CN114621721A - Polyurethane pouring sealant for low-density heat-insulation power battery - Google Patents
Polyurethane pouring sealant for low-density heat-insulation power battery Download PDFInfo
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- CN114621721A CN114621721A CN202210338617.9A CN202210338617A CN114621721A CN 114621721 A CN114621721 A CN 114621721A CN 202210338617 A CN202210338617 A CN 202210338617A CN 114621721 A CN114621721 A CN 114621721A
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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 55
- 238000009413 insulation Methods 0.000 title claims description 10
- 239000004005 microsphere Substances 0.000 claims abstract description 89
- 239000000945 filler Substances 0.000 claims abstract description 31
- 239000012948 isocyanate Substances 0.000 claims abstract description 23
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 23
- 229920005862 polyol Polymers 0.000 claims abstract description 22
- 150000003077 polyols Chemical class 0.000 claims abstract description 21
- 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
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 7
- 238000004382 potting Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 26
- 239000000853 adhesive Substances 0.000 claims description 25
- 230000001070 adhesive effect Effects 0.000 claims description 25
- 239000011521 glass Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 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
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 239000003431 cross linking reagent Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 230000033444 hydroxylation Effects 0.000 claims description 6
- 238000005805 hydroxylation reaction Methods 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 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
- 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
- 239000013530 defoamer Substances 0.000 claims 2
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000000306 component Substances 0.000 description 59
- 230000000052 comparative effect Effects 0.000 description 26
- 239000003292 glue Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000009472 formulation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000001509 sodium citrate Substances 0.000 description 7
- 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 description 7
- 229920005830 Polyurethane Foam Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000011496 polyurethane foam Substances 0.000 description 6
- 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
- 239000000126 substance Substances 0.000 description 5
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000005266 casting Methods 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
- 229920001971 elastomer Polymers 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 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
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 230000003139 buffering effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001739 density measurement 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
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 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
- 230000005484 gravity Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 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
- 230000003014 reinforcing effect Effects 0.000 description 1
- 231100000817 safety factor Toxicity 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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 hollow microspheres; the molar ratio of the isocyanate functional groups of the isocyanate to the hydroxyl functional groups of the polyhydric alcohol is 1-1.08. The hollow microspheres subjected to surface modification can be well dispersed in the polyurethane pouring sealant to form compact and mutually independent cavity structures, so that the polyurethane pouring sealant has excellent heat-insulating property and lower density.
Description
Technical Field
The invention belongs to the technical field of polyurethane pouring sealant, and particularly relates to a polyurethane pouring sealant for a low-density heat-insulation power battery.
Background
With the deep popularization of the environmental protection concept, the electric energy is gradually recognized by people as an environmental protection new energy, and further the electromotion of automobiles and two-wheeled vehicles is also popularized. The power battery is used as a core component of an electric system and consists of a plurality of battery monomers (namely battery cores), when the battery monomers cause membrane piercing due to various reasons such as mechanical deformation, extrusion, vibration and the like, the internal anode and the internal cathode are in direct contact to cause short circuit, the internal short circuit can generate a large amount of heat instantly, and the rapid conduction of the heat enables the whole power battery to be out of control thermally, so that the batteries and devices around the short circuit battery are adversely affected. In order to fully ensure the safety factors of the lithium battery, such as performance indexes of heat dissipation, buffering and shock absorption, water resistance, flame retardance, explosion resistance, electromagnetic interference resistance and the like, encapsulating materials are generally used.
In the pouring sealant industry, there are three major potting material systems, which are epoxy resin pouring sealant, organic silicon pouring sealant and polyurethane pouring sealant. The polyurethane pouring sealant has the advantages of good low-temperature resistance, wide adjustment range, high bonding strength, high cohesive strength and good damping efficiency, and gradually becomes the first choice of the pouring sealant for the power battery.
Conventional polyurethane potting glue usually can add fillers such as aluminium oxide, calcium carbonate, has also increased the density of glue when reinforcing glue heat conductivity, and this kind of potting glue coefficient of heat is higher, can't play thermal-insulated effect betterly when power battery takes place that internal short circuit produces a large amount of heats, consequently can't alleviate the problem that thermal runaway produces adverse effect to other electric cores in periphery.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the polyurethane pouring sealant for the low-density heat-insulation power battery, so as to solve the problems of overhigh density and overhigh heat conductivity coefficient in the polyurethane pouring sealant in the prior art and meet the new requirements of light weight and heat insulation in the field of power batteries.
According to a first aspect of the invention, a polyurethane pouring sealant for a low-density adiabatic dynamic battery is provided, 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 hollow microspheres; the molar ratio of isocyanate functional groups of the isocyanate to hydroxyl functional groups of the polyhydric alcohol is 1-1.08. The content of isocyanate functional groups of the isocyanate is similar to that of hydroxyl functional groups of the polyol, so that the full reaction of the isocyanate and the polyol can be ensured. The hollow microspheres with hollow structures are introduced into the polyurethane potting adhesive matrix, so that the heat conductivity coefficient and the overall density of a polyurethane potting adhesive product can be effectively reduced, the polyurethane potting adhesive for the low-density heat-insulation power battery provided by the invention has a good heat insulation effect and can keep light weight, and the polyurethane potting adhesive is applied to a lithium battery, so that the spreading of instantaneously generated heat is effectively blocked under an emergency condition, and the condition of thermal runaway is avoided. Regarding to introduce the hollow structure into the glue layer, the prior art generally forms hollow micro bubbles in the glue layer by means of chemical foaming, however, the foaming effect of such chemical foaming is greatly affected by the process field, it is difficult to controllably form hollow structures with similar shapes and uniform distribution in the glue layer in batches, which may adversely affect the controllability of the pouring sealant product. The molding process of the hollow microspheres is controllable, the hollow microspheres with similar shapes can be obtained in a batch prefabrication mode, and the hollow microspheres are filled in glue to keep the glue uniform, so that the stability and controllability of the volume, the glue and the performance of the pouring sealant are ensured. In addition, compared with hollow micro-bubbles formed by chemical foaming, the hollow micro-bubbles have obviously higher structural strength, and the introduction of the hollow micro-bubbles into polyurethane potting glue can ensure that the polyurethane potting glue formed by glue curing has enough strength and mechanical properties, so that the collapse of the potting glue due to the introduction of the hollow structure can be avoided. Moreover, the hollow microspheres are doped into the polyurethane potting adhesive, so that the spherical hollow microspheres can play a role of a ball bearing during gluing construction, the spreading of the polyurethane potting adhesive on a construction carrier is facilitated, and the construction performance of the polyurethane potting adhesive can be optimized. After the glue is cured and molded, the hollow microspheres in the colloid structure can offset the internal stress in the specification mode based on the spherical structure, and the condition of uneven shrinkage 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 0.2-0.6 g-cm-3。
Preferably, the heat conductivity coefficient of the hollow microspheres is 0.03-0.08 W.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 nearly 0.4 g-cm-3The heat conductivity coefficient can be reduced to 0.05W·m-1·K-1。
Preferably, the hollow microspheres comprise at least one of hollow glass microspheres, hollow silica microspheres and hollow phenolic resin microspheres.
Preferably, the low density filler comprises hollow glass microspheres.
Preferably, the hollow glass microspheres comprise at least one of the products of the Maanshan mineral institute under the brand numbers GS20, GS25 and GS 32.
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. And the hollow glass microspheres have a regular spherical structure, so that the total internal stress in each direction in the polyurethane adhesive layer is zero, and the polyurethane adhesive layer prepared by the hollow glass microspheres still keeps better dimensional stability under the condition of overheating or supercooling.
Preferably, the polymeric polyol includes at least one of a polyether polyol, a bio-based polyol.
Preferably, the isocyanate comprises at least one of diphenylmethane diisocyanate, polyphenylmethane polyisocyanate.
Preferably, the polyether polyol comprises at least one of difunctional polyether polyol with the molecular weight of 400-3000 and trifunctional polyether polyol with the molecular weight of 500-5000; the biological polyol is castor oil or a castor oil modifier.
Preferably, the polyether polyol comprises at least one of the products of Dow Town, Dow, Inc. under the product designation DL-1000D, DL-2000D, MN700, EP-330N; the bio-polyol comprises at least one of castor oil, product designation Sovermol-750, and product designation Sovermol-805, produced by BASF corporation.
Preferably, the MDI comprises at least one of liquefied MDI, MDI-50.
Preferably, the MDI comprises liquefied MDI.
Preferably, the liquefied MDI comprises product designation CDMDI-100L manufactured by Wanhua chemical group, Inc.
According to another aspect of the present invention, the present invention provides a method for preparing the polyurethane potting adhesive for the low-density heat-insulating power cell, comprising the following steps: preparing a component A: mixing the polyhydric alcohol and the low-density filler to obtain a component A; preparing a component B: adding isocyanate and low-density filler for mixing to obtain a component B; preparing a polyurethane pouring sealant: and mixing the component A and the component B to prepare the polyurethane pouring sealant. Because isocyanate is easy to react with water molecules to generate gas, bubbles in the product are formed, the vacuum dehydration operation is applied in the step of preparing the component A in the scheme, so that the side reaction of the isocyanate is reduced, the full reaction of the isocyanate and the polyol is ensured when the A, B components are mixed, and 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 preparation method firstly and respectively carries out primary mixing on the low-density filler in the reaction monomer polyhydric alcohol and the isocyanate, so that the low-density filler can be well dispersed in A, B components which participate in the preparation, and further, the low-density filler can be well dispersed in the polyurethane pouring sealant formed by mixing the A, B components. In the mixing process of the low-density filler and the organic component, the low-density filler with small specific gravity inevitably gathers towards the upper part of the organic component, compared with the one-step method for preparing the pouring sealant, the scheme has the advantages that the low-density filler is firstly preliminarily mixed with A, B components respectively containing two reaction monomers to ensure that the low-density filler can form compact and mutually independent cavity structures in the polyurethane pouring sealant, and further ensures that the polyurethane pouring sealant has excellent heat-insulating property and keeps better mechanical property.
Preferably, the mixing ratio of the component A to the component B 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 participating in the preparation of the component A and the component B, the method further comprises the step of modifying the hollow microspheres, and specifically comprises the following steps: the hollow microspheres are firstly subjected to surface hydroxylation by using a sodium hydroxide solution and then are treated by using a silane coupling agent.
Preferably, the hollow microspheres are pre-dispersed with sodium citrate before surface hydroxylation.
Preferably, the concrete operations for hydroxylating the surface of the hollow microsphere are as follows: adding the hollow microspheres into 0.1mol/L sodium citrate solution, performing ultrasonic dispersion for 0.5-1.5 hours until the hollow microspheres are fully dispersed, then adding 0.5mol/L NaOH solution into the hollow microspheres, continuing performing ultrasonic dispersion for 0.5-1.5 hours until the hollow microspheres are fully dispersed, heating, refluxing and stirring for 0.5-1.5 hours at 90 ℃, washing, filtering until the PH value is neutral, and drying for later use. 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, and more hydroxyl groups are exposed on the surfaces of more hollow microspheres, so that the silane coupling agent can form better coating on the surfaces of the hollow microspheres, and the compatibility of the hollow microspheres and matrix resin is further enhanced.
Preferably, the silane coupling agent is 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH 560).
Preferably, the specific operation of treating the hollow microspheres by the silane coupling agent is as follows: placing the hollow microsphere subjected to surface hydroxylation in CH3CH2And (3) sealing and stirring for 1-1.5 hours at normal temperature in a mixed solution with the mass ratio of OH to KH560 of 100:10, standing for layering, filtering to obtain an upper-layer floating material, 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, and 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 polyalcohol, the chain extension crosslinking agent, the flame retardant and the defoaming agent at 100-120 ℃, performing vacuum dehydration for 2-4 h, 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 continuously maintaining vacuum and stirring for 0.5-1 h to obtain a component A; in the step of preparing the component A, the feeding amount ratio of the polymeric polyol, the hollow microspheres, 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 by mass ratio.
Preferably, the step of preparing the component B further comprises the operation of adding a flame retardant and a defoaming agent, and specifically comprises the following steps: 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 the isocyanate, the hollow microspheres, the flame retardant and the defoaming agent is 15-30: 15-25: 5-10: 0-0.25 by mass ratio.
Preferably, the stirring speed in the step of preparing the component A and the component B is 30-60 rpm, and the vacuum degree is less than-94 KPa.
Preferably, the catalyst comprises at least one of an organotin-based, organobismuth-based, and organozinc-based catalyst.
Preferably, the catalyst comprises an organobismuth complex catalyst.
Preferably, the organobismuth composite catalyst comprises CUCAT-GF02, product number, manufactured by guangzhou yourun synthetic materials ltd.
Preferably, the functional group of the chain-extending crosslinking agent is a hydroxyl group, 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, cresyl diphenyl phosphate.
Preferably, the defoaming agent includes at least one of a silicone-based defoaming agent and a polymer-based defoaming agent.
Preferably, the defoaming agent includes at least one of BYK-066N, BYK-535, product number, manufactured by Pickering chemical Co.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example 1
Table 1 shows the formulation used for preparing the A component of the polyurethane potting adhesive for this example. The low density fillers in the following table are surface treated.
TABLE 1 formulation for preparing A component of polyurethane pouring sealant
Table 2 shows the formulation used for preparing the component B of the polyurethane potting adhesive for this example. The low density fillers in the following table are surface treated.
TABLE 2 formulation for preparing the B component of polyurethane casting glue
The raw materials required for the formulations of component a and component B were prepared according to tables 1 and 2 above, and the polyurethane potting adhesive in this example was prepared as follows:
step 1, modifying low-density filler: placing the hollow glass microsphere GS20 in CH3CH2And (3) sealing and stirring for 1 hour at normal temperature in a mixed solution with the mass ratio of OH to KH560 of 100:10, standing for layering, filtering to obtain an upper-layer floating material, and drying to obtain the final modified hollow microspheres.
Step 2, preparation of the component A: and (2) putting castor oil, DL-2000D, dipropylene glycol and diphenyl cresyl phosphate into a reaction kettle 1, uniformly stirring at 100-120 ℃, performing vacuum dehydration, cooling to 55-65 ℃ when the water content is lower than 500ppm, continuously putting GF02 and treated hollow glass microspheres GS20 into the reaction kettle 1, continuously keeping vacuum and cooling, and performing stirring operation for 0.5-1 h to obtain the component A.
Step 3, preparation of the component B: putting CDMDI-100L, diphenyl cresyl phosphate, hollow glass microspheres GS20 and BYK-A535 into a reaction kettle 2, and stirring for 1-2 hours at normal temperature in vacuum to obtain a component B.
Step 4, preparation of polyurethane pouring sealant: respectively stirring the A, B components uniformly in respective material barrels before use, transferring the materials into a transfer tank of a glue pouring device, keeping stirring and carrying out vacuum defoamation for 3-5 min, breaking vacuum by using nitrogen, and mixing in the glue pouring device while stirring to obtain the polyurethane pouring glue.
Wherein the stirring 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 speed is 5-20 rpm, and the vacuum degree is less than-94 KPa.
Example 2
Referring to the formula for preparing the component A and the component B in the example 1, the required raw materials are prepared, and the polyurethane pouring sealant in the example is prepared according to the following method:
step 1, modifying low-density filler: firstly, adding hollow glass microspheres GS20 into 0.1mol/L sodium citrate solution for ultrasonic dispersion for 0.5-1.5 hours until the hollow glass microspheres are fully dispersed, then adding 0.5mol/L NaOH solution 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 90 ℃, washing, filtering until the PH value is neutral, and drying for later use. Then, placing the hollow glass microsphere GS20 with the surface hydroxylated into CH3CH2And (3) sealing and stirring for 1 hour at normal temperature in a mixed solution with the mass ratio of OH to KH590 of 100:10, standing for layering, filtering to obtain an upper-layer floating substance, and drying to obtain the finally modified hollow microspheres.
Step 2, preparation of the component A: and (2) putting castor oil, DL-2000D, dipropylene glycol and diphenyl cresyl phosphate into a reaction kettle 1, uniformly stirring at 100-120 ℃, performing vacuum dehydration, cooling to 55-65 ℃ when the water content is lower than 500ppm, continuously putting GF02 and treated hollow glass microspheres GS20 into the reaction kettle 1, continuously keeping vacuum and cooling, and performing stirring operation for 0.5-1 h to obtain the component A.
Step 3, preparation of the component B: putting CDMDI-100L, diphenyl cresyl phosphate, hollow glass microspheres GS20 and BYK-A535 into a reaction kettle 2, and stirring for 1-2 hours at normal temperature in vacuum to obtain a component B.
Step 4, preparation of polyurethane pouring sealant: respectively stirring A, B components uniformly in respective charging barrels before use, transferring into a transfer tank of a glue pouring device, keeping stirring and defoaming in vacuum for 3-5 min, breaking vacuum by using nitrogen, and mixing in the glue pouring device while stirring to obtain the polyurethane pouring glue.
Wherein the stirring 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 speed is 5-20 rpm, and the vacuum degree is less than-94 KPa.
Example 3
The polyurethane pouring sealant of the comparative example is prepared by referring to the preparation method of the polyurethane pouring sealant provided in example 2: raw materials required by the formulas of the component A and the component B are prepared according to the example 1, the sodium citrate in the step 1 in the preparation method of the polyurethane pouring sealant provided by the example 2 is replaced by sodium dodecyl benzene sulfonate, and other specific operations and parameter settings are strictly consistent with the preparation method of the polyurethane pouring sealant provided by the example 2.
Example 4
The polyurethane pouring sealant of the comparative example is prepared by referring to the preparation method of the polyurethane pouring sealant provided in example 2: raw materials required by the formulas of the component A and the component B are prepared according to the example 1, 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 sulfate, and other specific operations 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 shows the formulation used for preparing the component A of the polyurethane potting adhesive for this comparative example. The low density fillers in the following tables are surface treated fillers.
TABLE 3 formulation for preparing polyurethane casting glue A component
Table 4 shows the formulation used for preparing the component B of the polyurethane potting adhesive for this comparative example. The fillers in the following tables are surface treated fillers.
TABLE 4 formulation for preparing polyurethane casting glue B component
The polyurethane pouring sealant of the comparative example is prepared by referring to the preparation method of the polyurethane pouring sealant provided in example 1: according to the raw materials required by the formula of the component A and the component B prepared in the above table 3 and table 4, the hollow glass microspheres GS20 in the steps 1 to 3 in the preparation method of the polyurethane pouring sealant provided in the embodiment 1 are replaced by spherical alumina, and other specific operations and parameter settings are strictly kept consistent with those of the preparation method of the polyurethane pouring sealant provided in the embodiment 1.
Comparative example 2
Refer to patent CN 113980233 a for preparation of polyurethane foam rubber to prepare polyurethane foam rubber of this comparative example.
Comparative example 3
The raw materials are prepared according to the formula of the polyurethane pouring sealant prepared in example 1, and the polyurethane pouring sealant of the comparative example is prepared according to the method for preparing the polyurethane pouring sealant prepared in example 1, wherein a silane coupling agent KH560 adopted in the modification treatment of the hollow glass microspheres GS20 in step 1 is replaced by KH 590.
Comparative example 4
The raw materials were prepared according to the recipe for preparing the polyurethane potting adhesive of example 1, and the polyurethane potting adhesive of the comparative example was prepared according to the method for preparing the polyurethane potting adhesive of example 1, wherein the silane coupling agent KH560 adopted in the modification treatment of the hollow glass microspheres GS20 in step 1 was replaced by KH 550.
Test example
1. Experimental construction mode
The polyurethane pouring sealant prepared in the examples 1-4 and the comparative examples 1-4 is used for carrying out related performance tests.
And (3) testing the density: the polyurethane potting adhesives prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to density measurement by a densitometer method.
And (3) testing the heat conductivity coefficient: the heat conductivity coefficient of the polyurethane pouring sealant prepared in examples 1-4 and comparative examples 1-3 was tested by referring to the standard of GB3399-1982 Plastic thermal conductivity coefficient test method Heat protection plate method.
Tensile strength, elongation test: the tensile length and elongation of the polyurethane pouring sealant prepared in examples 1-4 and comparative examples 1-4 are tested by referring to GB/T528-1998 determination of tensile stress strain property of vulcanized rubber or thermoplastic rubber.
2. Results of the experiment
The results of the performance test on the polyurethane potting compounds prepared in examples 1 to 4 and comparative examples 1 to 4 are shown in table 5: the experimental result shows that, referring to example 1 and comparative example 1 in the following table 5, the polyurethane potting adhesive prepared by the hollow glass microspheres has lower density and thermal conductivity than the polyurethane potting adhesive prepared by the solid silica microspheres, which indicates that the hollow glass microspheres adopted in the invention can better meet the requirement of lightweight power batteries while having better heat insulation performance, and moreover, although the mechanical performance of example 1 is reduced compared with comparative example 1, the normal use of the polyurethane potting adhesive is not affected. In embodiments 2 to 4, the hollow microspheres are pre-dispersed by using an anionic surfactant and then subjected to surface hydroxylation treatment by using a NaOH solution, so that more hydroxyl groups are exposed on the surfaces of the hollow microspheres, and a better grafting rate of the silane coupling agent on the surfaces of the hollow microspheres is ensured, thereby ensuring the close connectivity of the hollow microspheres and the matrix resin polyurethane, so that embodiments 2 to 4 have better tensile strength compared with embodiment 1, wherein embodiment 2 has better tensile strength, which means that the pre-dispersion effect of sodium citrate on the hollow microspheres is optimal, so that more hollow microsphere surfaces are hydroxylated by a sodium hydroxide solution, the grafting rate of the silane coupling agent on the surfaces of the hollow microspheres is the highest, and the hollow microspheres are connected with the matrix resin most tightly, thereby having better tensile strength. In comparative example 2, although the density and the thermal conductivity are both smaller than those of example 1, the tensile strength is nearly an order of magnitude lower than that of example 1, because in comparative example 2, the polyurethane foam is formed into a hollow structure in the polyurethane foam by using a chemical foaming method to reduce the density of the polyurethane material, so that the polyurethane foam has extremely low mechanical properties and cannot meet the normal use requirement of the power battery potting material. In addition, the polyurethane foam rubber has extremely poor flame retardant property, and is easy to cause combustion and has larger potential hazard if short circuit occurs inside the power battery to generate spark. The results of comparing example 1 with comparative example 3 and comparative example 4 by using another types of silane coupling agents KH590 and KH560 to modify the surfaces of the hollow microspheres in comparative example 3 and comparative example 4 show that the polyurethane prepared by using KH560 modified hollow microspheres has higher tensile strength and elongation than the polyurethane prepared by using KH590 and KH550 modified hollow microspheres, because KH590 and KH550 respectively contain active groups such as sulfydryl and amino groups, which are easy to react with isocyanate groups in isocyanate, on one hand, the reaction of the active groups with the isocyanate groups makes the reaction of polyol and the isocyanate insufficient, on the other hand, the reaction of the active groups with the isocyanate groups makes the viscosity of the B component increased, the hollow microspheres partially agglomerated, which affects the mixing of the hollow microspheres and the B component, and adversely affects the finally formed polyurethane pouring sealant.
TABLE 5 results of the performance test on the polyurethane potting compounds prepared in examples 1 to 4 and comparative examples 1 to 4
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the present invention.
Claims (11)
1. The polyurethane pouring sealant for the low-density heat-insulation power battery is characterized by comprising 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 hollow microspheres;
the molar ratio of the isocyanate functional groups of the isocyanate to the hydroxyl functional groups of the polyhydric alcohol is 1-1.08.
2. The polyurethane potting adhesive for thermally insulated power cells as claimed in claim 1, wherein the hollow microspheres comprise at least one of hollow glass microspheres, hollow silica microspheres, hollow phenolic resin microspheres.
3. The thermally insulated power cell polyurethane potting adhesive of claim 2, wherein the low density filler comprises hollow glass microspheres.
4. The low density thermally insulated dynamic battery polyurethane potting adhesive of claim 1, wherein the polymeric polyol comprises at least one of a polyether polyol, a bio-based polyol.
5. The polyurethane potting adhesive for a low density thermally insulated power cell of claim 1, wherein the isocyanate comprises at least one of diphenylmethane diisocyanate, polyphenylmethane polyisocyanate.
6. A method for preparing the polyurethane pouring sealant for the low-density heat insulation dynamic battery as claimed in any one of claims 1 to 5, which comprises the following steps:
preparing a component A: mixing the polymeric polyol and the low-density filler to obtain the component A;
preparing a component B: adding the isocyanate and the low-density filler for mixing to obtain the component B;
preparing a polyurethane pouring sealant: and mixing the component A and the component B to prepare the polyurethane pouring sealant.
7. The method of claim 6, wherein the polyurethane potting adhesive comprises: the mixing ratio of the component A to the component B is 1-3: 1 according to the mass ratio.
8. The method of claim 6, further comprising modifying the hollow microspheres before the low-density filler is used to participate in the preparation of the component A and the component B, and specifically comprising: and (3) carrying out surface hydroxylation on the hollow microspheres by adopting a sodium hydroxide solution and then treating the hollow microspheres by using a silane coupling agent.
9. The method of claim 8, wherein the silane coupling agent is 3- (2, 3-glycidoxy) propyltrimethoxysilane.
10. The method of claim 8, wherein the step of preparing the component a further comprises adding a catalyst, a chain-extending cross-linking agent, a flame retardant, and a defoamer, and specifically comprises: mixing the polyhydric alcohol, the chain extension cross-linking agent, the flame retardant and the defoaming agent at 100-120 ℃, and dehydrating in vacuum for 2-4 h, when the water content of a reaction system is lower than 500ppm, cooling the reaction system to 55-65 ℃, then adding the catalyst and the hollow microspheres into the reaction system, cooling, and simultaneously continuing to keep vacuum and stirring for 0.5-1 h to obtain the component A; in the step of preparing the component A, the feeding amount ratio of the polymeric polyol, the hollow microspheres, 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 by mass ratio.
11. The method of claim 8, wherein the step of preparing the component B further comprises adding a flame retardant and a defoamer, and the step of preparing the component B comprises the following steps: mixing the isocyanate, the hollow microspheres, the flame retardant and the 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 charging amount of the isocyanate, the hollow microspheres, the flame retardant and the defoaming agent is 15-30: 15-25: 5-10: 0-0.25 by mass ratio.
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| CN114989391A (en) * | 2022-07-15 | 2022-09-02 | 山东一诺威聚氨酯股份有限公司 | Bio-based low-pressure injection molding TPU (thermoplastic polyurethane) for packaging electronic components and preparation method thereof |
| CN115232596A (en) * | 2022-08-25 | 2022-10-25 | 东莞澳中新材料科技股份有限公司 | Polyurethane structural adhesive and preparation method thereof |
| CN115595091A (en) * | 2022-11-23 | 2023-01-13 | 江西天永诚高分子材料有限公司（Cn） | Ultralow-density and super-flame-retardant organic silicon heat-insulation pouring sealant and preparation method thereof |
| CN118027882A (en) * | 2024-03-11 | 2024-05-14 | 广东领跑新材料科技有限公司 | High-temperature quick-curing glue and preparation method thereof |
| WO2024182964A1 (en) * | 2023-03-06 | 2024-09-12 | Dow Global Technologies Llc | Low viscosity polyurethane pottant compositions |
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| 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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| 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 |
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| CN114989391A (en) * | 2022-07-15 | 2022-09-02 | 山东一诺威聚氨酯股份有限公司 | Bio-based low-pressure injection molding TPU (thermoplastic polyurethane) for packaging electronic components and preparation method thereof |
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| WO2024182964A1 (en) * | 2023-03-06 | 2024-09-12 | Dow Global Technologies Llc | Low viscosity polyurethane pottant compositions |
| CN118027882A (en) * | 2024-03-11 | 2024-05-14 | 广东领跑新材料科技有限公司 | High-temperature quick-curing glue and preparation method thereof |
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