Polyurethane material for power battery cushioning protection and preparation method and application thereof
By using polyurethane materials formulated with specific ratios of aliphatic polyoxypropylene polyols, styrene-acrylonitrile grafted polyols, and aromatic amine polyols, the challenges of lightweighting, flame retardancy, and expansion force mitigation in power battery buffer and protection materials have been solved, achieving efficient compression curve control and enhanced safety.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHANGHAI HUAFON NEW MATERIAL R&D TECH CO LTD
- Filing Date
- 2023-04-20
- Publication Date
- 2026-05-12
AI Technical Summary
Existing power battery buffer and protection materials cannot simultaneously meet the requirements of light weight, specific compression buffer performance, flame retardancy, low cost, heat insulation, aging resistance, temperature shock resistance, acid and alkali resistance, low water absorption rate, and low odor, and cannot effectively alleviate the expansion force when the battery module is in use.
Polyurethane materials are prepared by compounding aliphatic polyoxypropylene polyols, styrene-acrylonitrile grafted polyols and aromatic amine polyols with crosslinking agents, catalysts and other components in specific proportions. By adjusting the slope of the compression curve, the compression space is released in a gradient under different extrusion pressures. Combined with materials with low thermal conductivity and high flame retardancy, the pre-tightening force and expansion force relief requirements of battery modules are met.
It achieves gradient release of compression space of polyurethane material under different extrusion pressures, meets the pre-tightening force requirements during battery module assembly, effectively alleviates expansion force, and has V0-level flame retardant performance, low thermal conductivity, low density, low water absorption and low odor, meeting the comprehensive performance requirements of power battery packs.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of polyurethane materials technology, specifically relating to a polyurethane material for buffer protection of power batteries, its preparation method, and its application. Background Technology
[0002] With the rapid growth in demand for power batteries in recent years, research on power batteries has gradually increased. Power battery packs are generally located under the vehicle, close to the road surface, making them susceptible to external impacts or mechanical damage, which places higher demands on their safety.
[0003] Currently, the main buffer and protective materials used in power battery packs are elastomer materials, such as EPDM rubber. CN114316450A discloses a thermal protection material for lithium-ion batteries. By weight, the thermal protection material comprises the following components: 100 parts EPDM rubber, 20-70 parts silica, 5-10 parts KH550, 0.5-10 parts peroxide curing agent, 2-8 parts antioxidant, 0.2-5 parts accelerator, 5-15 parts boron nitride nanoparticles, 15-40 parts silica aerogel, and 20-80 parts ceramic filler. The invention also discloses a method for preparing the thermal protection material, including mixing, molding, and microwave vulcanization. The thermal protection material provided by this invention has a higher thermal conductivity than EPDM rubber at room temperature and can form a ceramic body of a certain strength through thermal reaction at high temperatures. This not only reduces the thermal conductivity but also effectively improves the flame retardant properties of the thermal protection material. Using this material as a separator between individual cells in a battery pack can prevent chain reactions during thermal runaway of the battery cell. However, the thermal protection material provided by this invention has a high density, cannot simultaneously meet the requirements for fluidity and flame retardancy, and has high production costs. The module has low lightweight standards and cannot meet the design requirements for high weight of battery cell modules. It also cannot simultaneously meet the requirements for light weight, specific compression buffer performance, flame retardancy, low cost, heat insulation, aging resistance, temperature shock resistance, acid and alkali resistance, low water absorption, and low odor. In addition, as a battery buffer pad in the battery module, it needs to achieve the pre-tightening force requirement in the battery module through the appropriate reaction force generated by compression, and effectively alleviate the expansion force generated during the use of the battery module. This places high demands on the compressibility performance of the material.
[0004] Therefore, there is a need to develop a polyurethane material that can meet specific compression curve requirements and has excellent overall performance. Summary of the Invention
[0005] To address the shortcomings of existing technologies, the present invention aims to provide a polyurethane material for buffer protection of power batteries, its preparation method, and its application. By selecting specific components A and B for combination, the resulting polyurethane material can meet specific compression curve requirements and also possesses excellent comprehensive performance. At the same time, the battery buffer pad made of the polyurethane material can release the compression space in a gradient under different extrusion forces, which can not only meet the pre-tightening force requirements during battery module assembly, but also effectively alleviate the expansion force generated during battery module use.
[0006] To achieve this objective, the present invention adopts the following technical solution:
[0007] In a first aspect, the present invention provides a polyurethane material for buffer protection of power batteries, the polyurethane material comprising component A and component B;
[0008] Component A comprises the following components in parts by weight:
[0009]
[0010] Component B comprises the following components in parts by weight:
[0011] 50-70 parts by weight of polyphenylmethane polyisocyanate
[0012] 30-40 parts by weight of diphenylmethane diisocyanate
[0013] 10-20 parts by weight of polyoxypropylene ether diol.
[0014] The aliphatic polyoxypropylene polyol may be 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, or 39 parts by weight.
[0015] The styrene-acrylonitrile grafted polyol can be 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, or 9.5 parts by weight, etc.
[0016] The aromatic amine polyol can be 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, or 9.5 parts by weight, etc.
[0017] The crosslinking agent can be 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, etc.
[0018] The catalyst can be 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, or 1.9 parts by weight, etc.
[0019] The foaming agent can be 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, or 7 parts by weight, etc.
[0020] The polyphenylmethane polyisocyanate can be in quantities of 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight, 64 parts by weight, 66 parts by weight, or 68 parts by weight.
[0021] The diphenylmethane diisocyanate may be in quantities of 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, or 39 parts by weight.
[0022] The polyoxypropylene ether diol can be 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, or 19 parts by weight, etc.
[0023] The polyurethane material provided by this invention comprises component A and component B. Component A includes a specific proportion of aliphatic polyoxypropylene polyol, styrene-acrylonitrile grafted polyol, aromatic amine polyol, crosslinking agent, catalyst, and foaming agent. Component B includes a specific proportion of polyphenylmethane polyisocyanate, diphenylmethane diisocyanate, and polyoxypropylene ether diol. By selecting specific proportions of aliphatic polyoxypropylene polyol, styrene-acrylonitrile grafted polyol, and aromatic amine polyol in component A for compounding, and combining them with specific proportions of crosslinking agent, catalyst, and foaming agent, the prepared polyurethane material can meet specific compression curve requirements and also possesses high flame retardancy, low thermal conductivity, low density, low water absorption, low odor, excellent aging resistance, temperature shock resistance, and acid and alkali resistance, exhibiting excellent overall performance. Simultaneously, the battery buffer pad made of the polyurethane material allows for gradient release of compression space under different extrusion forces, satisfying the pre-tightening force requirements during battery module assembly and effectively mitigating the expansion force generated during battery module use.
[0024] Specifically, firstly, the relative amounts of styrene-acrylonitrile grafted polyol and aromatic amine polyol in component A of the polyurethane material provided by this invention are crucial. Adjusting the mass ratio of styrene-acrylonitrile grafted polyol and aromatic amine polyol can control and design the slope of the front and back ends of the compression curve of the polyurethane material. Limiting the addition amounts of these two substances within the range specified by this invention can adjust the compression curve of the polyurethane material to a more suitable range, enabling it to release the compression space gradually under different extrusion pressures. This satisfies the pre-tightening force requirements during battery module assembly and effectively alleviates the expansion force generated during battery module use. Secondly, the selection of styrene-acrylonitrile grafted polyol and aromatic amine polyol is also crucial. The vinyl side chains grafted onto the main molecular chain of the styrene-acrylonitrile grafted polyol are organic fillers that can replace inorganic fillers. This not only gives polyurethane materials higher load-bearing capacity and better resilience, but also improves the cell structure and physical and mechanical properties of the polyurethane material. Furthermore, by adjusting its addition amount, the slope of the compression curve of the polyurethane material can be altered, particularly significantly affecting the compressive strength at higher compression rates. Meanwhile, the aromatic amine polyol contains phenolic aromatic rings and tertiary amine groups. The introduction of the benzene ring can give polyurethane foam materials excellent heat resistance, flame retardancy, and mechanical properties. Moreover, by adjusting its addition amount, the slope of the foam's compression curve can also be altered, particularly significantly affecting the compressive strength at lower compression rates.
[0025] In this invention, the aliphatic polyoxypropylene polyol is preferably any one of PN-400, PN-560, ST-481 or 4110, but is not limited thereto.
[0026] In this invention, the styrene-acrylonitrile grafted polyol is preferably any one of Jiangsu Changhua CHP-H30, Jiangsu Changhua CHP-H45 or Korean KPX KE-2045E, but is not limited thereto.
[0027] In this invention, the aromatic amine polyol is preferably Tianjin Petrochemical SY-6560 and / or Fangda Jinhua JH-4548, but is not limited thereto.
[0028] Preferably, the hydroxyl value of the aliphatic polyoxypropylene polyol is 300-1000 mgKOH / g, such as 400 mgKOH / g, 500 mgKOH / g, 600 mgKOH / g, 700 mgKOH / g, 800 mgKOH / g or 900 mgKOH / g.
[0029] Preferably, the aliphatic polyoxypropylene polyol has a functionality of not less than 3, such as 4, 5, 6, 7, 8 or 9.
[0030] Preferably, the hydroxyl value of the styrene-acrylonitrile grafted polyol is 20-40 mgKOH / g, such as 22 mgKOH / g, 24 mgKOH / g, 26 mgKOH / g, 28 mgKOH / g, 30 mgKOH / g, 32 mgKOH / g, 34 mgKOH / g, 36 mgKOH / g, or 38 mgKOH / g.
[0031] Preferably, the styrene-acrylonitrile grafted polyol is a styrene-acrylonitrile grafted polyol based on PO-EO copolyether triol.
[0032] Preferably, the solid content of the styrene-acrylonitrile grafted polyol is 20-50%, such as 25%, 30%, 35%, 40%, or 45%.
[0033] Preferably, the aromatic amine polyol is a Mannich aromatic amine polyol, which refers to a polyol with an aromatic ring in its molecular structure obtained by the Mannich reaction.
[0034] Preferably, the hydroxyl value of the aromatic amine polyol is 300-1000 mgKOH / g, such as 400 mgKOH / g, 500 mgKOH / g, 600 mgKOH / g, 700 mgKOH / g, 800 mgKOH / g or 900 mgKOH / g.
[0035] Preferably, the aromatic amine polyol is an aromatic polyoxypropylene polyol.
[0036] Preferably, the crosslinking agent has a functionality of not less than 3, such as 4, 5, 6, 7, 8 or 9.
[0037] As a preferred technical solution of the present invention, a crosslinking agent with a functionality of not less than 3 can react with the functional groups on the polymer chain to extend the molecular chain, increase the molecular weight, and increase the content of hard segments. It can also cause the molecular chain to crosslink to a certain extent, thereby improving the dimensional stability of polyurethane materials.
[0038] Preferably, the crosslinking agent comprises a small molecule alcohol or a small molecule amine.
[0039] Preferably, the small molecule alcohol includes any one or a combination of at least two of glycerol, trimethylolpropane, or pentaerythritol.
[0040] Preferably, the small molecule amine includes any one or a combination of at least two of triethanolamine, diethanolamine, or triisopropanolamine.
[0041] Preferably, the foaming agent comprises any one or a combination of at least two of cyclopentane, hydrofluorocarbon (HFC-365mfc), 1,1-dichloro-1-fluoroethane (HCFC-141b), or water.
[0042] Preferably, the catalyst comprises a reactive amine catalyst.
[0043] In this invention, the reactive amine catalyst is preferably Niax EF 680 or Niax EF 150. The above reactive amine catalyst can react with isocyanate groups, reduce VOC volatility, and make the system have good flowability during the reaction.
[0044] Preferably, component A further includes any one or a combination of at least two of plasticizers, flame retardants, or foam stabilizers.
[0045] Preferably, the content of plasticizer in component A is 5 to 20 parts by weight, such as 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, or 19 parts by weight.
[0046] Preferably, the plasticizer is an ester plasticizer.
[0047] Preferably, the ester plasticizer includes any one or a combination of at least two of the following: trioctyl trimellitate, tributyl citrate, acetylated tributyl citrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, or 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.
[0048] As a preferred technical solution of the present invention, the above-mentioned types of ester plasticizers have good compatibility with polyurethane materials, less migration, and significantly improved stability and synergy.
[0049] Preferably, the flame retardant content in component A is 15 to 30 parts by weight, such as 15.5 parts by weight, 16 parts by weight, 16.5 parts by weight, 17 parts by weight, 17.5 parts by weight, 18 parts by weight, 18.5 parts by weight, 19 parts by weight, or 19.5 parts by weight.
[0050] Preferably, the flame retardant includes a haloalkyl phosphate flame retardant and / or a haloalkyl polyphosphate flame retardant, and more preferably a combination of a haloalkyl phosphate flame retardant and a haloalkyl polyphosphate flame retardant.
[0051] In this invention, the halogenated alkyl phosphate flame retardant is preferably Yake FC-68 or Wansheng WSFR-118, and the halogenated alkyl polyphosphate flame retardant is preferably Wansheng WSFR-504L. The above two types of flame retardants have high molecular weights, and when used together, they also have the characteristics of low volatility and good durability, which can provide a stable flame retardant effect.
[0052] Preferably, the content of foam stabilizer in component A is 1 to 2 parts by weight, such as 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight or 1.8 parts by weight.
[0053] Preferably, the foam stabilizer includes a silicon-carbon surfactant.
[0054] In this invention, the foam stabilizer is preferably an organosiloxane having a silicon-carbon structure and possessing hydrolysis resistance, high activity, and high emulsification ability, such as DC193, L-6863, or B8423.
[0055] Preferably, the number average molecular weight of the polyoxypropylene ether diol is 400-1000 g / mol, such as 500 g / mol, 600 g / mol, 700 g / mol, 800 g / mol or 900 g / mol.
[0056] In this invention, the polyoxypropylene ether diol is preferably a well-designed D204, D210, or Jurong Ningwu NJ-207.
[0057] This invention improves the toughness of the final polyurethane material, reduces its heat of reaction, and enhances the dimensional stability of the product by introducing a polyether structure into component B.
[0058] Preferably, the mass ratio of component A to component B is 100:(80-150), for example, 100:82, 100:94, 100:106, 100:110, 100:120, 100:132, 100:136, 100:140 or 100:148, etc.
[0059] In a second aspect, the present invention provides a method for preparing a polyurethane material as described in the first aspect, the method comprising the following steps:
[0060] (1) Preparation of component A: Aliphatic polyoxypropylene polyol, styrene-acrylonitrile grafted polyol, aromatic amine polyol, crosslinking agent, catalyst, optional plasticizer, optional flame retardant and optional foam stabilizer are mixed in water, and foaming agent is added for mixing to obtain component A;
[0061] Preparation of component B: Polyoxypropylene ether diol was reacted with diphenylmethane diisocyanate, and then polyphenylmethane polyisocyanate was added and mixed to obtain component B;
[0062] (2) Mix the components A and B obtained in step (1) and cure them to obtain the polyurethane material.
[0063] Preferably, in the preparation of component A, the mixing temperature is 25-30°C, such as 25.5°C, 26°C, 26.5°C, 27°C, 27.5°C, 28°C, 28.5°C, 29°C, or 29.5°C.
[0064] Preferably, in the preparation of component B, the reaction temperature is 70-90°C, for example 72°C, 74°C, 76°C, 78°C, 80°C, 82°C, 84°C, 86°C or 88°C.
[0065] Preferably, in the preparation of component B, the reaction temperature is 40-60°C, for example 42°C, 44°C, 46°C, 48°C, 50°C, 52°C, 54°C, 56°C or 58°C.
[0066] Preferably, in the preparation of component B, the mixing temperature is 40-60 h, for example 42 h, 44 h, 46 h, 48 h, 50 h, 52 h, 54 h, 56 h or 58 h.
[0067] Preferably, in the preparation of component B, the mixing time is 0.5 to 1.5 h, for example, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1 h, 1.1 h, 1.2 h, 1.3 h or 1.4 h.
[0068] Preferably, the curing time in step (2) is 7 to 10 minutes, such as 7.2 minutes, 7.4 minutes, 7.6 minutes, 7.8 minutes, 8 minutes, 8.3 minutes, 8.6 minutes, 8.9 minutes, 9.2 minutes, 9.5 minutes or 9.8 minutes.
[0069] Preferably, step (2) includes a step of pouring into a mold before curing, and a step of demolding after curing.
[0070] Thirdly, the present invention provides an application of the polyurethane material as described in the first aspect as a buffer and protective material for power batteries.
[0071] Fourthly, the present invention provides a battery buffer pad, wherein the raw materials for preparing the battery buffer pad include the polyurethane material as described in the first aspect.
[0072] Compared with the prior art, the present invention has the following beneficial effects:
[0073] (1) The polyurethane material provided by the present invention is compounded by aliphatic polyoxypropylene polyol, styrene-acrylonitrile grafted polyol and aromatic amine polyol, and then the density is adjusted by catalyst. The compression curve of the polyurethane material can be adjusted to a specific required range, so that the obtained polyurethane material can release the compression space under different extrusion pressures. This can not only meet the pre-tightening force requirements during battery module assembly, but also effectively alleviate the expansion force generated during battery module use.
[0074] (2) The flame retardant properties of the polyurethane material provided by the present invention can reach the V0 flame retardant level, which can meet the flame retardant requirements of the power battery pack.
[0075] (3) The present invention uses a low thermal conductivity physical foaming agent, and the polyurethane foam material prepared therefrom has a low thermal conductivity, which can meet the requirements of battery pack insulation.
[0076] (3) The polyurethane material provided by the present invention uses a low-migration flame retardant and a low-odor reactive catalyst, which can reduce VOC emissions and meet the requirements of automobiles for low odor. Detailed Implementation
[0077] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.
[0078] The following is some information about the raw materials involved in the specific embodiments of this invention:
[0079] Aliphatic polyoxypropylene polyol PN-560: hydroxyl value is 560mgKOH / g, functionality is 4, and number-average molecular weight is 400;
[0080] Aliphatic polyoxypropylene polyol PN-400: hydroxyl value is 400mgKOH / g, functionality is 4, and number-average molecular weight is 560;
[0081] Aliphatic polyoxypropylene polyol ST-481: hydroxyl value is 480 mgKOH / g, functionality is 5, and number-average molecular weight is 580;
[0082] Aliphatic polyoxypropylene polyol 4110: hydroxyl value is 450 mgKOH / g, functionality is 4, and number-average molecular weight is 500.
[0083] Styrene-acrylonitrile grafted polyol CHP-H30: hydroxyl value is 25 mgKOH / g, functionality is 3, and number-average molecular weight is 6700;
[0084] Styrene-acrylonitrile grafted polyol CHP-H45: hydroxyl value is 21 mgKOH / g, functionality is 3, and number-average molecular weight is 8000;
[0085] Styrene-acrylonitrile grafted polyol KE-2045E: hydroxyl value is 30mgKOH / g, functionality is 3, and number-average molecular weight is 5600;
[0086] Mannich aromatic amine polyol SY-6560: hydroxyl value is 570mgKOH / g, functionality is 6, and number-average molecular weight is 600;
[0087] Mannich aromatic amine polyol JH-4548: hydroxyl value is 460 mgKOH / g, functionality is 4, and number-average molecular weight is 490;
[0088] Polyoxypropylene ether diol D204: Number average molecular weight is 400;
[0089] Polyoxypropylene ether diol D210: Number average molecular weight is 1000.
[0090] Example 1
[0091] A polyurethane material for buffer protection of power batteries, the preparation method of which includes the following steps:
[0092] (1) 40 kg of aliphatic polyoxypropylene polyol PN-560, 10 kg of styrene-acrylonitrile grafted polyol CHP-H30, 10 kg of Mannich aromatic amine polyol SY-6560, 10 kg of tributyl citrate, 10 kg of haloalkyl phosphate flame retardant FC-68, 5 kg of haloalkyl polyphosphate flame retardant WSFR-504L, 7 kg of glycerol, 1.5 kg of foam stabilizer DC193, 0.5 kg of reactive amine catalyst Niax EF 680, 1 kg of reactive amine catalyst Niax EF 150 and 0.5 kg of water were stirred at 28℃ for 3 h, 4.5 kg of foaming agent HFC-365mfc was added and stirred for 0.5 h, sealed and stored to obtain component A;
[0093] 10 kg of polyoxypropylene ether diol D204 and 30 kg of diphenylmethane diisocyanate (MDI) were reacted at 80 °C for 2.5 h. After adding 60 kg of polyphenylmethane polyisocyanate and stirring evenly, component B was obtained.
[0094] (2) Mix component A and component B obtained in step (1) at a mass ratio of 100:150, then inject the mixture into a 6mm thick mold, and demold after curing for 10 minutes to obtain the polyurethane material for buffer protection of power batteries.
[0095] Example 2
[0096] A polyurethane material for buffer protection of power batteries, the preparation method of which includes the following steps:
[0097] (1) 30 kg of aliphatic polyoxypropylene polyol PN-400, 5 kg of styrene-acrylonitrile grafted polyol CHP-H45, 10 kg of Mannich aromatic amine polyol JH-4548, 20 kg of trioctyl trimellitate, 15 kg of haloalkyl phosphate flame retardant WSFR-118, 5 kg of haloalkyl polyphosphate flame retardant WSFR-504L, 10 kg of trimethylolpropane, 1.5 kg of foam stabilizer L-6863, 0.5 kg of reactive amine catalyst Niax EF 680, 1 kg of reactive amine catalyst Niax EF 150 and 0.2 kg of water were stirred at 25°C for 3 h, 1.8 kg of foaming agent HFC-365mfc was added and stirred for 0.5 h, sealed and stored to obtain component A;
[0098] 20 kg of polyoxypropylene ether diol D210 and 30 kg of MDI were reacted in a reactor at 85 °C for 2 h. Then, 50 kg of polyphenylmethane polyisocyanate was added and stirred until homogeneous to obtain component B.
[0099] (2) Mix component A and component B obtained in step (1) at a ratio of 100:145, inject into a 6mm thick mold, and demold after curing for 8 minutes to obtain the polyurethane material for buffer protection of power batteries.
[0100] Example 3
[0101] A polyurethane material for buffer protection of power batteries, the preparation method of which includes the following steps:
[0102] (1) 40 kg of aliphatic polyoxypropylene polyol ST-481, 10 kg of styrene-acrylonitrile grafted polyol KE-2045E, 5 kg of Mannich aromatic amine polyol SY-6560, 5 kg of acetylacetic tributyl citrate, 15 kg of haloalkyl phosphate flame retardant FC-68, 12 kg of haloalkyl polyphosphate flame retardant WSFR-504L, 3 kg of triethanolamine, 2 kg of foam stabilizer B8423, 0.5 kg of reactive amine catalyst Niax EF 680, 1.5 kg of reactive amine catalyst Niax EF 150 and 1 kg of water were stirred at 30°C for 3 h, 5 kg of foaming agent HCFC-141b was added and stirred for 0.5 h, sealed and stored to obtain component A;
[0103] 10 kg of polyoxypropylene ether diol D204 and 40 kg of MDI were reacted in a reactor at 75°C for 3 h. 50 kg of polyphenylmethane polyisocyanate was then added and stirred until homogeneous to obtain component B.
[0104] (2) Mix component A and component B obtained in step (1) at a ratio of 100:120, inject into a 6mm thick mold, and demold after curing for 10 minutes to obtain the polyurethane material for buffer protection of power batteries.
[0105] Example 4
[0106] A polyurethane material for buffer protection of power batteries, the preparation method of which includes the following steps:
[0107] (1) 32.8 kg of aliphatic polyoxypropylene polyol 4110, 5 kg of styrene-acrylonitrile grafted polyol CHP-H30, 5 kg of Mannich aromatic amine polyol JH-4548, 12 kg of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 15 kg of haloalkyl phosphate flame retardant WSFR-118, 15 kg of haloalkyl polyphosphate flame retardant WSFR-504L, 5 kg of triisopropanolamine, 1 kg of foam stabilizer DC193, 0.4 kg of reactive amine catalyst Niax EF 680, 0.8 kg of reactive amine catalyst Niax EF 150 and 0.8 kg of water were stirred at 25°C for 3 h, 7.2 kg of cyclopentane was added and stirred for 0.5 h, sealed and stored to obtain component A;
[0108] 10 kg of polyoxypropylene ether diol D210 and 30 kg of diphenylmethane diisocyanate (MDI) were reacted at 80 °C for 2.5 h. After adding 70 kg of polyphenylmethane polyisocyanate and stirring evenly, component B was obtained.
[0109] (2) Mix component A and component B obtained in step (1) at a mass ratio of 100:80, then inject the mixture into a 6mm thick mold, and demold after curing for 10 minutes to obtain the polyurethane material for buffer protection of power batteries.
[0110] Example 5
[0111] A polyurethane material for buffer protection of power batteries differs from Example 1 only in that the halogenated alkyl phosphate flame retardant FC-68 is not added, and the amount of halogenated alkyl polyphosphate flame retardant WSFR-504L added is 15 kg. The other components, dosages and preparation methods are the same as in Example 1.
[0112] Example 6
[0113] A polyurethane material for buffer protection of power batteries differs from Example 1 only in that the halogenated alkyl polyphosphate flame retardant WSFR-504L is not added, and the amount of halogenated alkyl phosphate flame retardant FC-68 added is 15 kg. The other components, dosages and preparation methods are the same as in Example 1.
[0114] Example 7
[0115] A polyurethane material for buffer protection of power batteries differs from Example 1 only in that it does not contain tributyl citrate; all other components, dosages, and preparation methods are the same as in Example 1.
[0116] Comparative Example 1
[0117] A polyurethane material for buffer protection of power batteries, the preparation method of which includes the following steps:
[0118] (1) 40 kg of aliphatic polyoxypropylene polyol PN-560, 20 kg of Mannich aromatic amine polyol SY-6560, 10 kg of tributyl citrate, 10 kg of haloalkyl phosphate flame retardant FC-68, 5 kg of haloalkyl polyphosphate flame retardant WSFR-504L, 7 kg of glycerol, 1.5 kg of foam stabilizer DC193, 0.5 kg of reactive amine catalyst Niax EF 680, 1 kg of reactive amine catalyst Niax EF 150 and 0.5 kg of water were stirred at 28℃ for 3 h, 4.5 kg of foaming agent HFC-365mfc was added and stirred for 0.5 h, sealed and stored to obtain component A;
[0119] 10 kg of polyoxypropylene ether diol D204 and 30 kg of MDI were reacted at 80 °C for 2.5 h. After adding 60 kg of polyphenylmethane polyisocyanate and stirring evenly, component B was obtained.
[0120] (2) Mix component A and component B obtained in step (1) at a mass ratio of 100:150, then inject the mixture into a 6mm thick mold, and demold after curing for 10 minutes to obtain the polyurethane material for buffer protection of power batteries.
[0121] Comparative Example 2
[0122] A polyurethane material for buffer protection of power batteries, the preparation method of which includes the following steps:
[0123] (1) 40 kg of aliphatic polyoxypropylene polyol PN-560, 20 kg of styrene-acrylonitrile grafted polyol CHP-H30, 10 kg of tributyl citrate, 10 kg of haloalkyl phosphate flame retardant FC-68, 5 kg of haloalkyl polyphosphate flame retardant WSFR-504L, 7 kg of glycerol, 1.5 kg of foam stabilizer DC193, 0.5 kg of reactive amine catalyst Niax EF680, 1 kg of reactive amine catalyst Niax EF 150 and 0.5 kg of water were stirred at 28℃ for 3 h, 4.5 kg of foaming agent HFC-365mfc was added and stirred for 0.5 h, sealed and stored to obtain component A;
[0124] 10 kg of polyoxypropylene ether diol D204 and 30 kg of diphenylmethane diisocyanate (MDI) were reacted at 80 °C for 2.5 h. After adding 60 kg of polyphenylmethane polyisocyanate and stirring evenly, component B was obtained.
[0125] (2) Mix component A and component B obtained in step (1) at a mass ratio of 100:150, then inject the mixture into a 6mm thick mold, and demold after curing for 10 minutes to obtain the polyurethane material for buffer protection of power batteries.
[0126] Comparative Example 3
[0127] A polyurethane material for buffer protection of power batteries differs from Example 1 only in that the amount of styrene-acrylonitrile grafted polyol CHP-H30 added is 5 kg, and the amount of Mannich aromatic amine polyol SY-6560 added is 15 kg. Other components, amounts, and preparation methods are the same as in Example 1.
[0128] Comparative Example 4
[0129] A polyurethane material for buffer protection of power batteries differs from Example 1 only in that the amount of styrene-acrylonitrile grafted polyol CHP-H30 added is 15 kg, and the amount of Mannich aromatic amine polyol SY-6560 added is 5 kg. Other components, amounts, and preparation methods are the same as in Example 1.
[0130] Performance testing:
[0131] (1) Hardness: Tested using a Shore A hardness tester;
[0132] (2) Compression strength: The size of the test sample is 50×50×6mm, and the compression rate is 2mm / min. The compression strength of the test sample is recorded as the compression strength before aging at 85% humidity and 85℃ for 1000h after being directly compressed at 25℃ and 50% humidity. The compression strength of the sample after aging at 85% humidity and 85℃ for 1000h is recorded as the compression strength after aging at 85% humidity and 85℃ for 1000h.
[0133] The compressive strength was tested according to the test method provided in GB / T 8813.
[0134] The polyurethane materials provided in Examples 1-7 and Comparative Examples 1-4 were tested according to the above test methods, and the test results are shown in Table 1:
[0135] Table 1
[0136]
[0137]
[0138] According to the data in Table 1:
[0139] The polyurethane materials obtained in Examples 1-7 have a hardness of 82-85A, and their 10% compressive strength before aging at 85% humidity and 85℃ for 1000 hours is 4.2-4.5 MPa, 30% compressive strength is 6.1-6.4 MPa, 50% compressive strength is 7.6-8.1 MPa, and 70% compressive strength is 15.0-15.5 MPa. After aging at 85% humidity and 85℃ for 1000 hours, the 10% compressive strength is 4.4-4.8 MPa, 30% compressive strength is 6.5-6.7 MPa, 50% compressive strength is 8.3-8.5 MPa, and 70% compressive strength is 16.2-16.5 MPa.
[0140] Compared with Example 1, Comparative Example 1 did not use styrene-acrylonitrile grafted polyols, but only aliphatic polyoxypropylene polyols and Mannich aromatic amine polyols. The 10% and 30% compressive strengths met the required range, but the 50% and 70% compressive strengths were low. This is because the vinyl side chain in the styrene-acrylonitrile grafted polyol is an organic filler, which not only enables the polyurethane foam material to have high load-bearing capacity and good resilience, but also improves the foam cell structure and physical and mechanical properties, especially significantly affecting the compressive strength at larger compression rates.
[0141] Compared with Example 1, Comparative Example 2 did not use Mannich aromatic amine polyols, but only styrene-acrylonitrile grafted polyols and aliphatic polyoxypropylene polyols. The 10% and 30% compressive strengths were lower, while the 50% and 70% compressive strengths met the required range. This is because the Mannich aromatic amine polyol structure contains phenolic aromatic rings and tertiary amine groups. The introduction of benzene rings gives the polyurethane foam excellent heat resistance, flame retardancy and mechanical properties, and can change the slope of the foam compression curve, especially significantly affecting the compressive strength at smaller compression amounts.
[0142] Compared with Example 1, Comparative Example 3 reduced the amount of styrene-acrylonitrile grafted polyol and increased the amount of Mannich aromatic amine polyol, resulting in increased 10% and 30% compressive strengths and decreased 50% and 70% compressive strengths, thereby reducing the overall slope of the compression curve.
[0143] Compared with Example 1, Comparative Example 4 increased the amount of styrene-acrylonitrile grafted polyol and decreased the amount of Mannich aromatic amine polyol. Its 10% and 30% compressive strengths decreased, while its 50% and 70% compressive strengths increased, thereby increasing the overall slope of the compression curve.
[0144] The applicant declares that this invention illustrates a polyurethane material for buffer protection of power batteries, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of the raw materials in the product of this invention, additions of auxiliary components, and selection of specific methods, all fall within the protection and disclosure scope of this invention.
Claims
1. A polyurethane material for buffer protection of power batteries, characterized in that, The polyurethane material comprises component A and component B; Component A comprises the following components in parts by weight: 30-40 parts by weight of aliphatic polyoxypropylene polyol 5-10 parts by weight of styrene-acrylonitrile grafted polyol 5-10 parts by weight of aromatic amine polyol 3-10 parts by weight of crosslinking agent 1.2 to 2 parts by weight of catalyst 2-8 parts by weight of foaming agent; Component B comprises the following components in parts by weight: 50-70 parts by weight of polyphenylmethane polyisocyanate 30-40 parts by weight of diphenylmethane diisocyanate 10-20 parts by weight of polyoxypropylene ether diol; The aromatic amine polyol is Mannich aromatic amine polyol.
2. The polyurethane material according to claim 1, characterized in that, The hydroxyl value of the aliphatic polyoxypropylene polyol is 300~1000 mg KOH / g.
3. The polyurethane material according to claim 1, characterized in that, The functionality of the aliphatic polyoxypropylene polyol is not less than 3.
4. The polyurethane material according to claim 1, characterized in that, The hydroxyl value of the styrene-acrylonitrile grafted polyol is 20~40 mg KOH / g.
5. The polyurethane material according to claim 1, characterized in that, The styrene-acrylonitrile grafted polyol is a styrene-acrylonitrile grafted polyol based on PO-EO copolyether triol.
6. The polyurethane material according to claim 1, characterized in that, The solid content of the styrene-acrylonitrile grafted polyol is 20-50%.
7. The polyurethane material according to claim 1, characterized in that, The hydroxyl value of the aromatic amine polyol is 300~1000 mg KOH / g.
8. The polyurethane material according to claim 1, characterized in that, The crosslinking agent has a functionality of not less than 3.
9. The polyurethane material according to claim 1, characterized in that, The crosslinking agent includes small molecule alcohols or small molecule amines.
10. The polyurethane material according to claim 9, characterized in that, The small molecule alcohols include any one or a combination of at least two of glycerol, trimethylolpropane, or pentaerythritol.
11. The polyurethane material according to claim 9, characterized in that, The small molecule amine includes any one or a combination of at least two of triethanolamine, diethanolamine, or triisopropanolamine.
12. The polyurethane material according to claim 1, characterized in that, The foaming agent includes any one or a combination of at least two of cyclopentane, hydrofluorocarbon, 1,1-dichloro-1-fluoroethane, or water.
13. The polyurethane material according to claim 1, characterized in that, The catalyst includes reactive amine catalysts.
14. The polyurethane material according to claim 1, characterized in that, Component A further includes any one or a combination of at least two of plasticizers, flame retardants, or foam stabilizers.
15. The polyurethane material according to claim 14, characterized in that, The plasticizer content in component A is 5 to 20 parts by weight.
16. The polyurethane material according to claim 14, characterized in that, The plasticizer is an ester-based plasticizer.
17. The polyurethane material according to claim 16, characterized in that, The ester plasticizers include any one or a combination of at least two of the following: trioctyl trimellitate, tributyl citrate, acetylated tributyl citrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, or 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.
18. The polyurethane material according to claim 14, characterized in that, The flame retardant content in component A is 15-30 parts by weight.
19. The polyurethane material according to claim 14, characterized in that, The flame retardant includes haloalkyl phosphate flame retardants and / or haloalkyl polyphosphate flame retardants.
20. The polyurethane material according to claim 19, characterized in that, The flame retardant is a combination of haloalkyl phosphate flame retardants and haloalkyl polyphosphate flame retardants.
21. The polyurethane material according to claim 14, characterized in that, The content of foam stabilizer in component A is 1 to 2 parts by weight.
22. The polyurethane material according to claim 14, characterized in that, The foam stabilizer includes silicon-carbon surfactants.
23. The polyurethane material according to claim 1, characterized in that, The number-average molecular weight of the polyoxypropylene ether diol is 400~1000 g / mol.
24. The polyurethane material according to claim 1, characterized in that, The mass ratio of component A to component B is 100:(80~150).
25. A method for preparing a polyurethane material as described in any one of claims 1 to 24, characterized in that, The preparation method includes the following steps: (1) Preparation of component A: Aliphatic polyoxypropylene polyol, styrene-acrylonitrile grafted polyol, aromatic amine polyol, crosslinking agent, catalyst, optional plasticizer, optional flame retardant and optional foam stabilizer are mixed in water, and foaming agent is added for mixing to obtain component A; Preparation of component B: Polyoxypropylene ether diol was reacted with diphenylmethane diisocyanate, and then polyphenylmethane polyisocyanate was added and mixed to obtain component B; (2) Mix component A and component B obtained in step (1) and cure to obtain the polyurethane material.
26. The preparation method according to claim 25, characterized in that, In the preparation of component A, the mixing temperature is 25~30℃.
27. The preparation method according to claim 25, characterized in that, In the preparation of component B, the reaction temperature is 70~90℃.
28. The preparation method according to claim 25, characterized in that, In the preparation of component B, the reaction temperature is 40~60℃.
29. The preparation method according to claim 25, characterized in that, In the preparation of component B, the mixing temperature is 40~60℃.
30. The preparation method according to claim 25, characterized in that, In the preparation of component B, the mixing time is 0.5~1.5 h.
31. The preparation method according to claim 25, characterized in that, The curing time in step (2) is 7~10 min.
32. The preparation method according to claim 25, characterized in that, Step (2) includes a step of pouring into a mold before curing and a step of demolding after curing.
33. An application of the polyurethane material as described in any one of claims 1 to 24 as a buffer and protective material for power batteries.
34. A battery cushioning pad, characterized in that, The raw materials for preparing the battery buffer pad include the polyurethane material as described in any one of claims 1 to 24.