Noise-reduction and vibration-proof polyurethane foam for new energy automobile battery and preparation method of noise-reduction and vibration-proof polyurethane foam

Abstract

The invention discloses noise-reducing and vibration-proof polyurethane foam for a new energy automobile battery and a preparation method of the noise-reducing and vibration-proof polyurethane foam, and relates to the technical field of polyurethane. The preparation method specifically comprises the following steps: S1, uniformly mixing polyester polyol, a modifier, 1, 4-butanediol, deionized water, a mildew preventive, dibutyltin dilaurate and bis (2-dimethylaminoethyl) ether to obtain a component A; s2, dewatering polyester polyol, adding diisocyanate, heating, stirring and reacting to obtain a component B; s3, mixing the component A and the component B, stirring at a high speed, pouring into a mold, quickly closing the mold, curing, taking out, and curing to obtain the noise-reducing and vibration-proof polyurethane foam for the new energy automobile battery. According to the polyurethane foam prepared by the invention, the noise reduction, vibration prevention and flame retardant properties of the polyurethane foam are remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of polyurethane technology, specifically to a noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries and its preparation method. Background Technology

[0002] With the rapid development of the new energy vehicle industry, the performance and safety of the power battery, as the core energy component of the vehicle, directly determine the overall quality of the vehicle. In actual use, the battery pack faces two key challenges: First, during vehicle operation, road bumps, motor operation, and the charging and discharging process itself will generate continuous vibration and noise, affecting driving comfort. Long-term vibration may also lead to loosening of internal battery connections, structural fatigue, and shorten battery life. Second, lithium batteries have a risk of combustion in the state of thermal runaway, posing a safety hazard to drivers and passengers.

[0003] Polyurethane foam, as a porous material, has the characteristics of low density and low cost, and has certain buffering and noise reduction properties, but its flame retardancy is often insufficient. Although flame retardant can be added to improve flame retardancy, a large amount of addition will sacrifice the flexibility and vibration reduction effect of polyurethane foam, resulting in a reduction in noise reduction function. In addition, the ordinary physical blending of flame retardants has problems such as poor dispersion uniformity and easy migration leading to failure.

[0004] In summary, solving the above problems and preparing a noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries is of great significance. Summary of the Invention

[0005] The purpose of this invention is to provide a noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries and its preparation method, so as to solve the problems mentioned in the background art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries includes the following steps: S1: Polyester polyol, modifier, 1,4-butanediol, deionized water, mildew inhibitor, dibutyltin dilaurate, and bis(2-dimethylaminoethyl) ether are mixed evenly to obtain component A; S2: After dehydrating the polyester polyol, diisocyanate is added, and the mixture is heated and stirred to react, yielding component B; S3: Mix components A and B, stir at high speed, pour into a mold, close the mold quickly, remove after curing, and perform a curing treatment to obtain noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries.

[0007] Preferably, component A comprises the following raw materials, by mass parts: 35-45 parts polyester polyol, 15-20 parts modifier, 3-5 parts 1,4-butanediol, 0.3-0.5 parts deionized water, 0.5-0.8 parts mildew inhibitor, 0.02-0.04 parts dibutyltin dilaurate, and 0.2-0.25 parts bis(2-dimethylaminoethyl) ether; Component B comprises the following raw materials, by mass: 40-45 parts polyester polyol and 55-60 parts diisocyanate.

[0008] Preferably, the mass ratio of component A to component B is 100:85~95.

[0009] Preferably, during the preparation of component B, the temperature is 100~120℃ and the time is 2~4h; during the aging process, the temperature is 100~110℃ and the time is 18~24h.

[0010] Preferredly, the preparation method of the modifier includes the following steps: mixing unsaturated monomer and cassette catalyst evenly, heating to 80~85℃, adding methyl hydrogen silicone oil dropwise, stirring and reacting for 12~18h, washing with anhydrous ethanol, drying, and obtaining the modifier.

[0011] More preferably, the raw materials of the modifier include unsaturated monomers, cassiterite catalysts, and methyl hydrogen silicone oil in a mass ratio of 10:0.05~0.1:13~16.

[0012] More preferably, the unsaturated monomers include unsaturated monomer A and unsaturated monomer B in a mass ratio of 1.5 to 3:1; The preparation method of the unsaturated monomer A includes the following steps: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine are mixed evenly, stirred and reacted at 130~135℃ for 10h, and purified to obtain unsaturated monomer A. The preparation method of the unsaturated monomer B includes the following steps: cashew phenol glycidyl ether, triphenylphosphine, and hydroquinone are mixed evenly, heated to 90~100℃, acrylic acid is added dropwise, the adding time is controlled to be 1~1.5h, after the addition is completed, the reaction is stirred for 3~4h, purified, and unsaturated monomer B is obtained.

[0013] More preferably, the raw materials for the unsaturated monomer A include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine in a mass ratio of 9~9.5:5:0.2~0.3. The raw materials for the unsaturated monomer B include cashew phenol glycidyl ether, triphenylphosphine, hydroquinone, and acrylic acid in a mass ratio of 10:0.1~0.2:0.001~0.002:3.5~3.7.

[0014] Preferredly, the preparation process of the modifier involves the following steps: mixing unsaturated monomer A and cassette catalyst evenly, heating to 80-85°C, adding methyl hydrogen silicone oil dropwise over 1-2 hours, stirring for 4-6 hours, adding unsaturated monomer B, continuing stirring for 8-12 hours, washing with anhydrous ethanol, and drying to obtain the modifier.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: The present invention prepares unsaturated monomer A containing DOPO structure and unsaturated monomer B containing cashew phenol structure, and obtains modifiers by grafting them onto the methyl hydrogen silicone oil skeleton through hydrosilylation reaction. The modifiers are then introduced into the polyurethane foam system, which significantly improves the noise reduction, vibration damping and flame retardant properties of polyurethane foam.

[0016] The preparation method of unsaturated monomer A is as follows: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and allyl glycidyl ether undergo a ring-opening reaction of PH bond to epoxy group under triphenylphosphine catalysis to obtain unsaturated monomer A containing DOPO structure; the preparation method of unsaturated monomer B is as follows: cashew phenol glycidyl ether and acrylic acid undergo a ring-opening reaction of epoxy group and carboxyl group under triphenylphosphine catalysis and hydroquinone inhibition to obtain unsaturated monomer B containing cashew phenol structure; the preparation method of modifier is as follows: the carbon-carbon double bond of unsaturated monomer A and unsaturated monomer B undergoes a hydrosilylation reaction with active H in methyl hydrogen silicone oil under the condition of caster catalyst to obtain modifier.

[0017] Among them, unsaturated monomer A containing the DOPO structure has excellent flame retardant properties, but the phosphenanthrene ring is rigid and highly polar. Single grafting onto the polysiloxane chain segment results in a high grafting density, making the modifier hard and brittle. Adding it to the polyurethane system restricts the movement of the polysiloxane, leading to damping failure and decreased vibration damping performance. Furthermore, during foaming, the modifier has difficulty migrating to the cell walls, losing its ability to even out foam formation, resulting in uneven cell structure, easy breakage, and reduced noise reduction. Therefore, this invention further introduces unsaturated monomer B containing the cashew phenol structure. Its long-chain alkane has a certain plasticizing effect, which can optimize the movement of the chain segments and improve damping performance, thereby enhancing the noise reduction and vibration damping performance of the polyurethane foam. Meanwhile, in the early stages of combustion, the moderate decomposition of long-chain alkyl groups in the cashew phenol structure improves the toughness of the char layer and prevents it from cracking. Its aromatic structure helps to increase the residual carbon content and graphitization degree of the char layer, forming a denser heat and oxygen barrier together with DOPO and polysiloxane, greatly improving the flame retardant performance of polyurethane foam and increasing safety. At the same time, both unsaturated monomer A and unsaturated monomer B contain hydroxyl structures, so they can participate in the curing of polyurethane and prevent the flame retardant components from migrating and failing.

[0018] However, in the process of preparing modifiers from unsaturated monomers A and B via hydrosilylation, monomer A needs to be added first for grafting. This is because the flame-retardant group is relatively large, and grafting first allows it to preferentially occupy positions with less steric hindrance in the chain segment, initially forming a rigid skeleton. Then, when monomer B is introduced, the more flexible monomer B can be inserted between the rigid skeleton and the remaining Si-H grafts, forming a gradient structure that combines rigidity and flexibility, achieving efficient and uniform grafting, and significantly improving the noise reduction, vibration damping, and flame-retardant properties of polyurethane foam. However, when adding B first and then A, the long-chain structure of unsaturated monomer B will cause the siloxane backbone to be coated, hindering the approach of unsaturated monomer A and Si-H sites, thus reducing flame retardancy. Furthermore, the reactivity of acrylate double bonds is higher than that of allyl double bonds, and the simultaneous addition of unsaturated monomers A and B will also lead to a decrease in the grafting rate of unsaturated monomer A, thus reducing flame retardant properties. Detailed Implementation

[0019] 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.

[0020] It should be noted that the following quantities are by weight, and there are no special restrictions on the manufacturers of the raw materials involved in this invention. Exemplary examples include: polyester diol: polyethylene adipate, hydroxyl value 56 mg KOH / g; diisocyanate: diphenylmethane diisocyanate, purity ≥99%; antifungal agent, model NSO-80; cashew phenol glycidyl ether, brand WSCM-5110, epoxy value 0.2~0.28; methyl hydrogen silicone oil, model DY-H202, hydrogen content 1.5~1.6%; CAS number of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide: 35948-25-5; CAS number of allyl glycidyl ether: 106-92-3.

[0021] In the following examples, parts refer to parts by weight, and all raw materials mentioned above and others not mentioned are commercially available.

[0022] Example 1: A method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries includes the following steps: Step 1: Preparation of unsaturated monomer A: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine were mixed evenly and reacted at 130℃ for 10 h. After purification, unsaturated monomer A was obtained. The raw materials for unsaturated monomer A included 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine in a mass ratio of 9.2:5:0.2. Step 2: Preparation of unsaturated monomer B: Cashew phenol glycidyl ether, triphenylphosphine, and hydroquinone were mixed evenly and heated to 95°C. Acrylic acid was added dropwise, with the addition time controlled at 1 hour. After the addition was completed, the reaction was stirred for another 3 hours. The mixture was then purified to obtain unsaturated monomer B. The raw materials for unsaturated monomer B included cashew phenol glycidyl ether, triphenylphosphine, hydroquinone, and acrylic acid in a mass ratio of 10:0.1:0.001:3.6. Step 3: Preparation of the modifier: Unsaturated monomer A and caster catalyst are mixed evenly and heated to 80°C. Methyl hydrogen-containing silicone oil is added dropwise over 1 hour, and the mixture is stirred for 5 hours. Unsaturated monomer B is then added, and the mixture is stirred for another 10 hours. The mixture is washed with anhydrous ethanol and dried to obtain the modifier. The raw materials for the modifier include unsaturated monomers, caster catalyst, and methyl hydrogen-containing silicone oil in a mass ratio of 10:0.05:14. The unsaturated monomers include unsaturated monomer A and unsaturated monomer B in a mass ratio of 2:1. Step 4: Preparation of noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries: S1: Mix 40 parts of polyester polyol, 17 parts of modifier, 4 parts of 1,4-butanediol, 0.4 parts of deionized water, 0.6 parts of antifungal agent, 0.03 parts of dibutyltin dilaurate, and 0.2 parts of bis(2-dimethylaminoethyl) ether evenly to obtain component A; S2: After dehydrating 42 parts of polyester polyol, heat it to 100℃, add 58 parts of diisocyanate, stir and react for 3 hours to obtain component B; S3: Components A and B are mixed at a mass ratio of 100:90, stirred at high speed, poured into a mold, quickly closed, cured, and then removed and cured at 110℃ for 18 hours to obtain noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries.

[0023] Example 2: A method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries includes the following steps: Step 1: Preparation of unsaturated monomer A: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine were mixed evenly and reacted at 130℃ for 10 h. After purification, unsaturated monomer A was obtained. The raw materials for unsaturated monomer A included 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine in a mass ratio of 9.2:5:0.2. Step 2: Preparation of unsaturated monomer B: Cashew phenol glycidyl ether, triphenylphosphine, and hydroquinone were mixed evenly and heated to 95°C. Acrylic acid was added dropwise, with the addition time controlled at 1 hour. After the addition was completed, the reaction was stirred for another 3 hours. The mixture was then purified to obtain unsaturated monomer B. The raw materials for unsaturated monomer B included cashew phenol glycidyl ether, triphenylphosphine, hydroquinone, and acrylic acid in a mass ratio of 10:0.1:0.001:3.6. Step 3: Preparation of the modifier: Unsaturated monomer A and caster catalyst are mixed evenly and heated to 80°C. Methyl hydrogen-containing silicone oil is added dropwise over 1 hour, and the mixture is stirred for 5 hours. Unsaturated monomer B is then added, and the mixture is stirred for another 10 hours. The mixture is washed with anhydrous ethanol and dried to obtain the modifier. The raw materials for the modifier include unsaturated monomers, caster catalyst, and methyl hydrogen-containing silicone oil in a mass ratio of 10:0.05:14. The unsaturated monomers include unsaturated monomer A and unsaturated monomer B in a mass ratio of 2:1. Step 4: Preparation of noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries: S1: Mix 35 parts polyester polyol, 15 parts modifier, 3 parts 1,4-butanediol, 0.3 parts deionized water, 0.6 parts mildew inhibitor, 0.03 parts dibutyltin dilaurate, and 0.2 parts bis(2-dimethylaminoethyl) ether evenly to obtain component A; S2: After dehydrating 40 parts of polyester polyol, heat it to 100℃, add 55 parts of diisocyanate, stir and react for 3 hours to obtain component B; S3: Components A and B are mixed at a mass ratio of 100:85, stirred at high speed, poured into a mold, quickly closed, cured, and then removed and cured at 110℃ for 18 hours to obtain noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries.

[0024] Example 3: A method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries includes the following steps: Step 1: Preparation of unsaturated monomer A: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine were mixed evenly and reacted at 130℃ for 10 h. After purification, unsaturated monomer A was obtained. The raw materials for unsaturated monomer A included 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine in a mass ratio of 9.2:5:0.2. Step 2: Preparation of unsaturated monomer B: Cashew phenol glycidyl ether, triphenylphosphine, and hydroquinone were mixed evenly and heated to 95°C. Acrylic acid was added dropwise, with the addition time controlled at 1 hour. After the addition was completed, the reaction was stirred for another 3 hours. The mixture was then purified to obtain unsaturated monomer B. The raw materials for unsaturated monomer B included cashew phenol glycidyl ether, triphenylphosphine, hydroquinone, and acrylic acid in a mass ratio of 10:0.1:0.001:3.6. Step 3: Preparation of the modifier: Unsaturated monomer A and caster catalyst are mixed evenly and heated to 80°C. Methyl hydrogen-containing silicone oil is added dropwise over 1 hour, and the mixture is stirred for 5 hours. Unsaturated monomer B is then added, and the mixture is stirred for another 10 hours. The mixture is washed with anhydrous ethanol and dried to obtain the modifier. The raw materials for the modifier include unsaturated monomers, caster catalyst, and methyl hydrogen-containing silicone oil in a mass ratio of 10:0.05:14. The unsaturated monomers include unsaturated monomer A and unsaturated monomer B in a mass ratio of 2:1. Step 4: Preparation of noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries: S1: Mix 45 parts of polyester polyol, 20 parts of modifier, 5 parts of 1,4-butanediol, 0.5 parts of deionized water, 0.6 parts of mildew inhibitor, 0.03 parts of dibutyltin dilaurate, and 0.2 parts of bis(2-dimethylaminoethyl) ether evenly to obtain component A; S2: After dehydrating 45 parts of polyester polyol, heat it to 100℃, add 60 parts of diisocyanate, stir and react for 3 hours to obtain component B; S3: Components A and B are mixed at a mass ratio of 100:95, stirred at high speed, poured into a mold, quickly closed, cured, and then removed and cured at 110℃ for 18 hours to obtain noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries.

[0025] Comparative Example 1: Based on Example 1, unsaturated monomer A was introduced separately, and the rest of the process was the same as in Example 1, as follows: Step 1: Preparation of unsaturated monomer A: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine were mixed evenly and reacted at 130℃ for 10 h. After purification, unsaturated monomer A was obtained. The raw materials for unsaturated monomer A included 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine in a mass ratio of 9.2:5:0.2. Step 2: Preparation of the modifier: Unsaturated monomer A and caster catalyst are mixed evenly, heated to 80°C, and methyl hydrogen silicone oil is added dropwise over 1 hour. The mixture is stirred and reacted for 15 hours. The mixture is then washed with anhydrous ethanol and dried to obtain the modifier. The raw materials for the modifier include unsaturated monomer A, caster catalyst, and methyl hydrogen silicone oil in a mass ratio of 10:0.05:14. Step 3: Preparation of noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries: S1: Mix 40 parts of polyester polyol, 17 parts of modifier, 4 parts of 1,4-butanediol, 0.4 parts of deionized water, 0.6 parts of antifungal agent, 0.03 parts of dibutyltin dilaurate, and 0.2 parts of bis(2-dimethylaminoethyl) ether evenly to obtain component A; S2: After dehydrating 42 parts of polyester polyol, heat it to 100℃, add 58 parts of diisocyanate, stir and react for 3 hours to obtain component B; S3: Components A and B are mixed at a mass ratio of 100:90, stirred at high speed, poured into a mold, quickly closed, cured, and then removed and cured at 110℃ for 18 hours to obtain noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries.

[0026] Comparative Example 2: Based on Example 1, unsaturated monomer B was introduced first, followed by unsaturated monomer A. The remaining processes were the same as in Example 1, as detailed below: Step 1: Preparation of unsaturated monomer A: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine were mixed evenly and reacted at 130℃ for 10 h. After purification, unsaturated monomer A was obtained. The raw materials for unsaturated monomer A included 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine in a mass ratio of 9.2:5:0.2. Step 2: Preparation of unsaturated monomer B: Cashew phenol glycidyl ether, triphenylphosphine, and hydroquinone were mixed evenly and heated to 95°C. Acrylic acid was added dropwise, with the addition time controlled at 1 hour. After the addition was completed, the reaction was stirred for another 3 hours. The mixture was then purified to obtain unsaturated monomer B. The raw materials for unsaturated monomer B included cashew phenol glycidyl ether, triphenylphosphine, hydroquinone, and acrylic acid in a mass ratio of 10:0.1:0.001:3.6. Step 3: Preparation of the modifier: Unsaturated monomer B and castor catalyst are mixed evenly and heated to 80°C. Methyl hydrogen-containing silicone oil is added dropwise over 1 hour, and the mixture is stirred for 5 hours. Unsaturated monomer A is then added, and the mixture is stirred for another 10 hours. The mixture is washed with anhydrous ethanol and dried to obtain the modifier. The raw materials for the modifier include unsaturated monomers, castor catalyst, and methyl hydrogen-containing silicone oil in a mass ratio of 10:0.05:14. The unsaturated monomers include unsaturated monomer A and unsaturated monomer B in a mass ratio of 2:1. Step 4: Preparation of noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries: S1: Mix 40 parts of polyester polyol, 17 parts of modifier, 4 parts of 1,4-butanediol, 0.4 parts of deionized water, 0.6 parts of antifungal agent, 0.03 parts of dibutyltin dilaurate, and 0.2 parts of bis(2-dimethylaminoethyl) ether evenly to obtain component A; S2: After dehydrating 42 parts of polyester polyol, heat it to 100℃, add 58 parts of diisocyanate, stir and react for 3 hours to obtain component B; S3: Components A and B are mixed at a mass ratio of 100:90, stirred at high speed, poured into a mold, quickly closed, cured, and then removed and cured at 110℃ for 18 hours to obtain noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries.

[0027] Comparative Example 3: Based on Example 1, unsaturated monomers A and B are introduced simultaneously, and the remaining processes are the same as in Example 1, as follows: Step 1: Preparation of unsaturated monomer A: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine were mixed evenly and reacted at 130℃ for 10 h. After purification, unsaturated monomer A was obtained. The raw materials for unsaturated monomer A included 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine in a mass ratio of 9.2:5:0.2. Step 2: Preparation of unsaturated monomer B: Cashew phenol glycidyl ether, triphenylphosphine, and hydroquinone were mixed evenly and heated to 95°C. Acrylic acid was added dropwise, with the addition time controlled at 1 hour. After the addition was completed, the reaction was stirred for another 3 hours. The mixture was then purified to obtain unsaturated monomer B. The raw materials for unsaturated monomer B included cashew phenol glycidyl ether, triphenylphosphine, hydroquinone, and acrylic acid in a mass ratio of 10:0.1:0.001:3.6. Step 3: Preparation of the modifier: Unsaturated monomer A, unsaturated monomer B, and caster catalyst are mixed evenly, heated to 80°C, and methyl hydrogen-containing silicone oil is added dropwise over 1 hour. The mixture is stirred and reacted for 15 hours. The mixture is then washed with anhydrous ethanol and dried to obtain the modifier. The raw materials for the modifier include unsaturated monomers, caster catalyst, and methyl hydrogen-containing silicone oil in a mass ratio of 10:0.05:14. The unsaturated monomers include unsaturated monomer A and unsaturated monomer B in a mass ratio of 2:1. Step 4: Preparation of noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries: S1: Mix 40 parts of polyester polyol, 17 parts of modifier, 4 parts of 1,4-butanediol, 0.4 parts of deionized water, 0.6 parts of antifungal agent, 0.03 parts of dibutyltin dilaurate, and 0.2 parts of bis(2-dimethylaminoethyl) ether evenly to obtain component A; S2: After dehydrating 42 parts of polyester polyol, heat it to 100℃, add 58 parts of diisocyanate, stir and react for 3 hours to obtain component B; S3: Components A and B are mixed at a mass ratio of 100:90, stirred at high speed, poured into a mold, quickly closed, cured, and then removed and cured at 110℃ for 18 hours to obtain noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries.

[0028] Comparative Example 4: Based on Example 1, the introduction ratio of unsaturated monomers A and B was adjusted, while the remaining processes were the same as in Example 1, as detailed below: Step 1: Preparation of unsaturated monomer A: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine were mixed evenly and reacted at 130℃ for 10 h. After purification, unsaturated monomer A was obtained. The raw materials for unsaturated monomer A included 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine in a mass ratio of 9.2:5:0.2. Step 2: Preparation of unsaturated monomer B: Cashew phenol glycidyl ether, triphenylphosphine, and hydroquinone were mixed evenly and heated to 95°C. Acrylic acid was added dropwise, with the addition time controlled at 1 hour. After the addition was completed, the reaction was stirred for another 3 hours. The mixture was then purified to obtain unsaturated monomer B. The raw materials for unsaturated monomer B included cashew phenol glycidyl ether, triphenylphosphine, hydroquinone, and acrylic acid in a mass ratio of 10:0.1:0.001:3.6. Step 3: Preparation of the modifier: Unsaturated monomer A and caster catalyst are mixed evenly and heated to 80°C. Methyl hydrogen-containing silicone oil is added dropwise over 1 hour, and the mixture is stirred for 5 hours. Unsaturated monomer B is then added, and the mixture is stirred for another 10 hours. The mixture is washed with anhydrous ethanol and dried to obtain the modifier. The raw materials for the modifier include unsaturated monomers, caster catalyst, and methyl hydrogen-containing silicone oil in a mass ratio of 10:0.05:14. The unsaturated monomers include unsaturated monomer A and unsaturated monomer B in a mass ratio of 1:2. Step 4: Preparation of noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries: S1: Mix 40 parts of polyester polyol, 17 parts of modifier, 4 parts of 1,4-butanediol, 0.4 parts of deionized water, 0.6 parts of antifungal agent, 0.03 parts of dibutyltin dilaurate, and 0.2 parts of bis(2-dimethylaminoethyl) ether evenly to obtain component A; S2: After dehydrating 42 parts of polyester polyol, heat it to 100℃, add 58 parts of diisocyanate, stir and react for 3 hours to obtain component B; S3: Components A and B are mixed at a mass ratio of 100:90, stirred at high speed, poured into a mold, quickly closed, cured, and then removed and cured at 110℃ for 18 hours to obtain noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries.

[0029] Performance testing: (1) The sound absorption coefficient of the samples of each embodiment and comparative example at 2000 Hz was measured according to GB / T 18696.2; (2) The samples of each embodiment and comparative example were simulated to vibrate on an electromagnetic vibration table, and the vibration attenuation rate (122 Hz / 72 dB) was measured using a PCB 352C03 accelerometer; (3) The limiting oxygen index of the sample materials of each embodiment and comparative example was measured according to GB / T 2406; The experimental data are shown in the table below:

[0030] Conclusions: As shown in the table above, Comparative Example 1, which introduces unsaturated monomer A alone, has only a rigid DOPO structure, resulting in a hard and brittle modifier, hindered chain segment movement, and a significant decrease in noise reduction and vibration damping performance. Furthermore, due to the lack of synergistic flame-retardant effect from the cashew phenol structure, its flame retardancy is also somewhat reduced. In Comparative Example 2, unsaturated monomer B is introduced first, followed by unsaturated monomer A. Because monomer B, containing flexible long chains, preferentially grafts onto the polysiloxane chain segments, it hinders the subsequent approach of the larger rigid monomer A to the remaining Si-H active sites, leading to a decrease in the grafting rate of the flame-retardant structure and a decline in flame-retardant performance. Moreover, this structure cannot form an effective rigid skeleton support and gradient damping, resulting in reduced noise reduction and vibration damping performance. In Comparative Example 3, unsaturated monomers A and B are introduced simultaneously. Since unsaturated monomer B is easier to graft, it is difficult to form a gradient structure that combines rigidity and flexibility, resulting in decreased noise reduction and vibration damping performance. In Comparative Example 4, the introduction ratio of unsaturated monomers A and B is adjusted, reducing the content of rigid unsaturated monomer A and making it too flexible; therefore, its overall performance is lower than that of Example 1.

[0031] In summary, this invention prepares unsaturated monomer A containing a DOPO structure and unsaturated monomer B containing a cashew phenol structure, and then grafts them onto a methyl hydrogen silicone oil backbone via hydrosilylation reaction to obtain a modifier. When introduced into a polyurethane foam system, this modifier significantly improves the noise reduction, vibration damping, and flame retardant properties of polyurethane foam.

[0032] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries, characterized in that: Includes the following steps: S1: Polyester polyol, modifier, 1,4-butanediol, deionized water, mildew inhibitor, dibutyltin dilaurate, and bis(2-dimethylaminoethyl) ether are mixed evenly to obtain component A; S2: After dehydrating the polyester polyol, diisocyanate is added, and the mixture is heated and stirred to react, yielding component B; S3: Mix components A and B, stir at high speed, pour into a mold, close the mold quickly, remove after curing, and perform a curing treatment to obtain noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries.

2. The method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries according to claim 1, characterized in that: Component A comprises the following raw materials, by mass parts: 35-45 parts polyester polyol, 15-20 parts modifier, 3-5 parts 1,4-butanediol, 0.3-0.5 parts deionized water, 0.5-0.8 parts mildew inhibitor, 0.02-0.04 parts dibutyltin dilaurate, and 0.2-0.25 parts bis(2-dimethylaminoethyl) ether; Component B comprises the following raw materials, by mass: 40-45 parts polyester polyol and 55-60 parts diisocyanate.

3. The method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries according to claim 1, characterized in that: The mass ratio of component A to component B is 100:85~95.

4. The method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries according to claim 1, characterized in that: During the preparation of component B, the temperature is 100~120℃ and the time is 2~4h; during the aging process, the temperature is 100~110℃ and the time is 18~24h.

5. The method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries according to claim 1, characterized in that: The preparation method of the modifier includes the following steps: mixing unsaturated monomer and cassiterite catalyst evenly, heating to 80~85℃, adding methyl hydrogen silicone oil dropwise, stirring and reacting for 12~18h, washing with anhydrous ethanol, drying, and obtaining the modifier.

6. The method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries according to claim 5, characterized in that: The raw materials for the modifier include unsaturated monomers, cassiterite catalysts, and methyl hydrogen silicone oil in a mass ratio of 10:0.05~0.1:13~16.

7. The method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries according to claim 5, characterized in that: The unsaturated monomers include unsaturated monomer A and unsaturated monomer B in a mass ratio of 1.5 to 3:1; The preparation method of the unsaturated monomer A includes the following steps: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine are mixed evenly, stirred and reacted at 130~135℃ for 10h, and purified to obtain unsaturated monomer A. The preparation method of the unsaturated monomer B includes the following steps: cashew phenol glycidyl ether, triphenylphosphine, and hydroquinone are mixed evenly, heated to 90~100℃, acrylic acid is added dropwise, the adding time is controlled to be 1~1.5h, after the addition is completed, the reaction is stirred for 3~4h, purified, and unsaturated monomer B is obtained.

8. The method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries according to claim 7, characterized in that: The raw materials for the unsaturated monomer A include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, allyl glycidyl ether, and triphenylphosphine in a mass ratio of 9~9.5:5:0.2~0.

3. The raw materials for the unsaturated monomer B include cashew phenol glycidyl ether, triphenylphosphine, hydroquinone, and acrylic acid in a mass ratio of 10:0.1~0.2:0.001~0.002:3.5~3.

7.

9. The method for preparing noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries according to claim 5, characterized in that: The specific steps in the preparation of the modifier are as follows: unsaturated monomer A and cassette catalyst are mixed evenly, heated to 80-85°C, methyl hydrogen silicone oil is added dropwise over a period of 1-2 hours, the mixture is stirred for 4-6 hours, unsaturated monomer B is added, and the mixture is stirred for another 8-12 hours. The mixture is then washed with anhydrous ethanol, dried, and the modifier is obtained.

10. The noise-reducing and vibration-damping polyurethane foam for new energy vehicle batteries prepared by the method according to any one of claims 1 to 9.

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