CN114621721B - Polyurethane pouring sealant for low-density heat-insulating power battery - Google Patents
Polyurethane pouring sealant for low-density heat-insulating power battery Download PDFInfo
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- CN114621721B CN114621721B CN202210338617.9A CN202210338617A CN114621721B CN 114621721 B CN114621721 B CN 114621721B CN 202210338617 A CN202210338617 A CN 202210338617A CN 114621721 B CN114621721 B CN 114621721B
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 90
- 239000004814 polyurethane Substances 0.000 title claims abstract description 90
- 239000000565 sealant Substances 0.000 title claims abstract description 62
- 239000004005 microsphere Substances 0.000 claims abstract description 94
- 239000000945 filler Substances 0.000 claims abstract description 33
- 229920005862 polyol Polymers 0.000 claims abstract description 28
- 150000003077 polyols Chemical class 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 23
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims description 34
- 230000001070 adhesive effect Effects 0.000 claims description 34
- 238000004382 potting Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000013530 defoamer Substances 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 230000033444 hydroxylation Effects 0.000 claims description 5
- 238000005805 hydroxylation reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 abstract description 8
- 239000000306 component Substances 0.000 description 59
- 230000000052 comparative effect Effects 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- 238000009472 formulation Methods 0.000 description 15
- 239000003292 glue Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 230000002411 adverse Effects 0.000 description 5
- 239000004359 castor oil Substances 0.000 description 5
- 235000019438 castor oil Nutrition 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- SPAUYKHQVLTCOL-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C SPAUYKHQVLTCOL-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 208000034699 Vitreous floaters Diseases 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PUTZDSUOPCPZMG-UHFFFAOYSA-N P(=O)(O)(O)O.C1(=CC=CC=C1)C(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound P(=O)(O)(O)O.C1(=CC=CC=C1)C(C1=CC=CC=C1)C1=CC=CC=C1 PUTZDSUOPCPZMG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000009417 prefabrication Methods 0.000 description 1
- 231100000817 safety factor Toxicity 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- 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
- C09J175/08—Polyurethanes from polyethers
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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 provides a polyurethane pouring sealant for a low-density heat-insulating battery, which comprises the following components in percentage by weight: 20 to 48.75 percent of polyol, 7.5 to 30 percent of isocyanate and 15 to 50 percent of low-density filler; the low-density filler is a hollow microsphere; the molar ratio of isocyanate functional groups of the isocyanate to hydroxyl functional groups of the polyol is from 1 to 1.08. The hollow microspheres with the modified surfaces can be well dispersed in the polyurethane pouring sealant to form a compact and mutually independent cavity structure, so that the polyurethane pouring sealant has excellent heat insulation performance and low density.
Description
Technical Field
The invention belongs to the technical field of polyurethane pouring sealants, and particularly relates to a polyurethane pouring sealant for a low-density heat-insulation power battery.
Background
Along with the deep popularization of the environmental protection concept, the electric energy source is gradually recognized as an environmental protection new energy source, and further, the electric motor of the automobile and the two-wheel vehicle is popularized. The power battery is used as a core component of an electromotive system and consists of a plurality of battery cells (namely electric cores), when the battery cells are pierced by a diaphragm due to various reasons such as mechanical deformation, extrusion, vibration and the like, the internal positive electrode and the negative electrode are in direct contact to cause short circuit, a large amount of heat can be instantaneously generated by the internal short circuit, and the whole power battery is in thermal runaway due to rapid conduction of the heat, so that adverse effects are generated on the batteries and devices around the short circuit battery. In order to fully ensure the safety factors of the lithium battery, such as heat dissipation, buffering and damping, water resistance, flame retardance and explosion resistance, electromagnetic interference resistance and other performance indexes, generally, a potting material is used.
In the potting adhesive industry, there are mainly three potting material systems, namely epoxy potting adhesive, silicone potting adhesive and polyurethane potting adhesive. The polyurethane pouring sealant has good low temperature resistance, wide adjustment range, high adhesive strength, high cohesive strength and good damping efficiency, and gradually becomes the first choice of the power battery pouring sealant.
The conventional polyurethane pouring sealant is usually added with fillers such as aluminum oxide, calcium carbonate and the like, so that the density of glue water is increased while the heat conducting performance of the glue is enhanced, the pouring sealant has higher heat conducting coefficient, and the heat insulation effect cannot be better achieved when a large amount of heat is generated by internal short circuit of a power battery, so that the problem that adverse effects are caused to other peripheral battery cells by thermal runaway cannot be relieved.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the polyurethane pouring sealant for the low-density heat-insulation power battery, which solves the problems of overhigh density and overhigh heat conductivity coefficient in the polyurethane pouring sealant in the prior art and meets the new requirements of light weight and heat insulation in the field of power batteries.
According to the first aspect of the invention, the polyurethane pouring sealant for the low-density heat-insulating power battery comprises the following components in percentage by weight: 20 to 48.75 percent of polyol, 7.5 to 30 percent of isocyanate and 15 to 50 percent of low-density filler; the low-density filler is a hollow microsphere; the molar ratio of isocyanate functional groups of the isocyanate to hydroxyl functional groups of the polyol is from 1 to 1.08. The isocyanate functional groups of the isocyanate are similar to the hydroxyl functional groups of the polyol, so that the isocyanate and the polyol can be fully reacted. According to the invention, the hollow microspheres with the hollow structures are introduced into the polyurethane pouring sealant substrate, so that the heat conductivity coefficient and the overall density of the polyurethane pouring sealant product can be effectively reduced, the polyurethane pouring sealant for the low-density heat-insulating power battery provided by the invention not only has good heat insulation effect, but also can be kept light, and the polyurethane pouring sealant can be applied to a lithium battery, so that the heat transmission generated instantly can be effectively blocked under emergency conditions, and the occurrence of thermal runaway condition can be avoided. Regarding the introduction of hollow structures in the glue layer, the prior art generally forms hollow microbubbles in the glue layer by means of chemical foaming, however, the foaming effect of such chemical foaming is greatly affected by the process field, and it is difficult to controllably and batchwise form hollow structures with similar morphology and uniform distribution in the glue layer, so that the controllability of the pouring sealant product can be adversely affected. The molding process of the hollow microspheres is controllable, hollow microspheres with similar shapes can be obtained in a batch prefabrication mode, and the hollow microspheres are filled in glue so that the glue can be kept uniform, and therefore the stability and controllability of the volume, the glue and the performance of the pouring sealant are ensured. In addition, compared with the hollow microbubbles formed by chemical foaming, the hollow microspheres have obviously higher structural strength, and the polyurethane pouring sealant formed by curing the glue can have enough strength and mechanical property without collapsing the pouring sealant caused by the introduction of the hollow structure. In addition, the hollow microspheres are doped into the polyurethane potting adhesive, and the spherical hollow microspheres can play a role of a ball bearing during the adhesive coating construction, so that the polyurethane potting adhesive is beneficial to spreading on a construction carrier, and the construction performance of the polyurethane potting adhesive can be optimized. After the glue is solidified and formed, the hollow microspheres in the colloid structure can offset the internal stress in the specification mode based on the spherical structure, and the uneven shrinkage condition can not occur, so that the polyurethane pouring sealant containing the hollow microspheres has good dimensional stability and is not easy to deform.
Preferably, the density of the hollow microspheres is 0.2-0.6g.cm -3 。
Preferably, the hollow microsphere has a thermal conductivity of 0.03-0.08W.m -1 ·K -1 。
The performance parameters of the hollow microspheres meet the indexes, so that the overall density of the polyurethane pouring sealant prepared by the method can reach approximately 0.4 g.cm -3 The heat conductivity coefficient can be reduced to 0.05 W.m -1 ·K -1 。
Preferably, the hollow microspheres comprise at least one of hollow glass microspheres, hollow silica microspheres, hollow phenolic resin microspheres.
Preferably, the low density filler comprises hollow glass microspheres.
Preferably, the hollow glass microspheres comprise at least one of the product designations GS20, GS25, GS32 produced by the saddle mountain mining institute.
Compared with other hollow microspheres, the hollow glass microspheres adopted in the scheme have better strength and lower cost in the polyurethane adhesive layer prepared by the hollow glass microspheres. The hollow glass microspheres have regular spherical structures, so that the total internal stress of the hollow glass microspheres in all directions in the polyurethane adhesive layer is zero, and the polyurethane adhesive layer prepared by the hollow glass microspheres still maintains good dimensional stability under the condition of overheating or supercooling.
Preferably, the polyol comprises at least one of a polyether polyol, a bio-based polyol.
Preferably, the isocyanate comprises at least one of diphenylmethane diisocyanate and diphenylmethane polyisocyanate.
Preferably, the polyether polyol comprises at least one of a difunctional polyether polyol with a molecular weight of 400-3000 and a trifunctional polyether polyol with a molecular weight of 500-5000; the biological polyol is castor oil or castor oil modified substance.
Preferably, the polyether polyol comprises at least one of the product brands DL-1000D, DL-2000D, MN, EP-330N manufactured by Shandong blue Star Dong Co., ltd; the biological polyol comprises at least one of castor oil produced by Basiff corporation, the product brand is Sovermol-750, and the product brand is Sovermol-805.
Preferably, the MDI comprises at least one of liquefied MDI, MDI-50.
Preferably, the MDI comprises liquefied MDI.
Preferably, the liquefied MDI comprises CDMDI-100L manufactured by vanity chemical group co.
According to another aspect of the invention, the invention provides a method for preparing the polyurethane pouring sealant for the low-density heat-insulating power battery, which comprises the following steps: preparing a component A: mixing the polyol and the low-density filler to obtain a component A; and (3) preparing a component B: mixing isocyanate and low-density filler to obtain a component B; preparing polyurethane pouring sealant: and mixing the component A and the component B to prepare the polyurethane pouring sealant. As the isocyanate is easy to react with water molecules to generate gas, so that bubbles in the product are formed, the side reaction of the isocyanate is reduced by applying vacuum dehydration in the step of preparing the component A, the sufficient reaction of the isocyanate and the polyol during the mixing of the component A, B is ensured, and meanwhile, the adverse effect of the bubbles generated by the reaction of the isocyanate and the water on the polyurethane pouring sealant is avoided. In order to fully mix the low-density filler in the polyurethane pouring sealant, the low-density filler is firstly and primarily mixed in the reaction monomer polyol and isocyanate respectively in the preparation method, so that the low-density filler can be well dispersed in the A, B component which is prepared by the low-density filler, and further, the polyurethane pouring sealant formed by mixing the A, B components can also have good dispersibility. In the mixing process of the low-density filler and the organic component, the low-density filler with small specific gravity can be inevitably gathered towards the upper part of the organic component, and compared with the preparation of the pouring sealant by a one-step method, the low-density filler in the scheme is primarily mixed with A, B components respectively containing two reaction monomers, so that the low-density filler can form a compact and mutually independent cavity structure in the polyurethane pouring sealant, and further, the polyurethane pouring sealant is ensured to have excellent heat insulation performance and maintain good mechanical performance.
Preferably, the mixing ratio of the A component and the B component is 1-3:1.
Preferably, the mixing ratio of the A component and the B component is 1:1.
Preferably, before the low-density filler is used for preparing the A component and the B component, the method further comprises the step of modifying the hollow microspheres, specifically: the surface of the hollow microsphere is hydroxylated by sodium hydroxide solution and then treated by silane coupling agent.
Preferably, the hollow microspheres are pre-dispersed with sodium citrate prior to surface hydroxylation.
Preferably, the specific operations for hydroxylating the surface of the hollow microsphere are: adding the hollow microspheres into a sodium citrate solution with the concentration of 0.1mol/L for ultrasonic dispersion for 0.5-1.5 hours until the hollow microspheres are fully dispersed, then adding a NaOH solution with the concentration of 0.5mol/L into the hollow microspheres for continuous ultrasonic dispersion for 0.5-1.5 hours until the hollow microspheres are fully dispersed, then heating, refluxing and stirring for 0.5-1.5 hours at the temperature of 90 ℃, washing, filtering until the PH is neutral, and drying for standby. The hollow microspheres are well pre-dispersed in the sodium citrate solution due to electrostatic repulsion, so that more hollow microspheres are fully subjected to surface hydroxylation in the NaOH solution, more hydroxyl groups are exposed on the surfaces of more hollow microspheres, and the silane coupling agent can form better coating on the surfaces of the hollow microspheres, so that the compatibility of the hollow microspheres and matrix resin is enhanced.
Preferably, the silane coupling agent is 3- (2, 3-glycidoxy) propyl trimethoxysilane (KH 560).
Preferably, the specific operation of treating the hollow microspheres with the silane coupling agent is as follows: placing the hollow microsphere subjected to surface hydroxylation on CH 3 CH 2 And (3) in a mixed solution with the mass ratio of OH to KH560 of 100:10, sealing and stirring for 1-1.5 hours at normal temperature, standing and layering, filtering out upper-layer floaters, and drying to obtain the final modified hollow microspheres. The alkyl long chain on the surface of the hollow microsphere coated by the silane coupling agent can endow the hollow microsphere with lipophilicity, so that the dispersibility of the hollow microsphere in organic components can be improved.
Preferably, the step of preparing the component A further comprises the operation of adding a catalyst, a chain-extending cross-linking agent, a flame retardant and a defoaming agent, and specifically comprises the following steps: mixing the polyol, the chain extension crosslinking agent, the flame retardant and the defoamer at 100-120 ℃ and dehydrating in vacuum for 2-4 hours, cooling the reaction system to 55-65 ℃ when the water content of the reaction system is lower than 500ppm, then continuously adding the catalyst and the hollow microspheres into the first mixture, cooling, and simultaneously continuously maintaining vacuum and stirring for 0.5-1 hour to obtain a component A; in the step of preparing the component A, the ratio of the feeding amount of the polyatomic alcohol, the hollow microsphere, the catalyst, the chain extension crosslinking agent, the flame retardant and the defoaming agent is 20-32.5:5-25:0-0.05:0.5-2.5:5-10:0-0.1 according to the mass ratio.
Preferably, the step of preparing the component B further comprises the operation of adding a flame retardant and an antifoaming agent, specifically: mixing isocyanate, hollow microspheres, a flame retardant and a defoaming agent, and stirring for 1-2 hours at normal temperature under vacuum to obtain a component B; in the step of preparing the component B, the ratio of the feeding amount of isocyanate, hollow microspheres, flame retardant and defoamer is 15-30:15-25:5-10:0-0.25 according to the mass ratio.
Preferably, the stirring speed in the step of preparing the A component and the B component is 30-60 rpm, and the vacuum degree is less than-94 KPa.
Preferably, the catalyst comprises at least one of organotin-based, organobismuth-based, organozinc-based catalysts.
Preferably, the catalyst comprises an organobismuth composite catalyst.
Preferably, the organobismuth composite catalyst comprises CUCAT-GF02, available from Guangzhou Yourun synthetic materials Co.
Preferably, the chain-extending cross-linking agent functional group is hydroxyl and the functionality is 2-3.
Preferably, the chain-extending crosslinking agent comprises at least one of 1, 4-butanediol, 1, 3-propanediol, diethylene glycol, dipropylene glycol, trimethylolpropane, trimethylolethane and glycerol.
Preferably, the flame retardant comprises at least one of aluminum hypophosphite, melamine, triphenyl phosphate, resorcinol bis (diphenyl phosphate), bisphenol a-bis (diphenyl phosphate), tricresyl phosphate, and toluene diphenyl phosphate.
Preferably, the defoaming agent includes at least one of an organosilicon-based defoaming agent and a polymer-based defoaming agent.
Preferably, the defoamer comprises at least one of the product brands BYK-066N, BYK-535 manufactured by Pick chemical Co.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
Example 1
Table 1 is a formulation for the present example used to prepare the a-component of the polyurethane potting adhesive. The low-density filler in the following table is a surface-treated low-density filler.
Table 1 formulation for preparing polyurethane pouring sealant a component
Table 2 is the formulation of the B component used to prepare the polyurethane potting adhesive of this example. The low-density filler in the following table is a surface-treated low-density filler.
Table 2 formulation for preparing polyurethane pouring sealant B component
The raw materials required for the formulation of the a and B components were prepared as in tables 1 and 2 above, and the polyurethane potting adhesive in this example was prepared as follows:
step 1, modifying low-density filler: placing hollow glass microsphere GS20 on CH 3 CH 2 And (3) in a mixed solution with the mass ratio of OH to KH560 of 100:10, sealing and stirring for 1 hour at normal temperature, standing for layering, filtering out upper-layer floaters, and drying to obtain the final modified hollow microsphere.
Step 2, preparing the component A: adding castor oil, DL-2000D, dipropylene glycol and diphenyl toluene phosphate into a reaction kettle 1, stirring uniformly at 100-120 ℃ and dehydrating in vacuum, continuously adding GF02 and treated hollow glass microspheres GS20 into the reaction kettle 1 when the water content is lower than 500ppm and the temperature is reduced to 55-65 ℃, continuously maintaining vacuum and reducing the temperature, and stirring for 0.5-1 h to obtain the component A.
Step 3, preparation of a component B: adding CDMDI-100L, toluene diphenyl phosphate, hollow glass microspheres GS20 and BYK-A535 into a reaction kettle 2, and stirring for 1-2 h at normal temperature under vacuum to obtain a component B.
And 4, preparation of polyurethane pouring sealant: and (3) respectively stirring the A, B components in respective charging drums before use, transferring the components into a transfer tank of the glue pouring equipment, maintaining stirring, vacuum defoaming for 3-5 min, breaking vacuum by nitrogen, and mixing in the glue pouring equipment while stirring to obtain the polyurethane pouring sealant.
Wherein, the stirring rotation speed in the step 2 and the step 3 is 30-60 rpm, and the vacuum degree is less than-94 KPa; in the step 4, the stirring rotation speed is 5-20 rpm, and the vacuum degree is less than-94 KPa.
Example 2
The required raw materials were prepared with reference to the formulation for preparing the a-and B-components in example 1, and the polyurethane potting adhesive in this example was prepared as follows:
step 1, modifying low-density filler: firstly, adding hollow glass microspheres GS20 into a sodium citrate solution with the concentration of 0.1mol/L for ultrasonic dispersion for 0.5-1.5 hours until the hollow glass microspheres are fully dispersed, then adding a NaOH solution with the concentration of 0.5mol/L into the hollow glass microspheres for continuous ultrasonic dispersion for 0.5-1.5 hours until the hollow glass microspheres are fully dispersed, then heating, refluxing and stirring for 0.5-1.5 hours at the temperature of 90 ℃, washing, filtering until the PH is neutral, and drying for standby. Next, the surface-hydroxylated hollow glass microsphere GS20 was placed on CH 3 CH 2 And (3) in a mixed solution with the mass ratio of OH to KH590 of 100:10, sealing and stirring for 1 hour at normal temperature, standing for layering, filtering out upper-layer floaters, and drying to obtain the final modified hollow microsphere.
Step 2, preparing the component A: adding castor oil, DL-2000D, dipropylene glycol and diphenyl toluene phosphate into a reaction kettle 1, stirring uniformly at 100-120 ℃ and dehydrating in vacuum, continuously adding GF02 and treated hollow glass microspheres GS20 into the reaction kettle 1 when the water content is lower than 500ppm and the temperature is reduced to 55-65 ℃, continuously maintaining vacuum and reducing the temperature, and stirring for 0.5-1 h to obtain the component A.
Step 3, preparation of a component B: adding CDMDI-100L, toluene diphenyl phosphate, hollow glass microspheres GS20 and BYK-A535 into a reaction kettle 2, and stirring for 1-2 h at normal temperature under vacuum to obtain a component B.
And 4, preparation of polyurethane pouring sealant: and (3) respectively stirring the A, B components in respective charging drums before use, transferring the components into a transfer tank of the glue pouring equipment, maintaining stirring, vacuum defoaming for 3-5 min, breaking vacuum by nitrogen, and mixing in the glue pouring equipment while stirring to obtain the polyurethane pouring sealant.
Wherein, the stirring rotation speed in the step 2 and the step 3 is 30-60 rpm, and the vacuum degree is less than-94 KPa; in the step 4, the stirring rotation speed is 5-20 rpm, and the vacuum degree is less than-94 KPa.
Example 3
The polyurethane pouring sealant of this comparative example was prepared with reference to the polyurethane pouring sealant preparation method provided in example 2: the preparation of the formulation of the component A and the component B according to the raw materials required in the preparation of the example 1, the sodium citrate in the step 1 in the preparation method of the polyurethane pouring sealant provided in the example 2 is replaced by sodium dodecyl benzene sulfonate, and other specific operations and parameter settings are strictly consistent with those in the preparation method of the polyurethane pouring sealant provided in the example 2.
Example 4
The polyurethane pouring sealant of this comparative example was prepared with reference to the polyurethane pouring sealant preparation method provided in example 2: the preparation of the raw materials required for the formulation of the component A and the component B according to the preparation method of the example 1 is carried out by replacing sodium citrate in the step 1 in the preparation method of the polyurethane pouring sealant provided in the example 2 with sodium dodecyl sulfate, and other specific operation and parameter settings are strictly consistent with those of the preparation method of the polyurethane pouring sealant provided in the example 2.
Comparative example 1
Table 3 is the formulation of the comparative example used to prepare the a-component polyurethane potting adhesive. The low density filler in the following table is a surface treated filler.
Table 3 formulation for preparing polyurethane pouring sealant a component
Table 4 is the formulation of the comparative example used to prepare the B component of the polyurethane potting adhesive. The filler in the following table is the surface-treated filler.
Table 4 formulation for preparing polyurethane pouring sealant B component
The polyurethane pouring sealant of this comparative example was prepared with reference to the polyurethane pouring sealant preparation method provided in example 1: the hollow glass microspheres GS20 in steps 1 to 3 of the polyurethane pouring sealant preparation method provided in example 1 were replaced with spherical alumina according to the raw materials required for preparing the formulations of the component a and the component B in the above tables 3 and 4, and other specific operations and parameter settings were strictly consistent with the polyurethane pouring sealant preparation method provided in example 1.
Comparative example 2
The polyurethane foam of this comparative example was prepared by referring to the preparation method of polyurethane foam in patent CN 113980233A.
Comparative example 3
The raw materials were prepared with reference to the formulation for preparing the polyurethane potting adhesive of example 1, and the polyurethane potting adhesive of this comparative example was prepared with reference to the method for preparing the polyurethane potting adhesive of example 1, in which the silane coupling agent KH560 used for the modification treatment of the hollow glass microsphere GS20 in step 1 was replaced with KH590.
Comparative example 4
The raw materials were prepared with reference to the formulation for preparing the polyurethane potting adhesive of example 1, and the polyurethane potting adhesive of this comparative example was prepared with reference to the method for preparing the polyurethane potting adhesive of example 1, in which the silane coupling agent KH560 used for the modification treatment of the hollow glass microsphere GS20 in step 1 was replaced with KH550.
Test case
1. Experimental construction mode
The polyurethane potting adhesives prepared in examples 1 to 4 and comparative examples 1 to 4 were used for the performance test.
Density testing: the polyurethane potting adhesives prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to density testing by a gravity method.
And (3) heat conduction coefficient test: the polyurethane potting adhesives prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to thermal conductivity testing with reference to the standard of thermal protection plate method, test method for thermal conductivity of plastics, GB 3399-1982.
Tensile strength and elongation test: the polyurethane potting adhesives prepared in examples 1 to 4 and comparative examples 1 to 4 were tested for tensile length and elongation with reference to GB/T528-1998 Standard of measurement of tensile stress Strain properties of vulcanized rubber or thermoplastic rubber.
2. Experimental results
The results of the performance tests performed on the polyurethane potting adhesives prepared in examples 1 to 4 and comparative examples 1 to 4 are shown in table 5: experimental results show that referring to the example 1 and the comparative example 1 in the following Table 5, the polyurethane pouring sealant prepared by the hollow glass microspheres has lower density and heat conductivity coefficient than the polyurethane pouring sealant prepared by the solid silica microspheres, and the hollow glass microspheres adopted in the invention can better meet the requirement of light weight of the power battery while having better heat insulation performance, and moreover, although the mechanical performance of the example 1 is reduced compared with that of the comparative example 1, the normal use of the polyurethane pouring sealant is not affected. In examples 2 to 4, the hollow microspheres are subjected to surface hydroxylation treatment by using a NaOH solution after being pre-dispersed by adopting an anionic surfactant, so that more hydroxyl groups are exposed on the surfaces of the hollow microspheres, the silane coupling agent is ensured to have better grafting rate on the surfaces of the hollow microspheres, and further, the tight connectivity of the hollow microspheres and matrix resin polyurethane is ensured, so that examples 2 to 4 have better tensile strength compared with example 1, wherein example 2 has better tensile strength, the best pre-dispersion effect of sodium citrate on the hollow microspheres is represented, more surfaces of the hollow microspheres are hydroxylated by the NaOH solution, the grafting rate of the silane coupling agent on the surfaces of the hollow microspheres is highest, and the hollow microspheres are connected with matrix resin most tightly, so that the hollow microspheres have better tensile strength. In comparative example 2, although the density and thermal conductivity are smaller than those of example 1, the tensile strength is almost an order of magnitude lower than that of example 1 because the chemical foaming method is used to form a hollow structure in the polyurethane foam to reduce the density of the polyurethane material in comparative example 2, so that the polyurethane foam has extremely low mechanical properties and cannot meet the normal use requirements of the potting material for power batteries. In addition, the polyurethane foam adhesive has extremely poor flame retardant property, is easy to burn when sparks are generated due to short circuit in the power battery, and has high potential hazard. In comparative examples 3 and 4, the hollow microspheres are surface-modified by using silane coupling agents KH590 and KH560 of another type, and compared with comparative examples 3 and 4, the results show that the polyurethane prepared by using the hollow microspheres modified by KH560 has higher tensile strength and elongation than the hollow microspheres modified by KH590 and KH550, because the hollow microspheres comprise active groups such as mercapto groups and amino groups in KH590 and KH550 respectively and are easy to react with isocyanate groups in isocyanate, on one hand, the reaction of the active groups with the isocyanate groups leads to insufficient reaction of the polyol with the isocyanate, and on the other hand, the reaction of the active groups with the isocyanate groups leads to increased viscosity of the B component, so that the hollow microspheres are locally agglomerated, the mixing of the hollow microspheres with the B component is influenced, and the finally formed polyurethane pouring sealant is adversely affected.
TABLE 5 results of test on the related Properties of the polyurethane potting adhesive prepared in examples 1 to 4 and comparative examples 1 to 4
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The polyurethane pouring sealant for the low-density heat-insulating power battery is characterized by comprising the following components in percentage by weight: 20-48.75% of polyol, 7.5-30% of isocyanate and 34.375-50% of low-density filler; the low-density filler is a hollow microsphere; the molar ratio of isocyanate functional groups of the isocyanate to hydroxyl functional groups of the polyol is 1 to 1.08;
the method for preparing the polyurethane pouring sealant for the low-density heat-insulating power battery comprises the following steps:
preparing a component A: mixing the polyol and the low-density filler to obtain the component A;
and (3) preparing a component B: mixing the isocyanate and the low-density filler to obtain the component B;
preparing polyurethane pouring sealant: mixing the component A and the component B to prepare the polyurethane pouring sealant;
before the low-density filler is used for preparing the A component and the B component, the method further comprises the step of modifying the hollow microspheres, specifically: firstly, pre-dispersing the hollow microspheres by using sodium citrate, and then, carrying out surface hydroxylation on the hollow microspheres by using sodium hydroxide solution and then, treating the hollow microspheres by using a silane coupling agent;
the silane coupling agent is 3- (2, 3-glycidoxy) propyl trimethoxy silane.
2. The insulating power cell polyurethane potting adhesive of claim 1, wherein the hollow microspheres comprise at least one of hollow glass microspheres, hollow silica microspheres, hollow phenolic resin microspheres.
3. The insulating power cell polyurethane potting adhesive of claim 2, wherein the low density filler comprises hollow glass microspheres.
4. The low density, thermally insulating power cell polyurethane potting adhesive of claim 1, wherein the polyol comprises at least one of a polyether polyol, a bio-based polyol.
5. The low density heat insulating power cell polyurethane potting adhesive of claim 1, wherein the isocyanate comprises at least one of diphenylmethane diisocyanate, and diphenylmethane polyisocyanate.
6. The polyurethane potting adhesive for the heat-insulating power battery of claim 1, wherein: and the mixing ratio of the component A to the component B is 1-3:1 according to the mass ratio.
7. The polyurethane pouring sealant for the heat-insulating power battery according to claim 1, wherein the step of preparing the component A further comprises the operations of adding a catalyst, a chain-extending cross-linking agent, a flame retardant and a defoaming agent, and specifically comprises the following steps: mixing the polyol, the chain-extending cross-linking agent, the flame retardant and the defoamer at 100-120 ℃ and dehydrating in vacuum for 2-4 hours, cooling the reaction system to 55-65 ℃ when the water content of the reaction system is lower than 500ppm, then adding the catalyst and the hollow microspheres into the reaction system, cooling, and simultaneously continuously maintaining vacuum and stirring for 0.5-1 hour to obtain the component A;
in the step of preparing the component A, the ratio of the feeding amounts of the polyol, the hollow microsphere, the catalyst, the chain extension crosslinking agent, the flame retardant and the defoamer is 20-32.5:5-25:0-0.05:0.5-2.5:5-10:0-0.1 according to the mass ratio.
8. The polyurethane potting adhesive for heat-insulating power batteries according to claim 1, wherein the step of preparing the component B further comprises the operation of adding a flame retardant and an antifoaming agent, in particular: mixing the isocyanate, the hollow microspheres, the flame retardant and the defoamer, and stirring for 1-2 hours at normal temperature under vacuum to obtain the component B;
in the step of preparing the component B, the ratio of the feeding amount of the isocyanate, the hollow microspheres, the flame retardant and the defoamer is 15-30:15-25:5-10:0-0.25 according to the mass ratio.
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| CN115232596B (en) * | 2022-08-25 | 2023-11-07 | 东莞澳中新材料科技股份有限公司 | Polyurethane structural adhesive and preparation method thereof |
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|---|---|---|---|---|
| JP2000309769A (en) * | 1999-02-23 | 2000-11-07 | Sanyo Chem Ind Ltd | Urethane-based adhesive |
| CN106244084A (en) * | 2016-07-29 | 2016-12-21 | 合肥毅创钣金科技有限公司 | A kind of hollow glass micropearl strengthens the polyurethane foam glue of heat conductivity |
| CN113980637A (en) * | 2021-11-01 | 2022-01-28 | 烟台德邦科技股份有限公司 | Low-viscosity low-density polyurethane pouring sealant |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000309769A (en) * | 1999-02-23 | 2000-11-07 | Sanyo Chem Ind Ltd | Urethane-based adhesive |
| CN106244084A (en) * | 2016-07-29 | 2016-12-21 | 合肥毅创钣金科技有限公司 | A kind of hollow glass micropearl strengthens the polyurethane foam glue of heat conductivity |
| CN113980637A (en) * | 2021-11-01 | 2022-01-28 | 烟台德邦科技股份有限公司 | Low-viscosity low-density polyurethane pouring sealant |
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