Polyurethane foaming material for new energy automobile battery and integrated foaming process thereof

Abstract

This invention belongs to the field of foaming material technology, specifically relating to a polyurethane foaming material for new energy vehicle batteries and its integrated foaming process. The polyurethane foaming material for new energy vehicle batteries includes component A and component B. Component A, by weight, comprises: 30-50 parts polyol, 2-8 parts flame retardant, 5-15 parts composite filler, 0.2-0.8 parts foaming agent, and 0.05-0.2 parts catalyst; component B is isocyanate. This invention overcomes the problem of existing polyurethane foaming materials failing to provide comprehensive and effective protection by employing a self-made flame retardant, composite filler, and integrated foaming process. The polyurethane foaming material for new energy vehicle batteries provided by this invention exhibits excellent flame retardancy, mechanical properties, coolant penetration resistance, and stone impact resistance.

Description

Technical Field

[0001] This invention belongs to the field of foaming material technology, specifically relating to a polyurethane foaming material for new energy vehicle batteries and its integrated foaming process. Background Technology

[0002] Polyurethane foam materials are lightweight, have good cushioning, heat insulation and sound absorption properties, and are widely used in automobile manufacturing. For example, the applicant's previous research results: Chinese patent with authorization publication number CN116574237B discloses a foam material for automobile interior and its production process, which has high resilience and antibacterial properties.

[0003] In recent years, energy conservation, emission reduction, and low-carbon development have become an inevitable trend, and the development of new energy electric vehicles has been rapid. As the power source of new energy vehicles, the performance and safety of the battery pack directly determine the safety of the entire vehicle. In new energy vehicles, the battery pack is generally located under the chassis and exposed in a relatively open space. It not only needs to have excellent resistance to stone impacts, but also excellent flame retardancy and resistance to coolant corrosion.

[0004] In existing technologies, polyurethane foam materials used for battery pack protection are typically bonded to the surface of the battery pack. For example, Chinese patent CN120137138B discloses a polyurethane foam material, its preparation method, and a battery pack. The battery pack includes a housing with an upper and lower shell, a battery module contained between the upper and lower shells, and polyurethane foam material disposed on the sides and / or bottom of the housing. The polyurethane foam material is the aforementioned polyurethane foam material; the first surface of the polyurethane foam material is the surface that adheres to the side and / or bottom of the housing, and the second surface of the polyurethane foam material is the surface of the battery pack exposed to the outside. However, the power battery packs of new energy vehicles are typically large, complex, and extremely fragile. This packaging method cannot provide comprehensive and effective protection and is inefficient. Furthermore, the above-mentioned technical solutions do not address resistance to coolant corrosion. Currently, there have been battery thermal runaway fires caused by coolant corrosion of the battery; therefore, addressing coolant corrosion resistance is of great significance. Summary of the Invention

[0005] The purpose of this invention is to provide a polyurethane foam material for new energy vehicle batteries and its integrated foaming process. By using self-made flame retardants, composite fillers and integrated foaming processes, the invention overcomes the problem that existing polyurethane foam materials cannot provide comprehensive and effective protection. The polyurethane foam material for new energy vehicle batteries provided by this invention has excellent flame retardancy, mechanical properties, coolant penetration resistance and stone impact resistance.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] The first aspect of the present invention provides a polyurethane foam material for new energy vehicle batteries, comprising component A and component B. Component A comprises, by weight: 30-50 parts of polyol, 2-8 parts of flame retardant, 5-15 parts of composite filler, 0.2-0.8 parts of foaming agent, and 0.05-0.2 parts of catalyst; and component B is isocyanate.

[0008] In component A, the polyol may be 30 parts by weight, 32 parts by weight, 33 parts by weight, 35 parts by weight, 36 parts by weight, 38 parts by weight, or 40 parts by weight, etc.

[0009] The flame retardant can be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, or 8 parts by weight, etc.

[0010] The composite filler can be 5 parts by weight, 7 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, or 15 parts by weight, etc.

[0011] The foaming agent can be 0.2 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, or 0.8 parts by weight, etc.

[0012] The catalyst can be 0.05 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.12 parts by weight, 0.15 parts by weight, 0.18 parts by weight, or 0.2 parts by weight, etc.

[0013] In some embodiments, the polyol is a mixture of polycarbonate diol and sorbitol polyether polyol in a mass ratio of 3-6:4-7.

[0014] In some embodiments, the hydroxyl value of the polycarbonate diol is 100-150 mgKOH / g, such as 105 mgKOH / g, 110 mgKOH / g, 120 mgKOH / g, 130 mgKOH / g, 140 mgKOH / g, or 150 mgKOH / g.

[0015] In some embodiments, the hydroxyl value of the sorbitol polyether polyol is 300-500 mgKOH / g, such as 300 mgKOH / g, 350 mgKOH / g, 400 mgKOH / g, 450 mgKOH / g, 460 mgKOH / g, or 500 mgKOH / g.

[0016] By adopting the above technical solution, polyurethane molecular chains with appropriate hard and soft segments are obtained, thereby endowing polyurethane foam materials with excellent mechanical properties, resistance to coolant penetration and stone impact resistance.

[0017] In some embodiments, the flame retardant is prepared by mixing tetramethyltetravinylcyclotetrasiloxane, DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and an initiator, and performing an addition reaction under nitrogen protection to obtain an intermediate product; adding 4-hydroxybutylvinyl polyoxyethylene ether and dimethyl sulfoxide to the intermediate product, and then adding chloroplatinic acid catalyst, and performing a hydrosilylation reaction under nitrogen protection to obtain the flame retardant.

[0018] Using the above technical solution, the vinyl group in tetramethyltetravinylcyclotetrasiloxane first undergoes an addition reaction with the PH bond in DOPO, and then undergoes a hydrosilylation reaction with the vinyl group in 4-hydroxybutylvinyl polyoxyethylene ether. This yields a flame retardant with cyclotetrasiloxane as the core, branched by hydroxyl-containing polyoxyethylene ether segments and a DOPO structure. This flame retardant not only fully exerts its flame retardant effect in the system, but also participates in the reaction, improving the crosslinking density and cell structure of the polyurethane foam material. This results in the polyurethane foam material exhibiting excellent flame retardancy, mechanical properties, coolant penetration resistance, and stone impact resistance.

[0019] In some embodiments, the molar ratio of tetramethyltetravinylcyclotetrasiloxane, DOPO and 4-hydroxybutylvinyl polyoxyethylene ether is 1:3.8-4.2:3.8-4.2.

[0020] In some embodiments, the initiator is selected from at least one of azobisisobutyronitrile, azobisisobutyronitrile, and azobisisovalerate.

[0021] In some embodiments, the amount of the initiator added is 1-3% of the total mass of tetramethyltetravinylcyclotetrasiloxane and DOPO, such as 1%, 2% or 3%.

[0022] In some embodiments, the temperature of the addition reaction is 80-85°C, such as 80°C, 81°C, 82°C, 83°C, 84°C, or 85°C, and the time is 8-12 hours, such as 8 hours, 9 hours, 10 hours, 11 hours, or 12 hours.

[0023] In some embodiments, the amount of dimethyl sulfoxide added is 2 to 4 times the mass of 4-hydroxybutylvinyl polyoxyethylene ether.

[0024] In some embodiments, the chloroplatinic acid catalyst is an isopropanol solution containing 2-2.5% chloroplatinic acid.

[0025] In some embodiments, the amount of chloroplatinic acid catalyst added is 0.1-0.3% of the total mass of tetramethyltetravinylcyclotetrasiloxane and 4-hydroxybutylvinyl polyoxyethylene ether.

[0026] In some embodiments, the temperature of the hydrosilylation reaction is 60-90°C, such as 60°C, 65°C, 70°C, 75°C, 80°C, or 90°C, and the time is 2-8 hours, such as 2 hours, 3 hours, 5 hours, 6 hours, or 8 hours.

[0027] In some embodiments, the composite filler is prepared by adding methyl hydrogen-containing MQ type silicone resin, 4-hydroxybutyl vinyl polyoxyethylene ether and allyl glycidyl ether to dimethyl sulfoxide, adding chloroplatinic acid catalyst, and performing hydrosilylation reaction under nitrogen protection to obtain a modifier; adding aluminum silicate fiber and nano-sized glass powder to the modifier, impregnating, and vacuum drying after impregnation to obtain the final product.

[0028] Using the above technical solution, the silane-hydrogen bonds of methyl hydrogen-containing MQ type silicone resin undergo a hydrosilylation reaction with the double bonds in 4-hydroxybutyl vinyl polyoxyethylene ether and allyl glycidyl ether to prepare a modifier with a Si-O bond as the backbone three-dimensional structure containing hydroxyl groups, polyoxyethylene ether segments and epoxy groups. Impregnating aluminum silicate fibers and nano-sized glass powder in this modifier can fully utilize the coolant permeability resistance of aluminum silicate fibers and nano-sized glass powder while also improving the toughness of polyurethane foam materials.

[0029] In some embodiments, the molar ratio of the methyl hydrogen MQ type silicone resin, 4-hydroxybutyl vinyl polyoxyethylene ether, and allyl glycidyl ether is 10:1-4:1-4.

[0030] In some embodiments, the hydrogen content of the methyl hydrogen-containing MQ type silicone resin is 0.25-0.75%.

[0031] In some embodiments, the amount of dimethyl sulfoxide added is 1-2 times the total mass of methyl hydrogen MQ type silicone resin, 4-hydroxybutyl vinyl polyoxyethylene ether and allyl glycidyl ether.

[0032] In some embodiments, the chloroplatinic acid catalyst is an isopropanol solution containing 2-2.5% chloroplatinic acid.

[0033] In some embodiments, the amount of chloroplatinic acid catalyst added is 0.1-0.3% of the total mass of methyl hydrogen MQ type silicone resin, 4-hydroxybutyl vinyl polyoxyethylene ether and allyl glycidyl ether.

[0034] In some embodiments, the mass ratio of the aluminosilicate fiber, nano-sized glass powder, and modifier is 2-4:6-8:20-40.

[0035] In some embodiments, the temperature of the hydrosilylation reaction is 60-90°C, such as 60°C, 65°C, 70°C, 75°C, 80°C, or 90°C, and the time is 2-8 hours, such as 2 hours, 3 hours, 5 hours, 6 hours, or 8 hours.

[0036] In some embodiments, the immersion temperature is 30-50°C, such as 30°C, 35°C, 40°C, 45°C or 40°C, and the time is 1-2 hours, such as 1 hour, 1.2 hours, 1.5 hours, 1.6 hours or 2 hours.

[0037] In some embodiments, the foaming agent is selected from one or more combinations of water, n-pentane, and cyclopentane.

[0038] In some embodiments, the catalyst is a mixture of an amine catalyst and an organometallic catalyst in a mass ratio of 1-2:1-2.

[0039] In some embodiments, the amine catalyst is selected from at least one of triethylamine, triethylenediamine, dimethylethanolamine, dimethylaminoethanol, N-methylmorpholine, N,N-dimethylcyclohexylamine, N,N',N'-trimethylaminoethylpiperazine, tetraethylammonium hydroxide, imidazole, and 2-ethyl-4-methylimidazole.

[0040] In some embodiments, the organometallic catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, and bismuth trioctanoate.

[0041] By adopting the above technical solution, the balance between gelation reaction and foaming reaction is controlled, avoiding foam collapse due to excessively rapid foaming or insufficient foam strength due to delayed gelation reaction.

[0042] In some embodiments, the isocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

[0043] In some embodiments, the mass ratio of component A to component B is 2-4:1.

[0044] The second aspect of the present invention provides an integrated foaming process for polyurethane foam material for new energy vehicle batteries, comprising the following steps: mixing polyol, flame retardant, composite filler, foaming agent and catalyst uniformly to obtain component A; first injecting component A into a packaging box containing a battery pack; then injecting component B; and foaming to obtain the final product.

[0045] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0046] 1. This invention utilizes a self-made flame retardant with cyclotetrasiloxane as the core, branched by hydroxyl-containing polyoxyethylene ether segments and DOPO structure, and a self-made modifier with Si-O bond as the skeleton three-dimensional structure and hydroxyl-containing polyoxyethylene ether segments and epoxy groups to treat the composite filler, thereby enabling the polyurethane foam material to have excellent flame retardancy, mechanical properties, coolant penetration resistance and stone impact resistance.

[0047] 2. This invention adopts an integrated foaming process, which involves injecting unfoamed liquid material into the packaging box containing the battery pack and foaming it in situ on the surface of the battery pack. This forms a tight coating layer, avoiding the difficult-to-eliminate bonding gaps between traditional polyurethane foam materials and irregularly shaped battery cells. This provides the battery pack with excellent flame retardancy, mechanical properties, resistance to coolant penetration, and stone impact resistance. Detailed Implementation

[0048] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0049] Example 1

[0050] A polyurethane foam material for new energy vehicle batteries includes component A and component B. Component A comprises, by weight, 30 parts of polyol, 2 parts of flame retardant, 5 parts of composite filler, 0.4 parts of foaming agent, and 0.1 parts of catalyst. Component B is hexamethylene diisocyanate.

[0051] The mass ratio of component A to component B is 2.94:1.

[0052] The polyol is a mixture of polycarbonate diol and sorbitol polyether polyol in a mass ratio of 4:6.

[0053] The polycarbonate diol has a hydroxyl value of 102-118 mgKOH / g, manufactured by Shanghai Shuyu Chemical Co., Ltd., model number: SYHP1000.

[0054] The hydroxyl value of the sorbitol polyether polyol is 355-395 mgKOH / g, Shandong Yiborun New Material Technology Co., Ltd., polyether 6207.

[0055] The flame retardant is prepared by mixing tetramethyltetravinylcyclotetrasiloxane, DOPO and an initiator, and reacting them under nitrogen protection at 82°C for 10 hours to obtain an intermediate product; adding 4-hydroxybutylvinyl polyoxyethylene ether and dimethyl sulfoxide to the intermediate product, and then adding chloroplatinic acid catalyst, and reacting them under nitrogen protection at 80°C for 4 hours to obtain the flame retardant.

[0056] The molar ratio of tetramethyltetravinylcyclotetrasiloxane, DOPO and 4-hydroxybutylvinyl polyoxyethylene ether is 1:4:4.

[0057] The 4-hydroxybutylvinyl polyoxyethylene ether has a hydroxyl value of 20.0-23.0 mgKOH / g and an unsaturation degree of 0.27 mmol / g. (Wuhan Shanjiang Chemical Technology Co., Ltd.)

[0058] The initiator is azobisisobutyronitrile.

[0059] The amount of the initiator added is 1.5% of the total mass of tetramethyltetravinylcyclotetrasiloxane and DOPO.

[0060] The amount of dimethyl sulfoxide added is three times the mass of 4-hydroxybutylvinyl polyoxyethylene ether.

[0061] The chloroplatinic acid catalyst is an isopropanol solution containing 2% chloroplatinic acid.

[0062] The amount of chloroplatinic acid catalyst added is 0.2% of the total mass of tetramethyltetravinylcyclotetrasiloxane and 4-hydroxybutylvinyl polyoxyethylene ether.

[0063] The composite filler is prepared as follows: methyl hydrogen-containing MQ type silicone resin, 4-hydroxybutyl vinyl polyoxyethylene ether and allyl glycidyl ether are added to dimethyl sulfoxide, chloroplatinic acid catalyst is added, and under nitrogen protection, a hydrosilylation reaction is carried out at 80°C for 4 hours to obtain a modifier; aluminum silicate fiber and nano-sized glass powder are added to the modifier, impregnated at 40°C for 2 hours, and vacuum dried after impregnation to obtain the final product.

[0064] The molar ratio of the methyl hydrogen-containing MQ type silicone resin, 4-hydroxybutyl vinyl polyoxyethylene ether, and allyl glycidyl ether is 10:2:2.

[0065] The hydrogen content of the methyl hydrogen-containing MQ type silicone resin is 0.4±0.05%, Shandong Dayi Chemical Co., Ltd., HMQ103-0.4%.

[0066] The amount of dimethyl sulfoxide added is 1.5 times the total mass of methyl hydrogen MQ type silicone resin, 4-hydroxybutyl vinyl polyoxyethylene ether and allyl glycidyl ether.

[0067] The chloroplatinic acid catalyst is an isopropanol solution containing 2% chloroplatinic acid.

[0068] The amount of chloroplatinic acid catalyst added is 0.2% of the total mass of methyl hydrogen MQ type silicone resin, 4-hydroxybutyl vinyl polyoxyethylene ether and allyl glycidyl ether.

[0069] The mass ratio of the aluminum silicate fiber, nano-sized glass powder, and modifier is 3:7:30.

[0070] The aluminum silicate fiber has a mesh size of 4000.

[0071] The foaming agent is water and n-pentane in a mass ratio of 2:1.

[0072] The catalyst is a mixture of triethylamine and dibutyltin dilaurate in a mass ratio of 1:1.

[0073] The integrated foaming process for the polyurethane foam material used in new energy vehicle batteries includes the following steps: mixing polyol, flame retardant, composite filler, foaming agent and catalyst evenly to obtain component A; first injecting component A into a packaging box containing the battery pack; then injecting component B; and foaming to obtain the final product.

[0074] Example 2

[0075] The difference between this embodiment and Embodiment 1 is that: component A by weight includes 40 parts of polyol, 6 parts of flame retardant, 10 parts of composite filler, 0.6 parts of foaming agent, and 0.15 parts of catalyst; the mass ratio of component A to component B is 3.34:1; all other aspects are the same.

[0076] Example 3

[0077] The difference between this embodiment and Embodiment 1 is that: component A by weight includes 50 parts of polyol, 8 parts of flame retardant, 15 parts of composite filler, 0.8 parts of foaming agent, and 0.2 parts of catalyst; the mass ratio of component A to component B is 3.49:1; all other components are the same.

[0078] Comparative Example 1

[0079] The difference between this comparative example and Example 1 is that the flame retardant used is magnesium hydroxide; all other aspects are the same.

[0080] Comparative Example 2

[0081] The difference between this comparative example and Example 1 is that the flame retardant is tris(2-chloropropyl) phosphate; all other aspects are the same.

[0082] Comparative Example 3

[0083] The difference between this comparative example and Example 1 is that the flame retardant is prepared by mixing tetramethyltetravinylcyclotetrasiloxane, DOPO and an initiator, and then reacting them at 82°C for 10 hours under nitrogen protection to obtain the flame retardant.

[0084] The molar ratio of tetramethyltetravinylcyclotetrasiloxane to DOPO is 1:4.

[0085] The initiator is azobisisobutyronitrile.

[0086] The amount of the initiator added is 1.5% of the total mass of tetramethyltetravinylcyclotetrasiloxane and DOPO; all other aspects are the same.

[0087] Comparative Example 4

[0088] The difference between this comparative example and Example 1 is as follows: The flame retardant is prepared by mixing tetramethyltetravinylcyclotetrasiloxane, DOPO and an initiator, and reacting them under nitrogen protection at 82°C for 10 hours to obtain an intermediate product; vinyl-terminated polydimethylsiloxane (vinyl content of 0.8-1%, viscosity of 1000 mPa.s, Zhejiang Hengyecheng Organosilicon Co., Ltd.) and dimethyl sulfoxide are added to the intermediate product, and then chloroplatinic acid catalyst is added. Under nitrogen protection, the product is subjected to hydrosilylation reaction at 80°C for 4 hours to obtain the flame retardant.

[0089] The molar ratio of tetramethyltetravinylcyclotetrasiloxane, DOPO, and vinyl-terminated polydimethylsiloxane is 1:4:2.

[0090] The initiator is azobisisobutyronitrile.

[0091] The amount of the initiator added is 1.5% of the total mass of tetramethyltetravinylcyclotetrasiloxane and DOPO.

[0092] The amount of dimethyl sulfoxide added is three times the mass of 4-hydroxybutylvinyl polyoxyethylene ether.

[0093] The chloroplatinic acid catalyst is an isopropanol solution containing 2% chloroplatinic acid.

[0094] The amount of chloroplatinic acid catalyst added is 0.2% of the total mass of tetramethyltetravinylcyclotetrasiloxane and vinyl-terminated polydimethylsiloxane.

[0095] Comparative Example 5

[0096] The difference between this comparative example and Example 1 is that the composite filler is replaced with nano-silica with a particle size of 100nm; all other aspects are the same.

[0097] Comparative Example 6

[0098] The difference between this comparative example and Example 1 is as follows: The composite filler is prepared by adding tetramethylcyclotetrasiloxane, 4-hydroxybutylvinyl polyoxyethylene ether and allyl glycidyl ether to dimethyl sulfoxide, adding chloroplatinic acid catalyst, and performing a hydrosilylation reaction at 80°C for 4 hours under nitrogen protection to obtain a modifier; adding aluminum silicate fiber and nano-sized glass powder to the modifier, impregnating at 40°C for 2 hours, and vacuum drying after impregnation to obtain the final product.

[0099] The molar ratio of tetramethylcyclotetrasiloxane, 4-hydroxybutylvinyl polyoxyethylene ether, and allyl glycidyl ether is 1:2:2.

[0100] The amount of dimethyl sulfoxide added is 1.5 times the total mass of tetramethylcyclotetrasiloxane, 4-hydroxybutylvinyl polyoxyethylene ether, and allyl glycidyl ether.

[0101] The chloroplatinic acid catalyst is an isopropanol solution containing 2% chloroplatinic acid.

[0102] The amount of chloroplatinic acid catalyst added is 0.2% of the total mass of tetramethylcyclotetrasiloxane, 4-hydroxybutylvinyl polyoxyethylene ether, and allyl glycidyl ether; all other amounts are the same.

[0103] Comparative Example 7

[0104] The difference between this comparative example and Example 1 is as follows: The preparation method of the composite filler is as follows: methyl hydrogen-containing MQ type silicone resin, vinyl-terminated polydimethylsiloxane (vinyl content of 0.8-1%, viscosity of 1000 mPa.s, Zhejiang Hengyecheng Organosilicon Co., Ltd.), and allyl glycidyl ether are added to dimethyl sulfoxide, chloroplatinic acid catalyst is added, and under nitrogen protection, a hydrosilylation reaction is carried out at 80°C for 4 hours to obtain the modifier; aluminum silicate fiber and nano-sized glass powder are added to the modifier, impregnated at 40°C for 2 hours, and vacuum dried after impregnation to obtain the final product.

[0105] The molar ratio of the methyl hydrogen-containing MQ type silicone resin, the vinyl-terminated polydimethylsiloxane, and the allyl glycidyl ether is 10:1:2.

[0106] The hydrogen content of the methyl hydrogen-containing MQ type silicone resin is 0.4±0.05%, Shandong Dayi Chemical Co., Ltd., HMQ103-0.4%.

[0107] The amount of dimethyl sulfoxide added is 1.5 times the total mass of methyl hydrogen MQ type silicone resin, vinyl-terminated polydimethylsiloxane and allyl glycidyl ether.

[0108] The chloroplatinic acid catalyst is an isopropanol solution containing 2% chloroplatinic acid.

[0109] The amount of chloroplatinic acid catalyst added is 0.2% of the total mass of methyl hydrogen MQ type silicone resin, vinyl-terminated polydimethylsiloxane and allyl glycidyl ether; all other aspects are the same.

[0110] Comparative Example 8

[0111] The difference between this comparative example and Example 1 is as follows: the preparation method of the composite filler is as follows: methyl hydrogen-containing MQ type silicone resin and 4-hydroxybutyl vinyl polyoxyethylene ether are added to dimethyl sulfoxide, chloroplatinic acid catalyst is added, and under nitrogen protection, a hydrosilylation reaction is carried out at 80°C for 4 hours to obtain a modifier; aluminum silicate fiber and nano-sized glass powder are added to the modifier, impregnated at 40°C for 2 hours, and vacuum dried after impregnation to obtain the final product.

[0112] The molar ratio of the methyl hydrogen-containing MQ type silicone resin and 4-hydroxybutyl vinyl polyoxyethylene ether is 10:4.

[0113] The hydrogen content of the methyl hydrogen-containing MQ type silicone resin is 0.4±0.05%, Shandong Dayi Chemical Co., Ltd., HMQ103-0.4%.

[0114] The amount of dimethyl sulfoxide added is 1.5 times the total mass of methyl hydrogen MQ type silicone resin and 4-hydroxybutyl vinyl polyoxyethylene ether.

[0115] The chloroplatinic acid catalyst is an isopropanol solution containing 2% chloroplatinic acid.

[0116] The amount of chloroplatinic acid catalyst added is 0.2% of the total mass of methyl hydrogen MQ type silicone resin and 4-hydroxybutyl vinyl polyoxyethylene ether; all other amounts are the same.

[0117] Performance testing

[0118] 1. Tensile strength and elongation at break: Test standard: ASTM D 3574-08;

[0119] 2. Resistance to coolant penetration: Immerse in 50% ethylene glycol aqueous solution at 60℃ for 30 days and calculate the rate of weight change;

[0120] 3. Flame retardancy: Test standard: UL94, 2.5mm;

[0121] 4. Stone impact resistance: Test standard: ISO 20567-1-2017.

[0122] Test Results

[0123] Table 1

[0124]

[0125] As can be seen from Table 1, the polyurethane foam material provided by the present invention has high tensile strength and elongation at break, as well as excellent flame retardancy, coolant penetration resistance and stone impact resistance, thus effectively providing comprehensive and effective protection for new energy vehicle batteries.

[0126] Comparative Examples 1 and 2 used conventional flame retardants in the art, which not only led to a decrease in the flame retardancy of the obtained polyurethane foam materials, but also a decrease in mechanical properties, resistance to coolant penetration and resistance to stone impact.

[0127] The flame retardant prepared in Comparative Example 3 did not contain polyoxyethylene ether segments. The flame retardant prepared in Comparative Example 4 used siloxane segments to replace the hydroxyl-containing polyoxyethylene ether segments. The resulting polyurethane foam material showed a significant decrease in coolant permeability resistance and stone impact resistance. This indicates that the presence of hydroxyl-containing polyoxyethylene ether segments can improve the cell structure of polyurethane foam material, thereby improving its coolant permeability resistance and toughness.

[0128] Comparative Example 5 uses conventional fillers in the field, and the resulting polyurethane foam material not only has poor resistance to coolant penetration and stone impact, but also has reduced mechanical properties and flame retardancy.

[0129] In Comparative Example 6, the modifier for the composite filler was tetramethylcyclotetrasiloxane, which replaced the methyl hydrogen-containing MQ type silicone resin. In Comparative Example 7, the modifier for the composite filler was vinyl-terminated polydimethylsiloxane, which replaced 4-hydroxybutyl vinyl polyoxyethylene ether. Therefore, the resulting modifier did not contain hydroxyl groups or polyoxyethylene ether segments. In Comparative Example 8, the modifier for the composite filler did not contain allyl glycidyl ether, meaning it did not contain epoxy groups. The resulting polyurethane foam exhibited poor resistance to coolant permeability and stone impact. This indicates that only modifiers prepared using specific methyl hydrogen-containing MQ type silicone resin, 4-hydroxybutyl vinyl polyoxyethylene ether, and allyl glycidyl ether can effectively modify aluminosilicate fibers and nano-sized glass powder while simultaneously improving the toughness of the polyurethane foam.

[0130] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A polyurethane foaming material for new energy automobile batteries, comprising a component A and a component B, characterized in that, Component A comprises, by weight: 30-50 parts polyol, 2-8 parts flame retardant, 5-15 parts composite filler, 0.2-0.8 parts foaming agent, and 0.05-0.2 parts catalyst; Component B is isocyanate. The flame retardant is prepared by mixing tetramethyltetravinylcyclotetrasiloxane, DOPO and an initiator, and performing an addition reaction under nitrogen protection to obtain an intermediate product; adding 4-hydroxybutylvinyl polyoxyethylene ether and dimethyl sulfoxide to the intermediate product, and then adding chloroplatinic acid catalyst, and performing a hydrosilylation reaction under nitrogen protection to obtain the flame retardant. 2.The polyurethane foaming material for new energy automobile battery according to claim 1, characterized in that, The polyol is a mixture of polycarbonate diol and sorbitol polyether polyol in a mass ratio of 3-6:4-7.

3. The polyurethane foam material for new energy vehicle batteries according to claim 2, characterized in that, The hydroxyl value of the polycarbonate diol is 100-150 mg KOH / g; the hydroxyl value of the sorbitol polyether polyol is 300-500 mg KOH / g.

4. The polyurethane foam material for new energy vehicle batteries according to any one of claims 1-3, characterized in that, The composite filler is prepared by adding methyl hydrogen-containing MQ type silicone resin, 4-hydroxybutyl vinyl polyoxyethylene ether and allyl glycidyl ether to dimethyl sulfoxide, adding chloroplatinic acid catalyst, and performing hydrosilylation reaction under nitrogen protection to obtain a modifier; adding aluminum silicate fiber and nano-sized glass powder to the modifier, impregnating, and vacuum drying after impregnation to obtain the final product. 5.The polyurethane foaming material for new energy automobile battery according to claim 4, characterized in that, The hydrogen content of the methyl hydrogen-containing MQ type silicone resin is 0.25-0.75%. 6.The polyurethane foaming material for new energy automobile battery according to claim 5, characterized in that, The mass ratio of the aluminum silicate fiber, nano-sized glass powder, and modifier is 2-4:6-8:20-40.

7. The polyurethane foam material for new energy automobile battery according to any one of claims 1-3, characterized in that, The catalyst is a mixture of amine catalyst and organometallic catalyst in a mass ratio of 1-2:1-2. 8.The polyurethane foaming material for new energy automobile battery according to claim 7, characterized in that, The amine catalyst is selected from at least one of triethylamine, triethylenediamine, dimethylethanolamine, dimethylaminoethanol, N-methylmorpholine, N,N-dimethylcyclohexylamine, N,N',N'-trimethylaminoethylpiperazine, tetraethylammonium hydroxide, imidazole, and 2-ethyl-4-methylimidazolium; the organometallic catalyst is selected from at least one of dibutyltin dilaurate, stannous octoate, and bismuth trioctanoate. 9.The polyurethane foaming material for new energy automobile battery according to any one of claims 1-3, characterized in that, The isocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

10. The integrated foaming process for polyurethane foam material for new energy vehicle batteries according to any one of claims 1-9, characterized in that, The process includes the following steps: mixing polyol, flame retardant, composite filler, foaming agent and catalyst evenly to obtain component A; first injecting component A into a packaging box containing the battery pack, then injecting component B, and foaming to obtain the final product.

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