of flame retardant, 10-15 parts of light stabilizer and 3-5 parts of catalyst;
the heat insulation material is prepared by the following steps:
step S1: drying polyether polyol, triisocyanate and expanded perlite for 5-8h at the temperature of 50-60 ℃ for later use;
step S2: adding expanded perlite and polyether polyol into a reaction kettle, stirring for 5-10min under the condition that the rotating speed is 300-500r/min, adding a flame retardant, a light stabilizer and a catalyst, continuously stirring for 10-15min, adding a foaming agent, and continuously stirring for 10-15min to obtain a first mixture;
step S3: and (4) adding triisocyanate into the first mixture prepared in the step S2, fully stirring, adding into a mold, foaming for 30-40min at the temperature of 30-50 ℃, and curing for 5-8h at the temperature of 80-90 ℃ to prepare the heat insulation material.
Further, the hydroxyl value of the polyether polyol is 480-500mgKOH/g, the viscosity at 25 ℃ is 6500-9500mPa & s, the foaming agent is one or more of trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoroethane which are mixed in any proportion, and the catalyst is one or more of dibutyltin dilaurate, dibutyltin diacetate and stannous octoate which are mixed in any proportion.
Further, the flame retardant is prepared by the following steps:
step A1: dissolving p-nitrophenol in chloroform to prepare a p-nitrophenol solution, adding aluminum chloride and phosphorus oxychloride into a reaction kettle, adding the p-nitrophenol solution under the conditions that the rotating speed is 120-150r/min and the temperature is 60-70 ℃, reacting for 10-15h, adding deionized water, standing for 5-10min, filtering to remove a filtrate, distilling the filtrate at the temperature of 100-110 ℃ to remove a distillate to prepare an intermediate 1;
the reaction process is as follows:
step A2: adding tin powder and the intermediate 1 prepared in the step A1 into a reaction kettle, adding a hydrochloric acid solution at the rotation speed of 60-80r/min and the temperature of 3-5 ℃, heating to 90-95 ℃, reacting for 20-30min, adjusting the pH value of a reaction solution to 9-10, distilling to remove a solvent, adding a substrate and chloroethanol into the reaction kettle, introducing ethylene oxide, and reacting for 5-8h under the conditions that the temperature is 50-70 ℃ and the pressure is 2-3MPa to prepare an intermediate 2;
the reaction process is as follows:
step A3: adding the intermediate 2 prepared in the step A2 and phenyl dichlorophosphate into a reaction kettle, reacting for 6-8h at the conditions of the rotation speed of 120-110 ℃ and the temperature of 100-110 ℃ to prepare an intermediate 3, dissolving cyanuric chloride in ether to prepare a cyanuric chloride solution, adding ammonia water into the cyanuric chloride solution, reacting for 3-5h at the rotation speed of 100-120r/min and the temperature of 3-5 ℃, distilling to remove distillate at the temperature of 50-60 ℃ to prepare an intermediate 4, adding the intermediate 4, the intermediate 3 and benzene into the reaction kettle, adding potassium carbonate, and performing reflux reaction at the temperature of 90-95 ℃ for 5-8h to remove benzene to prepare an intermediate 5;
the reaction process is as follows:
step A4: dissolving the intermediate 5 prepared in the step A3 in acetone to prepare an intermediate 5 solution, dissolving piperazine in deionized water to prepare a piperazine solution, adding the intermediate 5 and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, stirring and adding half of the piperazine solution under the conditions that the temperature is 50-60 ℃ and the rotating speed is 120-plus-one at 150r/min, reacting for 1-1.5h, heating to 90-95 ℃, adding the rest piperazine solution, reacting for 2-3h, and removing ionized water and acetone under the conditions that the temperature is 110-plus-one at 120 ℃ to prepare the flame retardant.
The reaction process is as follows:
further, the molar ratio of the p-nitrophenol to the phosphorus oxychloride in the step A1 is 1:1, the dosage of the aluminum chloride is 5-8% of the mass of the p-nitrophenol, the dosage ratio of the tin powder, the intermediate 1 and the hydrochloric acid solution is 5g:9g:20mL, the concentration of the hydrochloric acid solution is 12mol/L, the dosage of the substrate, the chlorohydrin and the cyclohexane is 8g:3-5mL:5mL, the dosage molar ratio of the intermediate 2 and the phenyl dichlorophosphate in the step A3 is 1:1, the dosage ratio of the cyanuric chloride to the ammonia water is 3g:2mL, the mass fraction of the ammonia water is 20-30%, the dosage molar ratio of the intermediate 3 to the intermediate 4 is 1:1, the dosage molar ratio of the intermediate 5 to the piperazine in the step A4 is 1:1, and the dosage of the sodium hydroxide is 10-15% of the mass of the intermediate 5.
Further, the light stabilizer is prepared by the following steps:
step B1: dissolving cyanuric chloride in toluene to prepare cyanuric chloride solution, adding 2,2,6, 6-tetramethylpiperidine-4-ol, sodium hydroxide, methyl trioctyl ammonium chloride and toluene into a reaction kettle, stirring for 10-15min under the conditions of the rotating speed of 120-150r/min and the temperature of 25-30 ℃, adding the cyanuric chloride solution, reacting for 3-5h under the temperature of 30-35 ℃, filtering to remove filtrate, and distilling the filtrate under the temperature of 115-120 ℃ to prepare an intermediate 6;
the reaction process is as follows:
step B2: dissolving 2, 4-dihydroxy benzophenone in acetone to prepare a2, 4-dihydroxy benzophenone solution, adding cyanuric chloride, acetone and a sodium hydroxide solution into a reaction kettle, stirring for 5-10min under the condition that the rotation speed is 120-one-year-old 150r/min, adding the 2, 4-dihydroxy benzophenone solution, reacting for 5-8h under the condition that the temperature is 90-95 ℃, filtering to remove filtrate, and drying a filter cake to prepare the light stabilizer.
The reaction process is as follows:
further, the molar ratio of the cyanuric chloride to the 2,2,6, 6-tetramethylpiperidine-4-ol to the sodium hydroxide to the methyl trioctyl ammonium chloride in the step B1 is 1:1:2.5:0.01, the molar ratio of the 2, 4-dihydroxybenzophenone to the intermediate 6 in the step B2 is 2:1, the amount of the sodium hydroxide solution is the same as the amount of the 2, 4-dihydroxybenzophenone, and the mass fraction of the sodium hydroxide solution is 8-10%.
A preparation method of a high flame-retardant polyurethane external wall thermal insulation material for buildings specifically comprises the following steps:
step S1: drying polyether polyol, triisocyanate and expanded perlite for 5-8h at the temperature of 50-60 ℃ for later use;
step S2: adding expanded perlite and polyether polyol into a reaction kettle, stirring for 5-10min under the condition that the rotating speed is 300-500r/min, adding a flame retardant, a light stabilizer and a catalyst, continuously stirring for 10-15min, adding a foaming agent, and continuously stirring for 10-15min to obtain a first mixture;
step S3: and (4) adding triisocyanate into the first mixture prepared in the step S2, fully stirring, adding into a mold, foaming for 30-40min at the temperature of 30-50 ℃, and curing for 5-8h at the temperature of 80-90 ℃ to prepare the heat insulation material.
The invention has the beneficial effects that: the invention prepares a flame retardant in the process of preparing a high flame-retardant polyurethane exterior wall heat-insulating material for buildings, the flame retardant takes p-nitrophenol as a raw material, the p-nitrophenol reacts with phosphorus oxychloride to prepare an intermediate 1, the nitro group on the intermediate 1 is reduced to convert the nitro group into amino group, the amino group further reacts with chloroethanol to prepare an intermediate 2, the intermediate 2 reacts with phenyl dichlorophosphate to prepare an intermediate 3, cyanuric chloride reacts with ammonia water, only one chlorine atom of the cyanuric chloride reacts through temperature control to prepare an intermediate 4, the intermediate 4 reacts with the intermediate 3 to prepare an intermediate 5, the intermediate 5 reacts with piperazine to further polymerize to prepare the flame retardant, when the flame retardant burns, the flame retardant molecules can generate oxyacid of phosphorus, the oxyacid of phosphorus can catalyze hydroxyl-containing compounds to dehydrate into carbon, and further generate a coke layer on the surface of the heat-insulating material, the coke layer can separate oxygen and heat, further extinguish flame, and compared with the traditional phosphorus flame retardant, the flame retardant is not easy to separate from the heat insulation material, so that the flame retardance of the heat insulation material is more durable, the flame retardant effect is better, the light stabilizer is prepared, when the light stabilizer molecule is illuminated, the ortho-position of the carbonyl group contains hydroxyl to form intramolecular hydrogen bonds, so that the light stabilizer has a stable conjugated structure, can effectively absorb ultraviolet rays, after the ultraviolet rays are absorbed, the intramolecular hydrogen bonds are cleaved, the hydrogen bond ring is opened to form an ionic compound, the structure is unstable, redundant energy can be released by harmless heat energy to reach a stable state, further the hydrogen bonds are recovered to the original state, further the heat insulation material is protected from photochemical reaction, in addition, the molecule can generate nitroxide radicals after being illuminated, the nitroxide radicals can capture the free radicals generated by the material and can be inactivated to generate ester, the ester can react with peroxy radicals to regenerate the nitroxide radicals, thereby consuming light energy.
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.
Example 1
A high flame-retardant polyurethane exterior wall thermal insulation material for buildings is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol, 80 parts of triisocyanate, 10 parts of expanded perlite, 20 parts of trichlorofluoromethane, 10 parts of flame retardant, 10 parts of light stabilizer and 3 parts of dibutyltin dilaurate;
the heat insulation material is prepared by the following steps:
step S1: drying polyether polyol, triisocyanate and expanded perlite for 5 hours at the temperature of 50 ℃ for later use;
step S2: adding expanded perlite and polyether polyol into a reaction kettle, stirring for 5min under the condition that the rotating speed is 300r/min, adding a flame retardant, a light stabilizer and dibutyltin dilaurate, continuously stirring for 10min, adding trichlorofluoromethane, and continuously stirring for 10min to prepare a first mixture;
step S3: and (3) adding triisocyanate into the first mixture prepared in the step (S2), fully stirring, adding into a mold, foaming at the temperature of 30 ℃ for 30min, and curing at the temperature of 80 ℃ for 5h to prepare the heat-insulating material.
The flame retardant is prepared by the following steps:
step A1: dissolving p-nitrophenol in chloroform to prepare a p-nitrophenol solution, adding aluminum chloride and phosphorus oxychloride into a reaction kettle, adding the p-nitrophenol solution under the conditions of the rotating speed of 120r/min and the temperature of 60 ℃, reacting for 10 hours, adding deionized water, standing for 5 minutes, filtering to remove a filtrate, and distilling the filtrate at the temperature of 100 ℃ to remove a distillate to prepare an intermediate 1;
step A2: adding tin powder and the intermediate 1 prepared in the step A1 into a reaction kettle, adding a hydrochloric acid solution at the rotation speed of 60r/min and the temperature of 3 ℃, heating to 90 ℃, reacting for 20min, adjusting the pH value of a reaction solution to 9, distilling to remove a solvent, adding a substrate and chloroethanol into the reaction kettle, introducing ethylene oxide, and reacting for 5h at the temperature of 50 ℃ and the pressure of 2MPa to prepare an intermediate 2;
step A3: adding the intermediate 2 prepared in the step A2 and phenyl dichlorophosphate into a reaction kettle, reacting for 6 hours at the rotation speed of 120r/min and the temperature of 100 ℃ to prepare an intermediate 3, dissolving cyanuric chloride in diethyl ether to prepare a cyanuric chloride solution, adding ammonia water into the cyanuric chloride solution, reacting for 3 hours at the rotation speed of 100r/min and the temperature of 3 ℃, distilling at the temperature of 50 ℃ to remove distillate to prepare an intermediate 4, adding the intermediate 4, the intermediate 3 and benzene into the reaction kettle, adding potassium carbonate, performing reflux reaction for 5 hours at the temperature of 90 ℃, removing benzene, and preparing an intermediate 5;
step A4: dissolving the intermediate 5 prepared in the step A3 in acetone to prepare an intermediate 5 solution, dissolving piperazine in deionized water to prepare a piperazine solution, adding the intermediate 5 and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, stirring and adding half of the piperazine solution under the conditions of 50 ℃ and 120r/min of rotation speed, reacting for 1h, heating to 90 ℃, adding the rest piperazine solution, reacting for 2h, and removing deionized water and acetone under the condition of 110 ℃ to prepare the flame retardant.
The light stabilizer is prepared by the following steps:
step B1: dissolving cyanuric chloride in toluene to prepare cyanuric chloride solution, adding 2,2,6, 6-tetramethyl piperidine-4-ol, sodium hydroxide, methyl trioctyl ammonium chloride and toluene into a reaction kettle, stirring for 10min at the rotation speed of 120r/min and the temperature of 25 ℃, adding the cyanuric chloride solution, reacting for 3h at the temperature of 30 ℃, filtering to remove filtrate, and distilling the filtrate at the temperature of 115 ℃ to prepare an intermediate 6;
step B2: dissolving 2, 4-dihydroxy benzophenone in acetone to prepare 2, 4-dihydroxy benzophenone solution, adding the intermediate 6, acetone and sodium hydroxide solution into a reaction kettle, stirring for 5min under the condition that the rotation speed is 120r/min, adding the 2, 4-dihydroxy benzophenone solution, reacting for 5h under the condition that the temperature is 90 ℃, filtering to remove filtrate, and drying filter cakes to prepare the light stabilizer.
Example 2
A high flame-retardant polyurethane exterior wall thermal insulation material for buildings is prepared from the following raw materials in parts by weight: 110 parts of polyether polyol, 90 parts of triisocyanate, 13 parts of expanded perlite, 25 parts of trichlorofluoromethane, 15 parts of flame retardant, 13 parts of light stabilizer and 4 parts of dibutyltin dilaurate;
the heat insulation material is prepared by the following steps:
step S1: drying polyether polyol, triisocyanate and expanded perlite for 6 hours at the temperature of 55 ℃ for later use;
step S2: adding expanded perlite and polyether polyol into a reaction kettle, stirring for 8min under the condition that the rotating speed is 400r/min, adding a flame retardant, a light stabilizer and dibutyltin dilaurate, continuously stirring for 13min, adding trichlorofluoromethane, and continuously stirring for 13min to prepare a first mixture;
step S3: and (3) adding triisocyanate into the first mixture prepared in the step S2, fully stirring, adding into a mold, foaming at the temperature of 40 ℃ for 35min, and curing at the temperature of 85 ℃ for 6h to prepare the heat insulation material.
The flame retardant is prepared by the following steps:
step A1: dissolving p-nitrophenol in chloroform to prepare a p-nitrophenol solution, adding aluminum chloride and phosphorus oxychloride into a reaction kettle, adding the p-nitrophenol solution under the conditions of a rotating speed of 130r/min and a temperature of 65 ℃, reacting for 13 hours, adding deionized water, standing for 8 minutes, filtering to remove a filtrate, and distilling the filtrate at a temperature of 105 ℃ to remove a distillate to prepare an intermediate 1;
step A2: adding tin powder and the intermediate 1 prepared in the step A1 into a reaction kettle, adding a hydrochloric acid solution at the rotation speed of 70r/min and the temperature of 4 ℃, heating to the temperature of 95 ℃, reacting for 25min, adjusting the pH value of a reaction solution to 10, distilling to remove a solvent, adding a substrate and chloroethanol into the reaction kettle, introducing ethylene oxide, and reacting for 6h at the temperature of 60 ℃ and the pressure of 3MPa to prepare an intermediate 2;
step A3: adding the intermediate 2 prepared in the step A2 and phenyl dichlorophosphate into a reaction kettle, reacting for 7 hours at the rotation speed of 130r/min and the temperature of 105 ℃ to prepare an intermediate 3, dissolving cyanuric chloride in diethyl ether to prepare a cyanuric chloride solution, adding ammonia water into the cyanuric chloride solution, reacting for 4 hours at the rotation speed of 110r/min and the temperature of 4 ℃, distilling at the temperature of 55 ℃ to remove distillate to prepare an intermediate 4, adding the intermediate 4, the intermediate 3 and benzene into the reaction kettle, adding potassium carbonate, performing reflux reaction at the temperature of 95 ℃ for 6 hours, and removing benzene to prepare an intermediate 5;
step A4: dissolving the intermediate 5 prepared in the step A3 in acetone to prepare an intermediate 5 solution, dissolving piperazine in deionized water to prepare a piperazine solution, adding the intermediate 5 and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, stirring and adding half of the piperazine solution under the conditions of 55 ℃ and 130r/min of rotation speed, reacting for 1.5h, heating to 95 ℃, adding the rest piperazine solution, reacting for 3h, and removing deionized water and acetone under the condition of 115 ℃ to prepare the flame retardant.
The light stabilizer is prepared by the following steps:
step B1: dissolving cyanuric chloride in toluene to prepare cyanuric chloride solution, adding 2,2,6, 6-tetramethylpiperidine-4-ol, sodium hydroxide, methyl trioctyl ammonium chloride and toluene into a reaction kettle, stirring for 13min at the rotation speed of 130r/min and the temperature of 28 ℃, adding the cyanuric chloride solution, reacting for 4h at the temperature of 35 ℃, filtering to remove filtrate, and distilling the filtrate at the temperature of 120 ℃ to prepare an intermediate 6;
step B2: dissolving 2, 4-dihydroxy benzophenone in acetone to prepare 2, 4-dihydroxy benzophenone solution, adding the intermediate 6, acetone and sodium hydroxide solution into a reaction kettle, stirring for 8min under the condition that the rotation speed is 130r/min, adding the 2, 4-dihydroxy benzophenone solution, reacting for 6h under the condition that the temperature is 95 ℃, filtering to remove filtrate, and drying filter cakes to prepare the light stabilizer.
Example 3
A high flame-retardant polyurethane exterior wall thermal insulation material for buildings is prepared from the following raw materials in parts by weight: 120 parts of polyether polyol, 100 parts of triisocyanate, 15 parts of expanded perlite, 30 parts of trichlorofluoromethane, 20 parts of flame retardant, 15 parts of light stabilizer and 5 parts of dibutyltin dilaurate;
the heat insulation material is prepared by the following steps:
step S1: drying polyether polyol, triisocyanate and expanded perlite for 8 hours at the temperature of 60 ℃ for later use;
step S2: adding expanded perlite and polyether polyol into a reaction kettle, stirring for 10min under the condition that the rotating speed is 500r/min, adding a flame retardant, a light stabilizer and dibutyltin dilaurate, continuously stirring for 15min, adding trichlorofluoromethane, and continuously stirring for 15min to prepare a first mixture;
step S3: and (3) adding triisocyanate into the first mixture prepared in the step S2, fully stirring, adding into a mold, foaming at the temperature of 50 ℃ for 40min, and curing at the temperature of 90 ℃ for 8h to prepare the heat-insulating material.
The flame retardant is prepared by the following steps:
step A1: dissolving p-nitrophenol in chloroform to prepare a p-nitrophenol solution, adding aluminum chloride and phosphorus oxychloride into a reaction kettle, adding the p-nitrophenol solution under the conditions of the rotation speed of 150r/min and the temperature of 70 ℃, reacting for 15 hours, adding deionized water, standing for 10 minutes, filtering to remove a filtrate, and distilling the filtrate at the temperature of 110 ℃ to remove a distillate to prepare an intermediate 1;
step A2: adding tin powder and the intermediate 1 prepared in the step A1 into a reaction kettle, adding a hydrochloric acid solution at the rotation speed of 80r/min and the temperature of 5 ℃, heating to 95 ℃, reacting for 30min, adjusting the pH value of a reaction solution to 10, distilling to remove a solvent, adding a substrate and chloroethanol into the reaction kettle, introducing ethylene oxide, and reacting for 8h at the temperature of 70 ℃ and the pressure of 3MPa to prepare an intermediate 2;
step A3: adding the intermediate 2 prepared in the step A2 and phenyl dichlorophosphate into a reaction kettle, reacting for 8 hours at the rotation speed of 150r/min and the temperature of 110 ℃ to prepare an intermediate 3, dissolving cyanuric chloride in diethyl ether to prepare a cyanuric chloride solution, adding ammonia water into the cyanuric chloride solution, reacting for 5 hours at the rotation speed of 120r/min and the temperature of 5 ℃, distilling at the temperature of 60 ℃ to remove distillate to prepare an intermediate 4, adding the intermediate 4, the intermediate 3 and benzene into the reaction kettle, adding potassium carbonate, performing reflux reaction for 8 hours at the temperature of 95 ℃, removing benzene, and preparing an intermediate 5;
step A4: dissolving the intermediate 5 prepared in the step A3 in acetone to prepare an intermediate 5 solution, dissolving piperazine in deionized water to prepare a piperazine solution, adding the intermediate 5 and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, stirring and adding half of the piperazine solution under the conditions of temperature of 60 ℃ and rotation speed of 150r/min, reacting for 1.5h, heating to 95 ℃, adding the rest piperazine solution, reacting for 3h, and removing deionized water and acetone under the condition of temperature of 120 ℃ to prepare the flame retardant.
The light stabilizer is prepared by the following steps:
step B1: dissolving cyanuric chloride in toluene to prepare cyanuric chloride solution, adding 2,2,6, 6-tetramethylpiperidine-4-ol, sodium hydroxide, methyl trioctyl ammonium chloride and toluene into a reaction kettle, stirring for 15min at the rotation speed of 150r/min and the temperature of 30 ℃, adding the cyanuric chloride solution, reacting for 5h at the temperature of 35 ℃, filtering to remove filtrate, and distilling the filtrate at the temperature of 120 ℃ to prepare an intermediate 6;
step B2: dissolving 2, 4-dihydroxy benzophenone in acetone to prepare 2, 4-dihydroxy benzophenone solution, adding the intermediate 6, acetone and sodium hydroxide solution into a reaction kettle, stirring for 10min under the condition that the rotation speed is 150r/min, adding the 2, 4-dihydroxy benzophenone solution, reacting for 8h under the condition that the temperature is 95 ℃, filtering to remove filtrate, and drying filter cakes to prepare the light stabilizer.
Comparative example
The comparative example is a common polyurethane external wall thermal insulation material in the market.
The performance tests were performed on the insulation materials prepared in examples 1 to 3 and comparative example, and the test results are shown in table 1 below;
TABLE 1
From the above table 1, it can be seen that the flame retardant rating of the insulation material prepared in examples 1-3 is V0, the flame retardant rating is V0 after standing for 90 days, and the oxidation embrittlement phenomenon does not occur in GB/T16422.2-1999 standard after 36h of illumination, while the flame retardant rating of the insulation material prepared in the comparative example is V1, the flame retardant rating is V2 after standing for 90 days, and the oxidation embrittlement phenomenon occurs in GB/T16422.2-1999 standard after 24h of illumination, and the surface of the invention has good flame retardancy and light stability.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. A high flame retardant polyurethane exterior wall thermal insulation material for buildings is characterized in that: the feed is prepared from the following raw materials in parts by weight: 100-120 parts of polyether polyol, 80-100 parts of triisocyanate, 10-15 parts of expanded perlite, 20-30 parts of foaming agent, 10-20 parts of flame retardant, 10-15 parts of light stabilizer and 3-5 parts of catalyst;
the heat insulation material is prepared by the following steps:
step S1: drying polyether polyol, triisocyanate and expanded perlite for 5-8h at the temperature of 50-60 ℃ for later use;
step S2: adding expanded perlite and polyether polyol into a reaction kettle, stirring for 5-10min under the condition that the rotating speed is 300-500r/min, adding a flame retardant, a light stabilizer and a catalyst, continuously stirring for 10-15min, adding a foaming agent, and continuously stirring for 10-15min to obtain a first mixture;
step S3: and (4) adding triisocyanate into the first mixture prepared in the step S2, fully stirring, adding into a mold, foaming for 30-40min at the temperature of 30-50 ℃, and curing for 5-8h at the temperature of 80-90 ℃ to prepare the heat insulation material.
2. The high flame retardant polyurethane exterior wall insulation material for building according to claim 1, characterized in that: the polyether polyol has a hydroxyl value of 480-500mgKOH/g, a viscosity of 6500-9500 mPa.s at 25 ℃, a foaming agent which is one or more of trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoroethane which are mixed in any proportion, and a catalyst which is one or more of dibutyltin dilaurate, dibutyltin diacetate and stannous octoate which are mixed in any proportion.
3. The high flame retardant polyurethane exterior wall insulation material for building according to claim 1, characterized in that: the flame retardant is prepared by the following steps:
step A1: dissolving p-nitrophenol in chloroform to prepare a p-nitrophenol solution, adding aluminum chloride and phosphorus oxychloride into a reaction kettle, adding the p-nitrophenol solution under the conditions that the rotating speed is 120-150r/min and the temperature is 60-70 ℃, reacting for 10-15h, adding deionized water, standing for 5-10min, filtering to remove a filtrate, distilling the filtrate at the temperature of 100-110 ℃ to remove a distillate to prepare an intermediate 1;
step A2: adding tin powder and the intermediate 1 prepared in the step A1 into a reaction kettle, adding a hydrochloric acid solution at the rotation speed of 60-80r/min and the temperature of 3-5 ℃, heating to 90-95 ℃, reacting for 20-30min, adjusting the pH value of a reaction solution to 9-10, distilling to remove a solvent, adding a substrate and chloroethanol into the reaction kettle, introducing ethylene oxide, and reacting for 5-8h under the conditions that the temperature is 50-70 ℃ and the pressure is 2-3MPa to prepare an intermediate 2;
step A3: adding the intermediate 2 prepared in the step A2 and phenyl dichlorophosphate into a reaction kettle, reacting for 6-8h at the conditions of the rotation speed of 120-110 ℃ and the temperature of 100-110 ℃ to prepare an intermediate 3, dissolving cyanuric chloride in ether to prepare a cyanuric chloride solution, adding ammonia water into the cyanuric chloride solution, reacting for 3-5h at the rotation speed of 100-120r/min and the temperature of 3-5 ℃, distilling to remove distillate at the temperature of 50-60 ℃ to prepare an intermediate 4, adding the intermediate 4, the intermediate 3 and benzene into the reaction kettle, adding potassium carbonate, and performing reflux reaction at the temperature of 90-95 ℃ for 5-8h to remove benzene to prepare an intermediate 5;
step A4: dissolving the intermediate 5 prepared in the step A3 in acetone to prepare an intermediate 5 solution, dissolving piperazine in deionized water to prepare a piperazine solution, adding the intermediate 5 and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, stirring and adding half of the piperazine solution under the conditions that the temperature is 50-60 ℃ and the rotating speed is 120-plus-one at 150r/min, reacting for 1-1.5h, heating to 90-95 ℃, adding the rest piperazine solution, reacting for 2-3h, and removing ionized water and acetone under the conditions that the temperature is 110-plus-one at 120 ℃ to prepare the flame retardant.
4. The high flame retardant polyurethane exterior wall insulation material for building according to claim 3, characterized in that: the molar ratio of the p-nitrophenol to the phosphorus oxychloride in the step A1 is 1:1, the dosage of the aluminum chloride is 5-8% of the mass of the p-nitrophenol, the dosage ratio of the tin powder, the intermediate 1 and the hydrochloric acid solution is 5g:9g:20mL, the concentration of the hydrochloric acid solution is 12mol/L, the dosage of the substrate, the chlorohydrin and the cyclohexane is 8g:3-5mL:5mL, the dosage molar ratio of the intermediate 2 and the phenyl dichlorophosphate in the step A3 is 1:1, the dosage ratio of the cyanuric chloride to the ammonia water is 3g:2mL, the mass fraction of the ammonia water is 20-30%, the dosage molar ratio of the intermediate 3 to the intermediate 4 is 1:1, the dosage molar ratio of the intermediate 5 to the piperazine in the step A4 is 1:1, and the dosage of the sodium hydroxide is 10-15% of the mass of the intermediate 5.
5. The high flame retardant polyurethane exterior wall insulation material for building according to claim 1, characterized in that: the light stabilizer is prepared by the following steps:
step B1: dissolving cyanuric chloride in toluene to prepare cyanuric chloride solution, adding 2,2,6, 6-tetramethylpiperidine-4-ol, sodium hydroxide, methyl trioctyl ammonium chloride and toluene into a reaction kettle, stirring for 10-15min under the conditions of the rotating speed of 120-150r/min and the temperature of 25-30 ℃, adding the cyanuric chloride solution, reacting for 3-5h under the temperature of 30-35 ℃, filtering to remove filtrate, and distilling the filtrate under the temperature of 115-120 ℃ to prepare an intermediate 6;
step B2: dissolving 2, 4-dihydroxy benzophenone in acetone to prepare a2, 4-dihydroxy benzophenone solution, adding cyanuric chloride, acetone and a sodium hydroxide solution into a reaction kettle, stirring for 5-10min under the condition that the rotation speed is 120-one-year-old 150r/min, adding the 2, 4-dihydroxy benzophenone solution, reacting for 5-8h under the condition that the temperature is 90-95 ℃, filtering to remove filtrate, and drying a filter cake to prepare the light stabilizer.
6. The high flame retardant polyurethane exterior wall insulation material for building according to claim 5, characterized in that: the molar ratio of the cyanuric chloride to the 2,2,6, 6-tetramethylpiperidine-4-ol to the sodium hydroxide to the methyl trioctyl ammonium chloride in the step B1 is 1:1:2.5:0.01, the molar ratio of the 2, 4-dihydroxybenzophenone to the intermediate 6 in the step B2 is 2:1, the mass of the sodium hydroxide solution is the same as that of the 2, 4-dihydroxybenzophenone, and the mass fraction of the sodium hydroxide solution is 8-10%.
7. The preparation method of the high flame retardant polyurethane exterior wall thermal insulation material for the building according to claim 1, which is characterized by comprising the following steps: the method specifically comprises the following steps:
step S1: drying polyether polyol, triisocyanate and expanded perlite for 5-8h at the temperature of 50-60 ℃ for later use;
step S2: adding expanded perlite and polyether polyol into a reaction kettle, stirring for 5-10min under the condition that the rotating speed is 300-500r/min, adding a flame retardant, a light stabilizer and a catalyst, continuously stirring for 10-15min, adding a foaming agent, and continuously stirring for 10-15min to obtain a first mixture;
step S3: and (4) adding triisocyanate into the first mixture prepared in the step S2, fully stirring, adding into a mold, foaming for 30-40min at the temperature of 30-50 ℃, and curing for 5-8h at the temperature of 80-90 ℃ to prepare the heat insulation material.
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