CN113717347A - Polyurethane foam pouring sealant for battery unit and preparation method thereof - Google Patents
Polyurethane foam pouring sealant for battery unit and preparation method thereof Download PDFInfo
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- CN113717347A CN113717347A CN202111075273.9A CN202111075273A CN113717347A CN 113717347 A CN113717347 A CN 113717347A CN 202111075273 A CN202111075273 A CN 202111075273A CN 113717347 A CN113717347 A CN 113717347A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2190/00—Compositions for sealing or packing joints
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a polyurethane foam pouring sealant for a battery unit and a preparation method thereof. The polyurethane foam pouring sealant for the battery unit has the advantages of good fluidity, excellent flame retardant property and excellent environmental change resistance, is light in weight compared with the traditional polyurethane pouring sealant, and can reduce the dead weight of a new energy vehicle; the invention also provides a preparation method thereof, which comprises the steps of firstly preparing the polyol A component and the isocyanate B component, then adjusting the proportion of the polyol A component and the isocyanate B component in a charging bucket of a low-pressure casting machine, and injecting the mixture into a gap of a shell of a battery unit.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a polyurethane foam pouring sealant for a battery unit and a preparation method thereof.
Background
With the improvement of the requirements of national energy-saving and environment-friendly policies, the application and development of novel energy resources are widely regarded. Particularly, new energy automobiles are rapidly developed, in 2020, production and marketing are respectively completed by 136.6 thousands and 136.7 thousands, the production and marketing are respectively increased by 7.5% and 10.9% in the same ratio, and the production and marketing amount is high in innovation history. The capacity of the power battery is increased at a high speed, 9 months in 2020, the loading capacity of the power battery in China is 6.6GWH, the year-on-year ratio is increased by 66.4 percent, the ring ratio is increased by 28.3 percent, and the situation of continuous increase is kept. In order to protect a vehicle battery module, manufacturers generally fill a gap between a battery case and a battery cell with a potting adhesive, which is intended to provide mechanical stability and impact resistance to the battery module, and also to provide adhesion, flame retardancy, high temperature resistance, hydrolysis resistance, and electrical properties. Most of electronic pouring sealant materials in the current market are non-foaming materials, and a large amount of high-density filler is filled in some pouring sealants, so that the weight of a battery pack after pouring is greatly increased, and the dead weight of a new energy vehicle is influenced.
The polyurethane foam has lower density and better impact resistance. The polyurethane foam is adopted to fill the battery, so that the safety requirement of the battery can be well met, and the weight is light. Meanwhile, the harsh environment of the new energy battery causes high requirements on the flame retardance, the mechanical property, the hydrolysis and aging resistance, the high and low temperature impact resistance and the dimensional stability of the pouring sealant product. However, polyurethane foam pouring sealant products in the existing market are not specially designed for new energy batteries, and cannot meet the requirements of the new energy batteries. Patent CN 110392945 a provides a flame retardant-containing polyurethane foam potting adhesive for battery cells, the density of the potting adhesive is less than 0.5g/m3, the flame retardant rating is at least V2, the potting composition has low viscosity, and has sufficient fluidity to fill in the gaps of the battery cells. However, the patent does not mention the mechanical properties, environmental change resistance and electrical properties of the potting adhesive.
In conclusion, the polyurethane foam pouring sealant for the battery unit at present has the defect of overlarge density, and cannot meet the requirements of new energy batteries.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the polyurethane foam pouring sealant for the battery unit. The second purpose of the invention is to provide a preparation method of the polyurethane foam pouring sealant for the battery unit.
The produced polyurethane foam pouring sealant for the battery unit has relatively low density and good environmental change resistance and electrical performance.
In order to realize one of the purposes of the invention, the adopted technical scheme is as follows:
a polyurethane foam pouring sealant for a battery unit comprises a polyol A component and an isocyanate B component, wherein the polyol A component comprises the following components in parts by weight:
the isocyanate B component comprises the following components in parts by weight:
0-3 parts of a micromolecular chain extender;
97-100 parts of isocyanate;
in a preferred embodiment of the present invention, the special polyester polyol is polycarbonate polyol, and the molecular weight is 400-1500. The preferred functionality is 2.
The polycarbonate polyol has excellent hydrolysis resistance and ageing resistance, and the tensile strength and elongation of the foam can be increased by adding the polycarbonate diol into a hard foam system, so that the impact resistance is improved.
The addition of the polycarbonate diol can reduce the dimensional change rate of the rigid foam after the impact of high and low temperature environments. The addition of the polycarbonate diol can prevent the foam from becoming brittle at low temperature, which leads to fracture and damage of the potting adhesive layer.
The preferred polycarbonate diol is any one or more of T5651, T5650J or T5650E of asahi chemical company, japan.
In a preferred embodiment of the present invention, the vegetable oil-modified polyol is a high-functionality vegetable oil polyol containing a benzene ring, the functionality of the vegetable oil polyol is not less than 3, and the preferred functionality range is 3.0 to 5.0.
The vegetable oil modified polyol is prepared by taking castor oil, soybean oil, palm oil and cashew nut shell oil as raw materials;
or vegetable oil modified polyol prepared by taking vegetable oil glycolysis product, polybasic acid or anhydride containing benzene ring and micromolecular polyol as raw materials;
or the vegetable oil polyether polyol is prepared by taking vegetable oil, small molecular polyol and propylene oxide as raw materials.
Preference is given to polyester polyols, polyether polyols or copolymerization products of polyesters and polyether polyols.
In a preferred embodiment of the invention, the vegetable oil polyol has a viscosity of not more than 3000mPa · s.
Vegetable oil polyols prepared from cashew nut shell oil are preferred. The cashew nut shell oil contains a benzene ring and a long carbon chain with 15 carbons, so that the vegetable oil modified polyol has good heat resistance and hydrolytic aging resistance.
The vegetable oil polyol is preferably one or more of products NX-9001, NX-9008 and NX-9014 of Kadelian corporation. The vegetable oil modified polyol has a low acid value which is lower than 5 mgKOH.
Compared with propylene oxide micromolecule polyether polyol prepared by taking glycerol, sorbitol, trimethylolpropane and sucrose as initiators, the vegetable oil polyol with high functionality and benzene rings has better heat resistance and flame retardance.
In a preferred embodiment of the present invention, the flame retardant polyol contains any one or more of phosphorus, nitrogen, and halogen elements, and also contains at least one hydroxyl group.
The flame-retardant polyol reacts with isocyanate to fix the flame-retardant element on the chain segment of polyurethane, so that the migration of the flame-retardant element is prevented, and stable flame retardance is obtained.
The halogen element-containing flame-retardant polyol is preferably IXPLR B251 of Suwei company, Germany, the phosphorus element-containing flame-retardant polyol is preferably Exolite OP550 of Clariant company, and the nitrogen element-containing flame-retardant polyol is preferably Mannich polyol GX-9101 of Kadela company.
The flame retardant is preferably the above flame retardant which is in a liquid state at room temperature, and a combination of a plurality of the above flame retardants is preferably used. The flame retardant has a viscosity at 25 ℃ of less than 300mPaS, preferably less than 100 mPaS. Lower viscosity flame retardants can reduce the viscosity of the A component.
Further, the flame retardant is preferably a hydrolysis-resistant liquid flame retardant which stably exists in the polyol A component, and the hydrolysis-resistant liquid flame retardant is a phosphate or halogenated phosphate flame retardant.
The hydrolysis-resistant phosphate ester flame retardant is preferably K-400, a product of Jiayi chemical industry Co.Ltd, Suzhou; fyrol RDP, product of ICL.
The halogenated phosphate ester flame retardant is preferably a product of RaYNOL FR-300, ZiBORINOL chemical technology Co.
In a preferred embodiment of the invention, the blowing agent is water.
In a preferred embodiment of the present invention, the foam stabilizer is a silane stabilizer. Preferably NIAX L-5440 My Picture, Inc.
In a preferred embodiment of the present invention, the delayed-action catalyst is one or more of a delayed-action metal catalyst or a delayed-action amine blowing catalyst. The delayed metal catalyst is preferably UL-29, a product of Meiji corporation. The delayed action amine catalyst is preferably NIAX C-225, a product of Meiji corporation. The delayed catalyst provides longer cream time and better flowability.
In a preferred embodiment of the present invention, the small molecule chain extender is a small molecule diol containing a branch. Preferred is any one or more of 1,2 propylene glycol, dipropylene glycol or tripropylene glycol.
In a preferred embodiment of the invention, the isocyanate is a high functionality polymeric diphenylmethane diisocyanate (polymeric MDI).
The preferred functionality of the polymeric MDI is not less than 2.8, and the more preferred functionality of the polymeric MDI is not more than 3.2.
The preferred high functionality polymeric MDI is PM400, a wanhua chemical product; -RUBINATE 9257, product of henseme; PAPI20, dow product.
The isocyanate contains more high-functionality polymeric MDI structure, so that the structural strength of the polyurethane foam can be increased, and the dimensional stability and the hydrolysis resistance of the foam can be improved. The flame retardancy and heat resistance of the polyurethane foam can be remarkably improved.
The isocyanate B component is modified polymeric MDI obtained by reacting micromolecular dihydric alcohol with high-functionality polymeric diphenylmethane diisocyanate (polymeric MDI). When the modified polymeric MDI reacts with the polyol component, the micromolecular dihydric alcohol can be introduced into the system, and the mechanical strength, the hardness and the heat resistance of the foam pouring sealant are improved. Compared with the method of adding micromolecular dihydric alcohol into the polyol component, the method solves the problem of layering of micromolecular polyol and other components, and has good storage stability.
In order to obtain a battery pack with high energy density, battery cells in the power battery pack are arranged tightly, and gaps among the battery cells are small. In order to ensure that the pouring sealant can well fill gaps among battery cells, the viscosity of the pouring sealant needs to be controlled in a lower range, so that the viscosity of the component A of the polyhydric alcohol is 500-1000mPa & s; the viscosity of the isocyanate B component is preferably 1100-2000 mPas.
The power battery pack is arranged at the bottom of a vehicle, the battery pack can be subjected to different humidity and temperature and is used under the conditions of high temperature, high humidity or high temperature difference, the battery pouring sealant which does not meet the requirement can change the size, and the pouring sealant with large size change can cause the defects of cracking, bulging, deformation, strength reduction and the like of the power battery pack. Therefore, the battery potting adhesive must ensure dimensional stability under the environment of damp heat and high and low temperature. The size change rate of the battery pouring sealant is reduced by adding polycarbonate polyol, high-functionality isocyanate and benzene ring-containing vegetable oil polyol, and the durability of the power battery pack is ensured.
The invention relates to a preparation method of a polyurethane foam pouring sealant for a battery unit, which comprises the following steps:
(1) the preparation method of the polyol A component comprises the following steps:
adding the special polyester polyol, the vegetable oil modified polyether polyol, the flame-retardant polyether polyol and the flame retardant into a reaction kettle, stirring, then adding the delay catalyst and the foam stabilizer, stirring at 50-60 ℃, cooling to 30 ℃, adding water, continuing, and sealing for storage;
(2) isocyanate B component preparation step:
reacting the micromolecular chain extender with isocyanate in a reaction kettle at 75-85 ℃ for 2-3 hours to obtain a prepolymer of an isocyanate component B with isocyanate content of 28-31%; (3) mixing prepolymers of a polyol A component and an isocyanate B component in a mixing ratio range of 100:80-100, respectively injecting the prepolymers into a charging bucket of a low-pressure casting machine, adjusting the ratio, injecting the mixture into a gap of a shell provided with a battery unit, wherein the injection mass is one fourth to one half of the volume of the gap of the shell provided with the battery unit, and completely filling the gap of the shell provided with the battery unit with foam pouring sealant after foaming to obtain a battery module filled with polyurethane foam; the density of the polyurethane foam in the battery module is 200-450kg/m3And the final curing effect is achieved after curing for 7 days at 25 ℃.
The invention has the following beneficial effects:
1. the polyurethane foam pouring sealant prepared by the invention can reach the V0-grade flame retardant grade.
2. The polyurethane foam pouring sealant prepared by the invention has low density of 200-450kg/m 3. Compared with the common non-foaming pouring sealant, the density is greatly reduced. The dead weight of the battery is greatly reduced.
3. The mixed foam pouring sealant has low viscosity and good fluidity, and can well fill gaps among battery cores.
4. The foam pouring sealant adopts polycarbonate polyol, so that the tensile strength and the elongation of the foam can be increased, and the impact resistance can be improved. Meanwhile, the addition of the polycarbonate diol can improve the dimensional stability of the hard foam after high and low temperature impact resistance.
5. The foam pouring sealant adopts polyfunctional vegetable oil polyalcohol containing benzene rings, so that the product has excellent hydrolysis resistance and stability, and meanwhile, the foam pouring sealant has good heat resistance and low temperature resistance and has higher mechanical strength in high and low temperature environments.
6. The foam pouring sealant adopts high-functionality polymeric MDI, so that the structural strength of the polyurethane foam can be increased, and the dimensional stability and the hydrolysis resistance of the foam can be improved. The flame retardancy and heat resistance of the polyurethane foam can be remarkably improved.
Detailed Description
The working principle of the present invention is further explained with reference to the following embodiments:
the details of the partial products referred to below are given in table 1 below:
TABLE 1
Example 1
Adding 12.5kg of special polyester polyol T5650E, 41.3kg of vegetable oil modified polyol NX-9008,28.0kg of flame-retardant polyether polyol IXPLR B251 and 15.0kg of flame retardant RAYNOL FR-300 into a reaction kettle, stirring, and adding 0.2kg of flame retardant RAYNOL FR-300
Delay catalyst UL-29, 1.5kg foam stabilizer NIAX L-5440 at 50-60 deg.C stirring for 2h, cooling to 30 deg.C after stirring, adding 1.5kg distilled water, stirring for 1h, sealing and storing to obtain polyol A component. Viscosity 780mPa · s;
reacting 1KG of DPG with 99KG PM400 in a reaction kettle at 75-85 ℃ for 2-3 hours to obtain an isocyanate component B with 29.6% of isocyanate and viscosity of 1130mPa & s;
respectively injecting the polyol A component and the prepolymer B component into a charging bucket of a low-pressure casting machine, wherein the ratio of A to B is 100: and 88, injecting the foam pouring sealant into the gap of the shell provided with the battery unit, and completely filling the gap of the shell provided with the battery unit after foaming to obtain the battery module filled with the polyurethane foam. The density of the polyurethane foam in the battery module is 200kg/m3, and the final curing effect is achieved after curing for 7 days at 25 ℃. The performance test indexes are shown in Table 2.
Example 2
10.0kg of special polyester polyol T5650J, 35.0kg of vegetable oil modified polyol NX-9008, 15.0kg of vegetable oil modified polyether polyol NX-9014, 21.0kg of flame retardant polyether polyol Exolite OP550 and 15.8kg of flame retardant Fyrol RDP are added into a reaction kettle for stirring, then 0.8kg of delay catalyst NIAX C-225 and 1.0kg of foam stabilizer NIAX L-5440 are added into the reaction kettle for stirring at 50-60 ℃ for 2 hours, the temperature is reduced to 30 ℃ after the uniform stirring, 1.3kg of distilled water is added into the reaction kettle for stirring for 1 hour, and the mixture is sealed and stored to obtain the polyol A component. Viscosity 970mPa · s;
reacting 2KG of DPG with 98KG PM400 in a reaction kettle at 75-85 ℃ for 2-3 hours to obtain an isocyanate B component with 28.3% of isocyanate and viscosity of 1430mPa & s;
respectively injecting the polyol A component and the prepolymer B component into a charging bucket of a low-pressure casting machine, wherein the ratio of A to B is 100: and 88, injecting the foam pouring sealant into the gap of the shell provided with the battery unit, and completely filling the gap of the shell provided with the battery unit after foaming to obtain the battery module filled with the polyurethane foam. The density of the polyurethane foam in the battery module was 280kg/m3, and the final curing effect was achieved after curing at 25 ℃ for 7 days. The performance test indexes are shown in Table 2.
Example 3
20.0KG of special polyester polyol T5650E, 20.0KG of vegetable oil modified polyol NX-9008, 25.0KG of flame-retardant polyether polyol Exolit OP550, 20KG of cashew nut shell oil Mannich flame-retardant polyol GX-9101 and 10.5KG of flame retardant K-400 are added into a reaction kettle for stirring, then 1.5KG of delay catalyst NIAX C-225 and 2.0KG of foam stabilizer NIAX L-5440 are added into the reaction kettle for stirring at 50-60 ℃ for 2h, the temperature is reduced to 30 ℃ after the uniform stirring, 1.0KG of distilled water is added into the reaction kettle for stirring for 1h, and the mixture is sealed and stored to obtain the polyol A component. Viscosity 580mPa · s;
reacting 0.11KG of 1,2PG with 99.9KG PAPI20 in a reaction kettle at 75-85 ℃ for 2-3 hours to obtain an isocyanate B component with 30.2 percent of isocyanate group content and 1950mPa & s of viscosity;
respectively injecting the polyol A component and the prepolymer B component into a charging bucket of a low-pressure casting machine, wherein the ratio of A to B is 100: and 88, injecting the foam pouring sealant into the gap of the shell provided with the battery unit, and completely filling the gap of the shell provided with the battery unit after foaming to obtain the battery module filled with the polyurethane foam. The density of the polyurethane foam in the battery module was 330kg/m3, and the final curing effect was achieved after curing at 25 ℃ for 7 days. The performance test indexes are shown in Table 2.
Example 4
Adding 11.7kg of special polyester polyol T5651, 45.0kg of vegetable oil modified polyol NX-9001, 35.0kg of flame-retardant polyether polyol IXPLR B251 and 5.0kg of flame retardant RAYNOL FR-300 into a reaction kettle, stirring, and then adding 0.2kg of flame retardant RAYNOL FR-300
Delay catalyst UL-29, 0.8kg delay catalyst NIAX C-225, 1.5kg foam stabilizer NIAX L-5440 at 50-60 deg.C stirring for 2h, cooling to 30 deg.C after stirring, adding 0.8kg distilled water, stirring for 1h, sealing and storing to obtain polyol A component. Viscosity 920mPa · s;
3KG of TPG and 97KG of RUBINATE 9257 react for 2-3 hours at 75-85 ℃ in a reaction kettle to obtain an isocyanate component B with isocyanate content of 28.3 percent and viscosity of 1280mPa & s;
respectively injecting a polyol A component and a prepolymer B component into a charging bucket of a low-pressure casting machine, wherein A: B is 100: and 88, injecting the foam pouring sealant into the gap of the shell provided with the battery unit, and completely filling the gap of the shell provided with the battery unit after foaming to obtain the battery module filled with the polyurethane foam. The density of the polyurethane foam in the battery module was 400kg/m3, and the final curing effect was achieved after curing at 25 ℃ for 7 days. The performance test indexes are shown in Table 2.
Comparative example 1
Adding 57.5kg of vegetable oil polyol NX-9008,28.0kg of flame-retardant polyether polyol IXPLR B251 and 15.0kg of flame retardant RAYNOL FR-300 into a reaction kettle, stirring, adding 0.2kg of delayed catalyst UL-29 and 1.5kg of foam stabilizer NIAX L-5440, stirring for 2 hours at 50-60 ℃, cooling to 30 ℃ after uniformly stirring, adding 1.5kg of distilled water, stirring for 1 hour, and sealing for storage to obtain a polyol A component. A viscosity of 668mPa · s;
reacting 1KG of DPG with 99KG PM400 at 75-85 ℃ for 2-3 hours to obtain an isocyanate B component with 29.6% of isocyanate content and viscosity of 1130mPa & s;
respectively injecting the polyol A component and the prepolymer B component into a charging bucket of a low-pressure casting machine, wherein the ratio of A to B is 100: 88, and the foam pouring sealant completely fills the gap of the shell filled with the battery unit after foaming to obtain the battery module filled with the polyurethane foam. The density of the polyurethane foam in the battery module is 300kg/m3, and the final curing effect is achieved after curing for 7 days at 25 ℃. The performance test indexes are shown in Table 2.
Comparative example 2
Adding 11.7kg of special polyester polyol T5651, 45.0kg of polyether polyol NJ500, 28.0kg of flame-retardant polyether polyol IXPLR B251 and 15.0kg of flame retardant RAYNOL FR-300 into a reaction kettle, stirring, then adding 0.2kg of delay catalyst UL-29 and 1.5kg of foam stabilizer NIAX L-5440, stirring for 2h at 50-60 ℃, cooling to 30 ℃ after uniform stirring, adding 1.5kg of distilled water, stirring for 1h, and sealing and storing to obtain the polyol A component. Viscosity 534mPa · s;
reacting 1KG of DPG with 99KG PM400 at 75-85 ℃ for 2-3 hours to obtain an isocyanate B component with 29.6% of isocyanate content and viscosity of 1130mPa & s;
respectively injecting the polyol A component and the prepolymer B component into a charging bucket of a low-pressure casting machine, wherein the ratio of A to B is 100: 88, and the foam pouring sealant completely fills the gap of the shell filled with the battery unit after foaming to obtain the battery module filled with the polyurethane foam. The density of the polyurethane foam in the battery module is 300kg/m3, and the final curing effect is achieved after curing for 7 days at 25 ℃. The performance test indexes are shown in Table 2.
Comparative example 3
Adding 11.7kg of special polyester polyol T5651, 45.0kg of vegetable oil modified polyol NX-9001, 35.0kg of flame-retardant polyether polyol IXPLR B251 and 5.0kg of flame retardant RAYNOL FR-300 into a reaction kettle, stirring, and then adding 0.2kg of flame retardant RAYNOL FR-300
Delay catalyst UL-29, 0.8kg delay catalyst NIAX C-225, 1.5kg foam stabilizer NIAX L-5440 at 50-60 deg.C stirring for 2h, cooling to 30 deg.C after stirring, adding 0.8kg distilled water, stirring for 1h, sealing and storing to obtain polyol A component. Viscosity 920mPa · s;
reacting 3KG of TPG with 97KG PM200 in a reaction kettle at 75-85 ℃ for 2-3 hours to obtain an isocyanate component B with isocyanate content of 28.3% and viscosity of 680mPa & s;
respectively injecting a polyol A component and a prepolymer B component into a charging bucket of a low-pressure casting machine, wherein A: B is 100: and 88, injecting the foam pouring sealant into the gap of the shell provided with the battery unit, and completely filling the gap of the shell provided with the battery unit after foaming to obtain the battery module filled with the polyurethane foam. The density of the polyurethane foam in the battery module is 300kg/m3, and the final curing effect is achieved after curing for 7 days at 25 ℃. The performance test indexes are shown in Table 2.
Comparative example 4
Adding 12.5kg of special polyester polyol T5650E, 41.3kg of vegetable oil modified polyol NX-9008 and 43.0kg of flame retardant polyether polyol IXPLR B251 into a reaction kettle, stirring, adding 0.2kg of delay catalyst UL-29 and 1.5kg of foam stabilizer NIAX L-5440, stirring for 2 hours at 50-60 ℃, cooling to 30 ℃ after uniform stirring, adding 1.5kg of distilled water, stirring for 1 hour, and sealing for storage to obtain the polyol A component. Viscosity 2880mPa · s;
reacting 1KG of DPG with 99KG PM400 in a reaction kettle at 75-85 ℃ for 2-3 hours to obtain an isocyanate component B with 29.6% of isocyanate and viscosity of 1130mPa & s;
respectively injecting the polyol A component and the prepolymer B component into a charging bucket of a low-pressure casting machine, wherein the ratio of A to B is 100: and 100, injecting the foam pouring sealant into the gap of the shell provided with the battery unit, and completely filling the gap of the shell provided with the battery unit after foaming to obtain the battery module filled with the polyurethane foam. The density of the polyurethane foam in the battery module is 200kg/m3, and the final curing effect is achieved after curing for 7 days at 25 ℃. The performance test indexes are shown in Table 2.
TABLE 2 Performance test indexes
1. The flowability test criteria in table 2 are:
a sample of 500 to 1000 g of the potting adhesive composition was poured into a mould of dimensions 35cm x15cm x 20cm with 48 upright cylindrical cells of diameter 3.5cm and height 18cm in the mould using a low pressure foaming machine and tested at ambient temperature of 25 ℃. After the potting adhesive is cured, the level of the potting adhesive cured around the cylindrical battery unit is observed by naked eyes, and the following rating is given to the surface of the potting adhesive after being cured: extremely poor, good and excellent. "Excellent" corresponds to a tested position within the mold with less than 0.5cm of horizontal variation around the cell. The difference corresponds to the tested position in the mold, and the horizontal variation around the battery unit is more than or equal to 3cm
2. The mechanical property is tested by GB/T528-2009, and the test sample is cut into dumbbell shape and right angle for testing the mechanical property, the size is 25mm multiplied by 115mm multiplied by 3mm, and the testing temperature is 25 ℃.
3. The flame retardant property is tested by adopting GBT2408-2008, and a test sample is cut into the dimensions of 13mm multiplied by 125mm multiplied by 3mm, and the test temperature is 25 ℃.
4. The dimensional change rate was measured by GB T8811-.
5. The volume resistivity is tested by GB/T1410-2006, the sample is subjected to an aging test at 85 ℃/85% humidity, and the performance is tested after the sample is stored for 1000 hours in a constant-temperature constant-humidity aging box and is stored for 24 hours at 25 ℃/50% humidity after being taken out.
6. And (3) performing high-low temperature cyclic aging test at-40 ℃ to 85 ℃, storing the sample in a high-low temperature cyclic aging box for 1000h, wherein each 1h is a cyclic period, taking out the sample, storing the sample for 24h at 25 ℃/50% humidity, and testing the performance.
6. The test standard of the tensile strength loss rate after the damp heat aging is GB/T528-2009.
As can be seen from the examples and comparative examples:
comparative example 1 compared to example 1, the dimensional change ratio% (-40 ℃ -85 ℃ cycle 1000h) increased for all vegetable oil polyols and for special polyester polyols. The addition of the special polyester polyol improves the high and low temperature impact resistance of the foam pouring sealant, prevents the foam structure from brittle fracture, curling, bulging and the like under the action of long-term high and low temperature circulation, and practically reduces the size change rate after high and low temperature circulation.
Compared with the example 1, the common rigid foam polyether is adopted to replace the vegetable oil polyalcohol, so that the flame retardance of the foam pouring sealant is reduced, the tensile strength after hydrolysis resistance is reduced, and the dimensional stability is reduced. The vegetable oil polyalcohol has better hydrolysis resistance and heat resistance than common hard foam polyether, so the performance is better.
Comparative example 3 compared to example 4, the% dimensional change (% 40 ℃ C. -85 ℃ C. cycle 1000h) increased and the% dimensional change (% 85 ℃ C./85% humidity, 1000h) increased by replacing the higher functionality isocyanate with the slightly lower functionality isocyanate PM 200.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A polyurethane foam pouring sealant for a battery unit is composed of a polyol A component and an isocyanate B component, and is characterized in that the polyol A component comprises the following components in parts by weight:
the isocyanate B component comprises the following components in parts by weight:
0-3 parts of a micromolecular chain extender;
97-100 parts of isocyanate;
the special polyester polyol is polycarbonate polyol, and the molecular weight is 400-1500.
2. The polyurethane foam potting adhesive for battery cells as claimed in claim 1, wherein the functionality of the polycarbonate polyol is 2.
3. The polyurethane foam potting adhesive for battery cells as claimed in claim 1, wherein the vegetable oil-modified polyol is a vegetable oil polyol having a high functionality and containing a benzene ring, and the functionality of the vegetable oil polyol is not less than 3.
4. The polyurethane foam potting adhesive for battery cells as claimed in claim 1, wherein the vegetable oil-modified polyol is a vegetable oil-modified polyol prepared from castor oil, soybean oil, palm oil, cashew nut shell oil;
or vegetable oil modified polyol prepared by taking vegetable oil glycolysis product, polybasic acid or anhydride containing benzene ring and micromolecular polyol as raw materials;
or the vegetable oil polyether polyol is prepared by taking vegetable oil, small molecular polyol and propylene oxide as raw materials;
the vegetable oil polyol has a viscosity of not more than 3000mPa · s.
5. The polyurethane foam potting adhesive for battery cells as claimed in claim 3 or 4, wherein the vegetable oil-modified polyol acid value is less than 5 mgKOH.
6. The polyurethane foam potting adhesive for battery cells as claimed in claim 1, wherein the flame retardant polyol contains any one or more of phosphorus, nitrogen, halogen elements and at least one hydroxyl group.
7. The polyurethane foam potting adhesive for battery cells as claimed in claim 6, wherein the viscosity of the flame retardant is less than 300mPaS at 25 ℃.
8. The polyurethane foam potting adhesive for battery cells as claimed in claim 1, wherein the blowing agent is water;
the foam stabilizer is a silane stabilizer;
the delayed catalyst is one or more of delayed metal catalyst or delayed amine foaming catalyst;
the micromolecular chain extender is micromolecular dihydric alcohol containing a branched chain.
9. The polyurethane foam potting adhesive for battery cells as claimed in claim 1, wherein the isocyanate is high-functionality polymeric diphenylmethane diisocyanate (polymeric MDI), the functionality of the polymeric MDI being not less than 2.8;
the viscosity of the component A of the polyol is 500-1000 mPas; the viscosity of the isocyanate B component is preferably 1100-2000 mPas.
10. The method for preparing the polyurethane foam potting adhesive for battery cells as claimed in any one of claims 1 to 9, comprising the steps of:
(1) the preparation method of the polyol A component comprises the following steps:
adding the special polyester polyol, the vegetable oil modified polyether polyol, the flame-retardant polyether polyol and the flame retardant into a reaction kettle, stirring, then adding the delay catalyst and the foam stabilizer, stirring at 50-60 ℃, cooling to 30 ℃, adding water, continuing, and sealing for storage;
(2) isocyanate B component preparation step:
reacting the micromolecular chain extender with isocyanate in a reaction kettle at 75-85 ℃ for 2-3 hours to obtain a prepolymer of an isocyanate component B with isocyanate content of 28-31%;
(3) mixing prepolymers of a polyol A component and an isocyanate B component in a mixing ratio range of 100:80-100, respectively injecting the prepolymers into a charging bucket of a low-pressure casting machine, adjusting the ratio, injecting the mixture into a gap of a shell provided with a battery unit, wherein the injection mass is one fourth to one half of the volume of the gap of the shell provided with the battery unit, and completely filling the gap of the shell provided with the battery unit with foam pouring sealant after foaming to obtain a battery module filled with polyurethane foam; the density of the polyurethane foam in the battery module is 200-450kg/m3And the final curing effect is achieved after curing for 7 days at 25 ℃.
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| CN116042007A (en) * | 2022-12-29 | 2023-05-02 | 上海汇得科技股份有限公司 | Flame-retardant insulating coating for power battery and preparation method thereof |
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