Flame-retardant aerogel polyurethane thermal insulation material

Abstract

The invention relates to the technical field of thermal insulation materials, and discloses a flame-retardant aerogel polyurethane thermal insulation material, which is prepared by taking phosphonitrilic chloride trimer, diethanol amine, phenylphosphonic dichloride, diethanol amine and the like as raw materials to obtain an intermediate 3, and reacting the intermediate 3 with glycerol, epichlorohydrin and the like to obtain phosphorus-containing polyether polyol. Finally, the aerogel, triethanolamine, phosphorus-containing polyether polyol, toluene diisocynate and the like are subjected to a reaction and foaming, and the flame-retardant aerogel polyurethane thermal insulation material is obtained. The aerogel polyurethane thermal insulation material prepared by the preparation method disclosed by the invention has relatively good flame retardant property and thermal insulation property.

Description

Technical Field

[0001] The invention relates to the technical field of thermal insulation materials, in particular to a flame-retardant gas gel polyurethane thermal insulation material. Background Art

[0002] In an environment of increasing energy scarcity, energy supply and demand issues are becoming more and more serious. While vigorously developing sustainable renewable energy, finding new ways to save energy and reduce emissions has become one of the effective measures to solve energy problems. Building insulation materials have become an important part of the field of building energy conservation and have received widespread attention from researchers.

[0003] Polyurethane foam has good application prospects in thermal insulation materials due to its good thermal insulation properties, but its flame retardant properties are poor, which limits its application in building insulation materials. Therefore, how to improve its flame retardant properties to expand its application areas is a current research hotspot.

[0004] Aerogel is a porous material with a three-dimensional network structure. Its porous structure can effectively limit solid heat conduction and gas heat convection, so it has a low thermal conductivity and is widely used in aerospace, energy-saving buildings and other fields. Hexachlorocyclotriphosphazene is the most basic compound among phosphazene compounds. It has good flame retardant effect and can be widely used in fire retardant materials and self-extinguishing materials. Summary of the invention

[0005] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides a flame-retardant aerogel polyurethane thermal insulation material. The prepared aerogel polyurethane thermal insulation material has good thermal insulation effect and flame retardant effect.

[0006] (II) Technical solution A flame-retardant gas gel polyurethane thermal insulation material, wherein the flame-retardant gas gel polyurethane thermal insulation material is prepared by the following steps: Step (1), under nitrogen conditions, add glycerol, epichlorohydrin, ethylene oxide, intermediate 3, potassium hydroxide, and magnesium hydroxide into a reaction kettle, stir and disperse, react at 90-110° C. for 1-3 hours, and after the reaction is completed, perform vacuum distillation to obtain a phosphorus-containing polyether polyol; Step (2), stirring and mixing phosphorus-containing polyether polyol, toluene diisocyanate, dibutyltin dilaurate, aerogel, ethylene glycol and triethanolamine evenly, placing in a mold, standing and foaming for 20-50 minutes, and after the foaming is completed, placing in an oven for aging for 3-6 hours, and cooling to obtain a flame-retardant gas gel polyurethane thermal insulation material.

[0007] Preferably, in step (1), the mass ratio of glycerol, epichlorohydrin, ethylene oxide and intermediate 3 is 100:80-150:100-180:20-100.

[0008] Preferably, in step (1), the mass of potassium hydroxide is 0.2-0.6% of the total mass of glycerol, epichlorohydrin, ethylene oxide and intermediate 3.

[0009] Preferably, in step (2), the mass ratio of phosphorus-containing polyether polyol, toluene diisocyanate, dibutyltin dilaurate, aerogel, ethylene glycol and triethanolamine is 100:5-20:1-3:2-15:1.2-2:0.4-0.8.

[0010] Preferably, in step (2), the aerogel is a silicon-based aerogel or a magnesium-based aerogel.

[0011] Preferably, in step (1), the preparation method of intermediate 3 is as follows: S1. Under nitrogen conditions, hexachlorocyclotriphosphazene is added to acetonitrile solvent, stirred and dispersed, and then N,N-dimethylaniline and diethanolamine are added thereto, and the reaction is carried out at 75-80° C. for 12-20 hours. After the reaction is completed, the filtrate is filtered, and the filtrate is distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 1; S2, adding intermediate 1 to acetonitrile solvent, stirring and dispersing, then adding triethylamine and phenylphosphonic dichloride thereto, reacting at 5-10°C for 5-8h, heating to 50-60°C, reacting for 10-24h, and after the reaction, cooling to room temperature, filtering, washing with deionized water, and drying to obtain intermediate 2; S3. Add intermediate 2 to acetonitrile solvent, stir and disperse, then add triethylamine and diethanolamine, react at 5-10°C for 5-8h, heat to 50-60°C, react for 10-24h, after the reaction is completed, cool to room temperature, filter, wash with deionized water, and dry to obtain intermediate 3.

[0012] Preferably, in step S1, the molar ratio of hexachlorocyclotriphosphazene, N,N-dimethylaniline and diethanolamine is 1:6-10:3-4.

[0013] Preferably, in step S2, the molar ratio of intermediate 1, triethylamine and phenylphosphonic acid dichloride is 1:3-3.5:3.

[0014] Preferably, in step S3, the molar ratio of intermediate 2, triethylamine and diethanolamine is 1:3-4:3-4.5.

[0015] 3. Beneficial technical effects The present invention uses hexachlorocyclotriphosphazene and diethanolamine as raw materials and N,N-dimethylaniline as an acid-binding agent, and obtains intermediate 1 through reaction. Under the catalysis of triethylamine, phenylphosphonyl dichloride reacts with intermediate 1 and diethanolamine in sequence by adjusting the dosage ratio to obtain intermediate 3. The hexahydroxy contained in intermediate 3 reacts with propylene glycol, epichlorohydrin, etc. under the catalysis of potassium hydroxide to obtain phosphorus-containing polyether polyol. Finally, aerogel is used as a filler and triethanolamine is used as a foaming agent. According to a certain ratio, the phosphorus-containing polyether polyol is reacted with toluene diisocyanate, ethylene glycol, etc. to foam and obtain a flame-retardant gas gel polyurethane thermal insulation material.

[0016] The intermediate 3 prepared by the present invention has a novel structure and a simple preparation method. It contains a large amount of nitrogen and phosphorus, both of which are good flame retardant elements and can form a phosphorus-nitrogen synergistic system. The aerogel polyurethane thermal insulation material prepared by using it as a raw material has good flame retardant properties. In addition, the present invention uses silicon-based aerogel or magnesium-based aerogel as a filler. The aerogel itself has good thermal insulation properties. When added to polyurethane, the thermal insulation properties of the thermal insulation material can be improved. The aerogel polyurethane thermal insulation material prepared by the present invention has good flame retardant properties and thermal insulation properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the preparation route of intermediate 3. DETAILED DESCRIPTION

[0018] The following non-limiting embodiments may enable a person skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.

[0019] Example 1

[0020] (1) Under nitrogen conditions, 0.03 mol of hexachlorocyclotriphosphazene was added to acetonitrile solvent and stirred for dispersion. Then, 0.18 mol of N,N-dimethylaniline and 0.1 mol of diethanolamine were added thereto. The reaction was carried out at 80°C for 12 h. After the reaction was completed, the filtrate was filtered and vacuum distilled, washed with deionized water, and dried to obtain intermediate 1.

[0021] (2) 0.08 mol of intermediate 1 was added to acetonitrile solvent, stirred and dispersed, and then 0.25 mol of triethylamine and 0.24 mol of phenylphosphonic acid dichloride were added thereto. The reaction was carried out at 10°C for 5 h, and the temperature was raised to 55°C and the reaction was carried out for 24 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with deionized water, and dried to obtain intermediate 2.

[0022] (3) 0.02 mol of intermediate 2 was added to acetonitrile solvent, stirred and dispersed, and then 0.06 mol of triethylamine and 0.09 mol of diethanolamine were added thereto. The reaction was carried out at 10°C for 8 h, and then the temperature was raised to 60°C and the reaction was carried out for 16 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with deionized water, and dried to obtain intermediate 3.

[0023] (4) Under nitrogen conditions, 20 g of propylene glycol, 30 g of epichlorohydrin, 30 g of ethylene oxide, 4 g of intermediate 3, 0.4 g of potassium hydroxide, and 150 g of magnesium hydroxide were added to a reactor, stirred and dispersed, and reacted at 105° C. for 2 h. After the reaction was completed, the mixture was distilled under reduced pressure to obtain a phosphorus-containing polyether polyol.

[0024] (5) 20 g of phosphorus-containing polyether polyol, 1 g of toluene diisocyanate, 0.6 g of dibutyl tin dilaurate, 0.4 g of silicone aerogel, 0.4 g of ethylene glycol, and 0.1 g of triethanolamine were stirred and mixed evenly, placed in a mold, and allowed to stand for foaming for 50 min. After the foaming was completed, the mixture was placed in an oven for aging for 5 h and cooled to obtain a flame-retardant gas gel polyurethane thermal insulation material.

[0025] The flame retardant grade of the flame retardant gas gel polyurethane thermal insulation material prepared by this process is A grade.

[0026] Example 2

[0027] (1) Under nitrogen conditions, 0.03 mol of hexachlorocyclotriphosphazene was added to acetonitrile solvent and stirred for dispersion. Then, 0.2 mol of N,N-dimethylaniline and 0.12 mol of diethanolamine were added thereto. The reaction was carried out at 75°C for 20 h. After the reaction was completed, the filtrate was filtered and vacuum distilled, washed with deionized water, and dried to obtain intermediate 1.

[0028] (2) 0.08 mol of intermediate 1 was added to acetonitrile solvent, stirred and dispersed, and then 0.25 mol of triethylamine and 0.24 mol of phenylphosphonic acid dichloride were added thereto. The reaction was carried out at 10°C for 6 h, and then the temperature was raised to 55°C and the reaction was carried out for 12 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with deionized water, and dried to obtain intermediate 2.

[0029] (3) 0.02 mol of intermediate 2 was added to acetonitrile solvent, stirred and dispersed, and then 0.07 mol of triethylamine and 0.09 mol of diethanolamine were added thereto. The reaction was carried out at 10°C for 6 h, and the temperature was raised to 55°C and the reaction was carried out for 18 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with deionized water, and dried to obtain intermediate 3.

[0030] (4) Under nitrogen conditions, 20 g of propylene glycol, 30 g of epichlorohydrin, 36 g of ethylene oxide, 10 g of intermediate 3, 0.5 g of potassium hydroxide, and 150 g of magnesium hydroxide were added to a reactor, stirred and dispersed, and reacted at 95° C. for 2 h. After the reaction was completed, the mixture was distilled under reduced pressure to obtain a phosphorus-containing polyether polyol.

[0031] (5) 20 g of phosphorus-containing polyether polyol, 3 g of toluene diisocyanate, 0.5 g of dibutyl tin dilaurate, 1 g of silicone aerogel, 0.3 g of ethylene glycol, and 0.16 g of triethanolamine were stirred and mixed evenly, placed in a mold, and allowed to stand for foaming for 40 min. After the foaming was completed, the mixture was placed in an oven for aging for 6 h and cooled to obtain a flame-retardant gas gel polyurethane thermal insulation material.

[0032] The flame retardant grade of the flame retardant gas gel polyurethane thermal insulation material prepared by this process is A grade.

[0033] Example 3

[0034] (1) Under nitrogen conditions, 0.03 mol of hexachlorocyclotriphosphazene was added to acetonitrile solvent and stirred for dispersion. Then, 0.3 mol of N,N-dimethylaniline and 0.09 mol of diethanolamine were added thereto. The reaction was carried out at 80°C for 18 h. After the reaction was completed, the filtrate was filtered and the filtrate was distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 1.

[0035] (2) Add 0.08 mol of intermediate 1 to acetonitrile solvent, stir and disperse, then add 0.28 mol of triethylamine and 0.24 mol of phenylphosphonic acid dichloride, react at 10°C for 6 h, heat to 55°C, react for 24 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water, and dry to obtain intermediate 2.

[0036] (3) Add 0.02 mol of intermediate 2 to acetonitrile solvent, stir and disperse, then add 0.07 mol of triethylamine and 0.08 mol of diethanolamine, react at 5°C for 5 h, heat to 60°C, react for 24 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water, and dry to obtain intermediate 3.

[0037] (4) Under nitrogen conditions, 20 g of propylene glycol, 20 g of epichlorohydrin, 25 g of ethylene oxide, 15 g of intermediate 3, 0.5 g of potassium hydroxide, and 150 g of magnesium hydroxide were added to a reactor, stirred and dispersed, and reacted at 110° C. for 2 h. After the reaction was completed, the mixture was distilled under reduced pressure to obtain a phosphorus-containing polyether polyol.

[0038] (5) 20 g of phosphorus-containing polyether polyol, 4 g of toluene diisocyanate, 0.2 g of dibutyl tin dilaurate, 23 g of silicone aerogel, 0.24 g of ethylene glycol, and 0.08 g of triethanolamine were stirred and mixed evenly, placed in a mold, and allowed to stand for foaming for 20 min. After the foaming was completed, the mixture was placed in an oven for aging for 5 h and cooled to obtain a flame-retardant gas gel polyurethane thermal insulation material.

[0039] The flame retardant grade of the flame retardant gas gel polyurethane thermal insulation material prepared by this process is A grade.

[0040] Example 4

[0041] (1) Under nitrogen conditions, 0.03 mol of hexachlorocyclotriphosphazene was added to acetonitrile solvent and stirred for dispersion. Then, 0.2 mol of N,N-dimethylaniline and 0.1 mol of diethanolamine were added thereto. The reaction was carried out at 80°C for 20 h. After the reaction was completed, the filtrate was filtered and the filtrate was distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 1.

[0042] (2) 0.08 mol of intermediate 1 was added to acetonitrile solvent, stirred and dispersed, and then 0.26 mol of triethylamine and 0.24 mol of phenylphosphonic acid dichloride were added thereto. The reaction was carried out at 5°C for 8 h, and then the temperature was raised to 60°C and the reaction was carried out for 10 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with deionized water, and dried to obtain intermediate 2.

[0043] (3) 0.02 mol of intermediate 2 was added to acetonitrile solvent, stirred and dispersed, and then 0.08 mol of triethylamine and 0.06 mol of diethanolamine were added thereto. The reaction was carried out at 5°C for 8 h, and then the temperature was raised to 50°C and the reaction was carried out for 10 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with deionized water, and dried to obtain intermediate 3.

[0044] (4) Under nitrogen conditions, 20 g of propylene glycol, 20 g of epichlorohydrin, 36 g of ethylene oxide, 18 g of intermediate 3, 0.64 g of potassium hydroxide, and 150 g of magnesium hydroxide were added to a reactor, stirred and dispersed, and reacted at 90° C. for 3 h. After the reaction was completed, the mixture was distilled under reduced pressure to obtain a phosphorus-containing polyether polyol.

[0045] (5) 20 g of phosphorus-containing polyether polyol, 3 g of toluene diisocyanate, 0.4 g of dibutyl tin dilaurate, 2.5 g of magnesium aerogel, 0.3 g of ethylene glycol, and 0.16 g of triethanolamine were stirred and mixed evenly, placed in a mold, and allowed to stand for foaming for 40 min. After the foaming was completed, the mixture was placed in an oven for aging for 5 h and cooled to obtain a flame-retardant gas gel polyurethane thermal insulation material.

[0046] The flame retardant grade of the flame retardant gas gel polyurethane thermal insulation material prepared by this process is A grade.

[0047] Example 5

[0048] (1) Under nitrogen conditions, 0.03 mol of hexachlorocyclotriphosphazene was added to acetonitrile solvent and stirred for dispersion. Then, 0.25 mol of N,N-dimethylaniline and 0.12 mol of diethanolamine were added thereto. The reaction was carried out at 80°C for 20 h. After the reaction was completed, the filtrate was filtered, and the filtrate was distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 1.

[0049] (2) 0.08 mol of intermediate 1 was added to acetonitrile solvent, stirred and dispersed, and then 0.24 mol of triethylamine and 0.24 mol of phenylphosphonic acid dichloride were added thereto. The reaction was carried out at 6°C for 7 h, and then the temperature was raised to 50°C and the reaction was carried out for 12 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with deionized water, and dried to obtain intermediate 2.

[0050] (3) Add 0.02 mol of intermediate 2 to acetonitrile solvent, stir and disperse, then add 0.06 mol of triethylamine and 0.09 mol of diethanolamine, react at 10°C for 6 h, heat to 55°C, react for 12 h. After the reaction is completed, cool to room temperature, filter, wash with deionized water, and dry to obtain intermediate 3.

[0051] (4) Under nitrogen conditions, 20 g of propylene glycol, 16 g of epichlorohydrin, 20 g of ethylene oxide, 20 g of intermediate 3, 0.12 g of potassium hydroxide, and 150 g of magnesium hydroxide were added to a reactor, stirred and dispersed, and reacted at 95° C. for 1 h. After the reaction was completed, the mixture was distilled under reduced pressure to obtain a phosphorus-containing polyether polyol.

[0052] (5) 20 g of phosphorus-containing polyether polyol, 3 g of toluene diisocyanate, 0.4 g of dibutyl tin dilaurate, 3 g of magnesium aerogel, 0.35 g of ethylene glycol, and 0.15 g of triethanolamine were stirred and mixed evenly, placed in a mold, and allowed to stand for foaming for 50 min. After the foaming was completed, the mixture was placed in an oven for aging for 5 h and cooled to obtain a flame-retardant gas gel polyurethane thermal insulation material.

[0053] The flame retardant grade of the flame retardant gas gel polyurethane thermal insulation material prepared by this process is A grade.

[0054] Comparative Example 1 The difference between this comparative example and Example 1 is that in step (5), no silica aerogel powder is contained.

[0055] Thermal insulation performance test: The aerogel polyurethane thermal insulation material was prepared into a hollow block of 30cm×30cm×30cm, an induction thermocouple was placed inside to measure the internal temperature, the opening was sealed, and the block was placed in a constant temperature box and heated from the initial temperature to 70°C. The heating was turned off, and the time required for heating and cooling was recorded.

[0056] Initial temperature / ℃ Heating time / min Cooling time / min Example 1 25 63 46 Example 2 25 68 51 Example 3 25 74 57 Example 4 25 78 59 Example 5 25 80 61 Comparative Example 1 25 52 38 As can be seen from the table, the thermal insulation performance of Comparative Example 2 of Examples 1-5 is the worst, with a heating time of 52 minutes from 25°C to 79°C and a cooling time of 38 minutes. As the amount of silica aerogel powder increases, the heating time and cooling time of the material increase, indicating that the thermal insulation performance of the material is good. Therefore, the aerogel polyurethane thermal insulation material prepared by the present invention has good thermal insulation performance.

[0057] For any technician familiar with the art, without departing from the scope of the technical solution of the present invention, the technical content disclosed above can be used to make many possible changes and modifications to the technical solution of the present invention, or modified into equivalent embodiments with equivalent changes. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention should still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A flame-retardant gel polyurethane thermal insulation material, characterized in that: The flame-retardant gas gel polyurethane thermal insulation material is prepared by the following steps: Step (1), under nitrogen conditions, add glycerol, epichlorohydrin, ethylene oxide, intermediate 3, potassium hydroxide, and magnesium hydroxide into a reaction kettle, stir and disperse, react at 90-110° C. for 1-3 hours, and after the reaction is completed, perform vacuum distillation to obtain a phosphorus-containing polyether polyol; Step (2), stirring and mixing phosphorus-containing polyether polyol, toluene diisocyanate, dibutyltin dilaurate, aerogel, ethylene glycol and triethanolamine evenly, placing in a mold, standing and foaming for 20-50 minutes, and after the foaming is completed, placing in an oven for aging for 3-6 hours, and cooling to obtain a flame-retardant gas gel polyurethane thermal insulation material.

2. The flame-retardant gas gel polyurethane thermal insulation material according to claim 1, characterized in that: In the step (1), the mass ratio of glycerol, epichlorohydrin, ethylene oxide and intermediate 3 is 100:80-150:100-180:20-100.

3. The flame-retardant gas gel polyurethane thermal insulation material according to claim 1, characterized in that: In the step (1), the mass of potassium hydroxide is 0.2-0.6% of the total mass of glycerol, epichlorohydrin, ethylene oxide and intermediate 3.

4. The flame-retardant gas gel polyurethane thermal insulation material according to claim 1, characterized in that: In the step (2), the mass ratio of phosphorus-containing polyether polyol, toluene diisocyanate, dibutyltin dilaurate, aerogel, ethylene glycol and triethanolamine is 100:5-20:1-3:2-15:1.2-2:0.4-0.

8.

5. The flame-retardant gas gel polyurethane thermal insulation material according to claim 1, characterized in that: In the step (2), the aerogel is a silicon-based aerogel or a magnesium-based aerogel.

6. The flame-retardant gas gel polyurethane thermal insulation material according to claim 1, characterized in that: In the step (1), the preparation method of intermediate 3 is as follows: S1. Under nitrogen conditions, hexachlorocyclotriphosphazene is added to acetonitrile solvent, stirred and dispersed, and then N,N-dimethylaniline and diethanolamine are added thereto, and the reaction is carried out at 75-80° C. for 12-20 hours. After the reaction is completed, the filtrate is filtered, and the filtrate is distilled under reduced pressure, washed with deionized water, and dried to obtain intermediate 1; S2, adding intermediate 1 to acetonitrile solvent, stirring and dispersing, then adding triethylamine and phenylphosphonic dichloride thereto, reacting at 5-10°C for 5-8h, heating to 50-60°C, reacting for 10-24h, and after the reaction, cooling to room temperature, filtering, washing with deionized water, and drying to obtain intermediate 2; S3. Add intermediate 2 to acetonitrile solvent, stir and disperse, then add triethylamine and diethanolamine, react at 5-10°C for 5-8h, heat to 50-60°C, react for 10-24h, after the reaction is completed, cool to room temperature, filter, wash with deionized water, and dry to obtain intermediate 3.

7. The flame-retardant gas gel polyurethane thermal insulation material according to claim 6, characterized in that: In the step S1, the molar ratio of hexachlorocyclotriphosphazene, N,N-dimethylaniline and diethanolamine is 1:6-10:3-4.

8. The flame-retardant gas gel polyurethane thermal insulation material according to claim 6, characterized in that: In the step S2, the molar ratio of the intermediate 1, triethylamine and phenylphosphonic acid dichloride is 1:3-3.5:

3.

9. The flame-retardant gas gel polyurethane thermal insulation material according to claim 6, characterized in that: In the step S3, the molar ratio of the intermediate 2, triethylamine and diethanolamine is 1:3-4:3-4.5.

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