Preparation process of aging-resistant flame-retardant polyurethane foaming material

Abstract

This invention relates to the field of polyurethane foam materials, specifically, to a preparation process for an aging-resistant and flame-retardant polyurethane foam material. The preparation process includes the preparation of a composite flame retardant, the preparation of component A, and the preparation of the polyurethane foam material. This invention integrates the composite flame retardant into the cross-linked network of the polyurethane foam material via chemical bonds. The composite flame retardant is prepared by grafting a phosphorus-containing flame-retardant structure onto the cage-like polysilsesquioxane structure after a ring-opening reaction between the epoxy groups in glycidyl etheroxypropyl cage-like polysilsesquioxane or octacyclooxycyclohexylethyl cage-like polysilsesquioxane and the acidic hydroxyl groups in diphenyl phosphate. The composite flame retardant of this invention is less prone to migration, precipitation, or loss, and improves the rigidity and aging resistance of the polyurethane matrix through its rigid cage structure and benzene rings, thereby improving flame retardant performance while reducing adverse effects on the mechanical properties of the foam material.

Description

Technical Field

[0001] This invention relates to the field of polyurethane foam materials, specifically, to a preparation process for an aging-resistant and flame-retardant polyurethane foam material. Background Technology

[0002] Polyurethane foam is lightweight and has high specific strength due to its unique pore structure. It is produced by reacting isocyanates and polyols with catalysts, surfactants, and foaming agents, and consists of repeating urethane functional groups. It is widely used in exterior wall insulation, building decoration, automotive parts, and many other fields. However, polyurethane foam has relatively poor flame retardant and aging resistance. Untreated polyurethane foam has an oxygen index of only about 17, classifying it as flammable. To meet flame retardant requirements, 13-20% flame retardant is added during the preparation of polyurethane foam. However, the compressive and tensile strengths of polyurethane foam typically decrease with increasing flame retardant dosage, making the material brittle. Furthermore, the addition of solid flame retardant powder can disrupt the surface tension of the bubble film, affecting the foaming effect; while the addition of liquid flame retardants not only acts as a plasticizer, making the polyurethane foam softer, but also migrates from the interior to the surface after prolonged use, causing the material to become sticky and releasing VOCs, significantly reducing its flame retardant effect.

[0003] Based on this, a preparation process for aging-resistant and flame-retardant polyurethane foam material is proposed. Summary of the Invention

[0004] The purpose of this invention is to provide a preparation process for an aging-resistant and flame-retardant polyurethane foam material, so as to achieve the goal of maintaining good mechanical properties while satisfying the flame-retardant and aging-resistant properties of polyurethane foam material.

[0005] To achieve the above objectives, the present invention provides a preparation process for an aging-resistant and flame-retardant polyurethane foam material, the preparation process comprising: S1. Preparation of composite flame retardants A cage-like polysilsesquioxane containing epoxy groups was dissolved in anhydrous toluene, and then diphenyl phosphate was added. A boron trifluoride diethyl ether complex catalyst was added dropwise, and the mixture was stirred for 10-20 minutes. The temperature was raised to 50-60°C, and the reaction was stirred for 4-6 hours. After the reaction was completed, the mixture was rotary evaporated at 60-70°C to 40-50% of the original volume of the reaction system to obtain a reaction solution. The reaction solution was cooled to room temperature, and the product was added to anhydrous ethanol to precipitate the product. The product was then washed 2-3 times with anhydrous ethanol and dried under vacuum at 50-60°C to obtain a composite flame retardant.

[0006] Preferably, the epoxy-containing cage-like polysilsesquioxane is glycidyl etheroxypropyl cage-like polysilsesquioxane or octacyclooxycyclohexylethyl cage-like polysilsesquioxane.

[0007] Preferably, the molar ratio of the epoxy-containing cage-like polysilsesquioxane to diphenyl phosphate is 1:8.2 to 8.5.

[0008] Preferably, the amount of the catalyst boron trifluoride diethyl ether complex added is 1 to 2% of the total mass of the cage-like polysilsesquioxane containing epoxy groups and diphenyl phosphate.

[0009] Preferably, the mass ratio of the epoxy-containing cage-like polysilsesquioxane to anhydrous toluene is 1:12 to 14.

[0010] Preferably, the stirring rate of the stirring reaction is 150-250 r / min.

[0011] Preferably, the volume ratio of the reaction solution to anhydrous ethanol is 1:4 to 5.

[0012] The glycidyl etheroxypropyl cage-like polysilsesquioxane or octacyclooxycyclohexylethyl cage-like polysilsesquioxane contains eight epoxy groups, and the diphenyl phosphate contains one acidic hydroxyl group. Under the action of a catalyst, the epoxy groups in the glycidyl etheroxypropyl cage-like polysilsesquioxane or octacyclooxycyclohexylethyl cage-like polysilsesquioxane undergo ring-opening reaction with the acidic hydroxyl group of the diphenyl phosphate, thereby grafting the diphenyl phosphate and generating a new secondary hydroxyl group.

[0013] Preparation of S2 and A components The composite flame retardant is heated and melted to obtain a liquid composite flame retardant. The oligomeric polyol is preheated to 80-100℃, and then the liquid composite flame retardant is added. The mixture is vacuum stirred at 110-120℃ to dehydrate until no bubbles are generated. After cooling to room temperature, water, polyether-modified silicone oil, triethanolamine, dibutyltin dilaurate, and titanium dioxide are added and stirred rapidly for 2-3 minutes. The mixture is then sealed and stored to obtain component A.

[0014] Preferably, the heating and melting temperature is 90–100°C.

[0015] Preferably, the oligomeric polyol is one or more of polyether polyol, polycarbonate polyol, polyester polyol, aromatic polyol, and aliphatic polyol.

[0016] Preferably, in component A, the raw materials are as follows by weight: 95-105 parts of oligomeric polyol, 10-15 parts of composite flame retardant, 2-3 parts of water, 1.5-2.5 parts of polyether-modified silicone oil, 0.5-1.5 parts of triethanolamine, 0.1-0.3 parts of dibutyltin dilaurate, and 1-2 parts of titanium dioxide.

[0017] Preferably, the rapid stirring rate is 1500-2000 r / min.

[0018] S3. Preparation of polyurethane foam materials Using isocyanate as component B; quickly mix components A and B for 20-30 seconds and pour into a mold, foam at 40-50℃ for 30-40 minutes, cool and demold, and let stand at room temperature for 1-2 days to obtain polyurethane foam material.

[0019] Preferably, the rapid mixing rate is 2500-3000 r / min.

[0020] Preferably, the isocyanate is diphenylmethylene diisocyanate or polymethylene polyphenyl isocyanate or a mixture thereof.

[0021] Preferably, the isocyanate index during foaming is 1.05 to 1.2.

[0022] Preferably, the mass ratio of component A to component B is 1:1.3 to 1.55.

[0023] The composite flame retardant obtained from S1 has newly formed secondary hydroxyl groups. These secondary hydroxyl groups can react with the isocyanate groups (-NCO) in component B to form urethane bonds, allowing the composite flame retardant to integrate into the cross-linked network of the polyurethane foam. The formation of these chemical bonds makes the composite flame retardant more stable and less prone to migration and precipitation within the polyurethane foam. The cage-like polysilsesquioxane and benzene ring structures in the composite flame retardant improve the material's thermal stability and aging resistance, while phosphorus provides a flame-retardant effect and avoids excessive damage to the mechanical properties of the foam material caused by small-molecule phosphate esters.

[0024] The glycidyl etheroxypropyl cage-like polysilsesquioxane / octacyclooxycyclohexylethyl cage-like polysilsesquioxane used in this invention was purchased from Hubei Changyao Biotechnology Co., Ltd.

[0025] By adopting the above technical solution, the beneficial effects of the present invention are as follows: 1. This invention first utilizes the epoxy groups in glycidyl etheroxypropyl cage-like polysilsesquioxane or octacyclooxycyclohexylethyl cage-like polysilsesquioxane to undergo a ring-opening reaction with the acidic hydroxyl groups in diphenyl phosphate, grafting a phosphorus-containing flame-retardant structure onto the cage-like polysilsesquioxane structure, thereby obtaining a composite flame retardant containing phosphorus, a cage-like polysilsesquioxane structure, and a benzene ring structure. This composite flame retardant combines the char-promoting effect of phosphorus-based flame retardants with the heat-insulating and char-reinforcing effects of cage-like polysilsesquioxane, thus improving the flame-retardant performance of polyurethane foam materials.

[0026] 2. In this invention, the composite flame retardant is incorporated into the cross-linked network of polyurethane foam material in the form of chemical bonds. Compared with traditional physically added flame retardants, the composite flame retardant of this invention has better compatibility in the material and is less prone to migration, precipitation or loss, which is beneficial to maintaining the long-term stable flame retardant performance of the material.

[0027] 3. The composite flame retardant of the present invention can not only exert a flame retardant effect, but also improve the rigidity and aging resistance of the polyurethane matrix through a rigid cage structure and benzene rings, thereby improving the flame retardant performance while reducing the adverse effects on the mechanical properties of the foam material.

[0028] 4. The composite flame retardant of the present invention contains a benzene ring structure and a rigid cage structure, which can improve the rigidity of the material molecular chain segments and slow down the degradation of polyurethane chain segments during thermo-oxidative aging. At the same time, the composite flame retardant is fixed in the polyurethane network through chemical reaction, which can reduce the loss of flame retardant components during long-term use, thereby improving the aging resistance and service life of polyurethane foam materials. Detailed Implementation

[0029] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0030] Example 1: A preparation process for an aging-resistant and flame-retardant polyurethane foam material, the preparation process comprising: S1. Preparation of composite flame retardants Glycidyl etheroxypropyl cage-like polysilsesquioxane was dissolved in anhydrous toluene, then diphenyl phosphate was added, and boron trifluoride diethyl ether complex catalyst was added dropwise. The mixture was stirred for 15 min, heated to 55 °C, and stirred for 5 h. After the reaction was completed, the mixture was rotary evaporated at 65 °C to 45% of the original volume of the reaction system to obtain the reaction solution. The reaction solution was cooled to room temperature, and the product was added to anhydrous ethanol to precipitate the product. The product was then washed three times with anhydrous ethanol and dried under vacuum at 55 °C for 8 h to obtain the composite flame retardant.

[0031] The molar ratio of glycidyl etheroxypropyl cage-like polysilsesquioxane to diphenyl phosphate is 1:8.4.

[0032] The amount of the catalyst boron trifluoride diethyl ether complex added is 1.5% of the total mass of glycidyl etheroxypropyl cage-like polysilsesquioxane and diphenyl phosphate.

[0033] The mass ratio of the glycidyl etheroxypropyl cage-like polysilsesquioxane to anhydrous toluene is 1:13.

[0034] The stirring rate of the stirring reaction is 200 r / min.

[0035] The volume ratio of the reaction solution to anhydrous ethanol is 1:4.5.

[0036] Preparation of S2 and A components The composite flame retardant was heated and melted to obtain a liquid composite flame retardant. Polyether polyol 4110 was preheated at 90°C, and then the liquid composite flame retardant was added. The mixture was vacuum stirred at 115°C to dehydrate until no bubbles were generated. After cooling to room temperature, water, polyether modified silicone oil, triethanolamine, dibutyltin dilaurate, and titanium dioxide were added and stirred rapidly for 3 minutes. The mixture was then sealed and stored to obtain component A.

[0037] The heating and melting temperature is 95°C.

[0038] The raw materials in Component A, by weight, are: 100 parts of polyether polyol 4110, 13 parts of composite flame retardant, 2.5 parts of water, 2 parts of polyether modified silicone oil, 1 part of triethanolamine, 0.2 parts of dibutyltin dilaurate, and 1.5 parts of titanium dioxide.

[0039] The polyether polyol 4110 has an effective component content of 99.5% and a hydroxyl value of 420-460 mgKOH / g.

[0040] The tin content of the dibutyltin dilaurate is 18%.

[0041] The rapid stirring rate is 1800 r / min.

[0042] S3. Preparation of polyurethane foam materials PM200 polymerized MDI was used as component B; components A and B were quickly mixed for 25 seconds and poured into a mold, foamed at 45°C for 35 minutes, cooled and demolded, and then left to stand at room temperature for 2 days to obtain polyurethane foam material.

[0043] The rapid mixing rate is 2800 r / min.

[0044] The NCO mass fraction in the PM200 polymerized MDI is 31%.

[0045] The isocyanate index during foaming is 1.15.

[0046] The mass ratio of component A to component B is 1:1.4.

[0047] Example 2: A preparation process for an aging-resistant and flame-retardant polyurethane foam material, the preparation process comprising: S1. Preparation of composite flame retardants Glycidyl etheroxypropyl cage-like polysilsesquioxane was dissolved in anhydrous toluene, then diphenyl phosphate was added, and boron trifluoride diethyl ether complex catalyst was added dropwise. The mixture was stirred for 10 min, heated to 60 °C, and stirred for 4 h. After the reaction was completed, the mixture was rotary evaporated at 60 °C to 50% of the original volume of the reaction system to obtain the reaction solution. The reaction solution was cooled to room temperature, and the product was added to anhydrous ethanol to precipitate the product. The product was then washed twice with anhydrous ethanol and dried under vacuum at 50 °C for 8 h to obtain the composite flame retardant.

[0048] The molar ratio of glycidyl etheroxypropyl cage-like polysilsesquioxane to diphenyl phosphate is 1:8.2.

[0049] The amount of the catalyst boron trifluoride diethyl ether complex added is 1% of the total mass of glycidyl etheroxypropyl cage-like polysilsesquioxane and diphenyl phosphate.

[0050] The mass ratio of the glycidyl etheroxypropyl cage-like polysilsesquioxane to anhydrous toluene is 1:12.

[0051] The stirring rate of the stirring reaction is 150 r / min.

[0052] The volume ratio of the reaction solution to anhydrous ethanol is 1:4.

[0053] Preparation of S2 and A components The composite flame retardant was heated and melted to obtain a liquid composite flame retardant. Polyether polyol 4110 was preheated to 80°C, and then the liquid composite flame retardant was added. The mixture was vacuum stirred at 110°C to dehydrate until no bubbles were generated. After cooling to room temperature, water, polyether modified silicone oil, triethanolamine, dibutyltin dilaurate, and titanium dioxide were added and stirred rapidly for 3 minutes. The mixture was then sealed and stored to obtain component A.

[0054] The heating and melting temperature is 90°C.

[0055] The raw materials in Component A, by weight, are: 95 parts of polyether polyol 4110, 10 parts of composite flame retardant, 2 parts of water, 1.5 parts of polyether modified silicone oil, 0.5 parts of triethanolamine, 0.1 parts of dibutyltin dilaurate, and 1 part of titanium dioxide.

[0056] The polyether polyol 4110 has an effective component content of 99.5% and a hydroxyl value of 420-460 mgKOH / g.

[0057] The tin content of the dibutyltin dilaurate is 18%.

[0058] The rapid stirring rate is 1500 r / min.

[0059] S3. Preparation of polyurethane foam materials PM200 polymerized MDI was used as component B; components A and B were quickly mixed for 30 seconds and poured into a mold, foamed at 40°C for 30 minutes, cooled and demolded, and then left to stand at room temperature for 2 days to obtain polyurethane foam material.

[0060] The rapid mixing rate is 2500 r / min.

[0061] The NCO mass fraction in the PM200 polymerized MDI is 31%.

[0062] The isocyanate index during foaming is 1.05.

[0063] The mass ratio of component A to component B is 1:1.3.

[0064] Example 3: A preparation process for an aging-resistant and flame-retardant polyurethane foam material, the preparation process comprising: S1. Preparation of composite flame retardants Glycidyl etheroxypropyl cage-like polysilsesquioxane was dissolved in anhydrous toluene, then diphenyl phosphate was added, and boron trifluoride diethyl ether complex catalyst was added dropwise. The mixture was stirred for 20 min, heated to 50 °C, and stirred for 6 h. After the reaction was completed, the mixture was rotary evaporated at 70 °C to 40% of the original volume of the reaction system to obtain the reaction solution. The reaction solution was cooled to room temperature, and the product was added to anhydrous ethanol to precipitate the product. The product was then washed three times with anhydrous ethanol and dried under vacuum at 60 °C for 8 h to obtain the composite flame retardant.

[0065] The molar ratio of glycidyl etheroxypropyl cage-like polysilsesquioxane to diphenyl phosphate is 1:8.5.

[0066] The amount of the catalyst boron trifluoride diethyl ether complex added is 2% of the total mass of glycidyl etheroxypropyl cage-like polysilsesquioxane and diphenyl phosphate.

[0067] The mass ratio of the glycidyl etheroxypropyl cage-like polysilsesquioxane to anhydrous toluene is 1:14.

[0068] The stirring rate of the stirring reaction is 250 r / min.

[0069] The volume ratio of the reaction solution to anhydrous ethanol is 1:5.

[0070] Preparation of S2 and A components The composite flame retardant was heated and melted to obtain a liquid composite flame retardant. Polyether polyol 4110 was preheated to 100°C, and then the liquid composite flame retardant was added. The mixture was vacuum stirred at 120°C to dehydrate until no bubbles were generated. After cooling to room temperature, water, polyether modified silicone oil, triethanolamine, dibutyltin dilaurate, and titanium dioxide were added and stirred rapidly for 2 minutes. The mixture was then sealed and stored to obtain component A.

[0071] The heating and melting temperature is 100°C.

[0072] The raw materials in Component A, by weight, are: 105 parts of polyether polyol 4110, 15 parts of composite flame retardant, 3 parts of water, 2.5 parts of polyether modified silicone oil, 1.5 parts of triethanolamine, 0.3 parts of dibutyltin dilaurate, and 2 parts of titanium dioxide.

[0073] The polyether polyol 4110 has an effective component content of 99.5% and a hydroxyl value of 420-460 mgKOH / g.

[0074] The tin content of the dibutyltin dilaurate is 18%.

[0075] The rapid stirring rate is 2000 r / min.

[0076] S3. Preparation of polyurethane foam materials PM200 polymerized MDI was used as component B; components A and B were quickly mixed for 20 seconds and poured into a mold, foamed at 50°C for 40 minutes, cooled and demolded, and then left to stand at room temperature for 2 days to obtain polyurethane foam material.

[0077] The rapid mixing rate is 3000 r / min.

[0078] The NCO mass fraction in the PM200 polymerized MDI is 31%.

[0079] The isocyanate index during foaming is 1.2.

[0080] The mass ratio of component A to component B is 1:1.55.

[0081] Comparative Example 1: The composite flame retardant was removed, and equal amounts of glycidyl etheroxypropyl cage-like polysilsesquioxane and triphenyl phosphate were directly blended with other raw materials of component A in S2. The rest was the same as in Example 1, and this was used as Comparative Example 1.

[0082] Comparative Example 2: The composite flame retardant was removed, and equal amounts of glycidyl etheroxypropyl cage-like polysilsesquioxane and diethyl hydroxymethylphosphonate were directly blended with other raw materials of component A in S2. The rest was the same as in Example 1, and this was used as Comparative Example 2.

[0083] Comparative Example 3: Diphenyl phosphate in S1 was replaced with diethyl hydroxymethylphosphonate, and all other steps were the same as in Example 1.

[0084] Comparative Example 4: The composite flame retardant was removed, and triphenyl phosphate was directly used to replace the composite flame retardant in S2 and blended with the other raw materials of component A. Everything else was the same as in Example 1. This was used as Comparative Example 4.

[0085] The polyurethane foam materials prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance testing, as shown in Table 1.

[0086] Compression performance test method: Cut polyurethane foam material into 30mm×30mm×30mm cubes, use the compression mode of a universal tensile testing machine, the compression percentage is 10%, and the compression speed is 10mm / min.

[0087] Table 1

[0088] The polyurethane foam materials prepared in Examples 1-3 and Comparative Examples 1-4 were placed in a 90°C thermal aging chamber for 1000 hours and then tested for compression and flame retardancy.

[0089]

[0090] As can be seen from Table 1, the polyurethane foam materials prepared in Examples 1-3 have good mechanical properties and flame retardant effects.

[0091] Since diphenyl phosphate contains acidic hydroxyl groups, if it is added directly to component A, it will react with the alkaline triethanolamine and affect the foaming performance. Therefore, comparative examples 1 and 4 selected triphenyl phosphate, which has a similar structure and performance to diphenyl phosphate but does not contain acidic hydroxyl groups and contains three benzene rings. This will not interfere with the catalytic effect of triethanolamine and allow foaming to proceed smoothly.

[0092] The compressive strength of Comparative Example 1 decreased significantly, and the limiting oxygen index also decreased slightly. This is because triphenyl phosphate has a plasticizing effect in the foamed material, leading to softening of the polymer network structure and lower compressive strength. Simultaneously, the uneven distribution of glycidyl etheroxypropyl cage-like polysilsesquioxane and the presence of a small amount of side reaction with isocyanate resulted in increased local crosslinking and uneven stress distribution, further reducing strength. Triphenyl phosphate exists in a free state during foaming, thus its uneven distribution during foaming leads to a slight reduction in flame retardant effect. In Comparative Example 1, triphenyl phosphate cannot form chemical bonds with the foamed material, therefore it easily migrates during aging, resulting in a decrease in strength and flame retardant properties after aging.

[0093] The compressive strength of the polyurethane foam material in Comparative Example 2 decreased the most, even more than that in Comparative Example 1. This is because diethyl hydroxymethylphosphonate contains only one hydroxyl group, which reacts with isocyanate, affecting the crosslinking density of the polymer network in the foam material. Compared with diphenyl phosphate in Example 1 and triphenyl phosphate in Comparative Example 1, diethyl hydroxymethylphosphonate lacks a benzene ring. Therefore, although it has a cage-like structure, the aging resistance of Comparative Example 2 is slightly worse than that of Example 1 and Comparative Example 1. Since there is a chemical bond between diethyl hydroxymethylphosphonate and the foam material in Comparative Example 2, it is less prone to migration than Comparative Example 1. Although its flame retardant effect after aging is not as good as that of Example 1, it is worse than that of Comparative Example 1.

[0094] The compressive strength, aging compressive strength, and flame retardant effect of the polyurethane foam material in Comparative Example 3 were all inferior to those in Example 1, further demonstrating that the benzene ring in diphenyl phosphate can not only improve the rigidity of the polyurethane foam material, but also improve the aging resistance of the material.

[0095] The compressive strength, aging compressive strength, and flame retardant effect of the polyurethane foam material in Comparative Example 4 were all inferior to those in Comparative Example 1. This indicates that glycidyl etheroxypropyl cage-like polysilsesquioxane can not only improve the mechanical properties of polyurethane foam materials, but also enhance the flame retardant effect through the synergistic effect of silicon and phosphorus. However, triphenyl phosphate cannot form chemical bonds with the foam material, so it is easy to migrate during the aging process, resulting in a decrease in strength and flame retardant performance after aging.

[0096] Unless otherwise specified, all proportions and percentages mentioned in this invention are mass proportions and mass percentages; all raw materials are commercially available.

[0097] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely preferred examples and are not intended to limit the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation process for an aging-resistant and flame-retardant polyurethane foam material, characterized in that, The preparation process includes the preparation of composite flame retardant, the preparation of component A, and the preparation of polyurethane foam material; The preparation of component A is as follows: the composite flame retardant is heated and melted to obtain a liquid composite flame retardant; the oligomeric polyol is preheated to 80-100°C, and then the liquid composite flame retardant is added. The mixture is then vacuum stirred at 110-120°C to dehydrate until no bubbles are generated. After cooling to room temperature, water, polyether-modified silicone oil, triethanolamine, dibutyltin dilaurate, and titanium dioxide are added and stirred rapidly for 2-3 minutes. The mixture is then sealed and stored to obtain component A.

2. The preparation process of an aging-resistant and flame-retardant polyurethane foam material according to claim 1, characterized in that, The composite flame retardant is prepared by dissolving a cage-like polysilsesquioxane containing epoxy groups in anhydrous toluene, adding diphenyl phosphate, adding boron trifluoride diethyl ether complex as a catalyst, stirring for 10-20 minutes, heating to 50-60°C, stirring for 4-6 hours, and after the reaction is complete, rotary evaporating at 60-70°C to 40-50% of the original volume of the reaction system to obtain a reaction solution; cooling to room temperature, adding the reaction solution to anhydrous ethanol to precipitate the product, washing with anhydrous ethanol 2-3 times, and vacuum drying at 50-60°C to obtain the composite flame retardant.

3. The preparation process of an aging-resistant and flame-retardant polyurethane foam material according to claim 2, characterized in that, The cage-like polysilsesquioxane containing epoxy groups is glycidyl etheroxypropyl cage-like polysilsesquioxane or octacyclooxycyclohexylethyl cage-like polysilsesquioxane.

4. The preparation process of an aging-resistant and flame-retardant polyurethane foam material according to claim 2, characterized in that, The molar ratio of the epoxy-containing cage-like polysilsesquioxane to diphenyl phosphate is 1:8.2-8.5; The amount of the catalyst boron trifluoride diethyl ether complex added is 1-2% of the total mass of the cage-like polysilsesquioxane containing epoxy groups and diphenyl phosphate; The mass ratio of the epoxy-containing cage-like polysilsesquioxane to anhydrous toluene is 1:12-14.

5. The preparation process of an aging-resistant and flame-retardant polyurethane foam material according to claim 2, characterized in that, The stirring rate of the stirring reaction is 150–250 r / min; The volume ratio of the reaction solution to anhydrous ethanol is 1:4 to 5.

6. The preparation process of an aging-resistant and flame-retardant polyurethane foam material according to claim 1, characterized in that, The heating and melting temperature is 90–100°C; The oligomeric polyol is one or more of polyether polyol, polycarbonate polyol, polyester polyol, aromatic polyol, and aliphatic polyol.

7. The preparation process of an aging-resistant and flame-retardant polyurethane foam material according to claim 1, characterized in that, The raw materials in component A, by weight, are as follows: 95-105 parts of oligomeric polyol, 10-15 parts of composite flame retardant, 2-3 parts of water, 1.5-2.5 parts of polyether-modified silicone oil, 0.5-1.5 parts of triethanolamine, 0.1-0.3 parts of dibutyltin dilaurate, and 1-2 parts of titanium dioxide. The rapid stirring rate is 1500–2000 r / min.

8. The preparation process of an aging-resistant and flame-retardant polyurethane foam material according to claim 1, characterized in that, The polyurethane foam material is prepared by using isocyanate as component B; rapidly mixing components A and B for 20-30 seconds and pouring the mixture into a mold; foaming at 40-50°C for 30-40 minutes; cooling and demolding; and then allowing it to stand at room temperature for 1-2 days to obtain the polyurethane foam material.

9. The preparation process of an aging-resistant and flame-retardant polyurethane foam material according to claim 8, characterized in that, The rapid mixing rate is 2500–3000 r / min; The isocyanate is diphenylmethylene diisocyanate or polymethylene polyphenyl isocyanate or a mixture thereof; The isocyanate index during foaming is 1.05 to 1.

2.

10. The preparation process of an aging-resistant and flame-retardant polyurethane foam material according to claim 8, characterized in that, The mass ratio of component A to component B is 1:1.3 to 1.55.

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