Polyol component, potting composition containing the polyol component, polyurethane foam and battery product
The use of a polyol component with specific solid flame retardants enhances the flame retardancy and insulation of polyurethane foams, addressing the inefficiencies of traditional materials in high-energy density battery applications.
Patent Information
- Application Number
- PCT/CN2024/143129
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-01-03
- Filing Date
- 2024-12-27
- Publication Date
- 2025-07-10
AI Technical Summary
Traditional polyurethane potting materials fail to meet current high flame retardant efficiency and rating requirements, posing a risk in battery applications with increasing energy density.
A polyol component comprising a nitrogen-containing or metal-free phosphorus-containing solid flame retardant, along with a metal organophosphate solid flame retardant, is used to enhance the flame retardancy of polyurethane compositions for battery applications.
The solution provides polyurethane foams with high elasticity, good electrical insulation, and effective flame retardancy, protecting battery cells from thermal runaway.
Smart Images

Figure PCTCN2024143129-FTAPPB-I100001 
Figure PCTCN2024143129-FTAPPB-I100002 
Figure PCTCN2024143129-FTAPPB-I100003
Abstract
Description
Polyol component, potting composition containing the polyol component, polyurethane foam and battery productTechnical Field
[0001] The invention relates to a polyol component, a potting composition containing the polyol component, and a polyurethane foam prepared from the potting composition. The present invention also relates to a battery product comprising the foam prepared from the potting composition.Background Art
[0002] As the development of electric vehicles advances, motor vehicle manufacturers are tending to build batteries with ever increasing energy density to extend mileage, and as a result, the risk of battery failure and internal overheating is becoming critical. Polyurethane potting materials are a hot topic of research as a solution for battery "thermal runaway" .
[0003] Traditional potting materials usually acquire a certain degree of flame retardancy through the addition of liquid flame retardants and / or small amounts of solid flame retardants. However, they are unable to meet the current high flame retardant efficiency and flame retardant rating requirements.Summary of the Invention
[0004] An objective of the present invention is to overcome the problem in the prior art mentioned above and provide a polyurethane potting composition with high flame retardancy.
[0005] Surprisingly, the inventors have found that the abovementioned objective can be achieved by the polyol components and polyurethane potting composition of the invention.
[0006] In a first aspect of the present invention, a polyol component is provided, comprising the following components:
[0007] (a-1) at least one polyol reactive to isocyanate,
[0008] (a-2) a chain extender and / or a crosslinker,
[0009] (a-3) a blowing agent,
[0010] (a-4) optionally a catalyst,
[0011] (a-5) a solid flame retardant, and
[0012] (a-6) optionally an additive and / or an aid,
[0013] wherein the solid flame retardant comprises an FR-1 flame retardant and an FR-2 flame retardant, the FR-1 flame retardant is a nitrogen-containing solid flame retardant, a metal-free phosphorus-containing solid flame retardant or a combination thereof, the FR-2 flame retardant is a metal organophosphate solid flame retardant, the FR-1 flame retardant accounts for 8 to 20 weight%of the total weight of the polyol component, and the FR-2 flame retardant accounts for 5 to 25 weight%of the total weight of the polyol component.
[0014] In a second aspect of the present invention, a potting composition for a battery is provided, the potting composition being obtained by reacting at least the following components:
[0015] an isocyanate component, comprising:
[0016] (b-1) at least one isocyanate, and
[0017] (b-2) optionally a second flame retardant,
[0018] and the polyol component according to the first aspect of the invention.
[0019] In a third aspect of the invention, a battery product is provided, comprising:
[0020] battery cells; and
[0021] a polyurethane foam located between the battery cells, prepared in accordance with the potting composition described in the second aspect of the present invention.
[0022] It was unexpectedly discovered that in the present invention, a product prepared from the above-described polyol component and potting composition shows high elasticity, good electrical insulation and good flame retardancy.Detailed Description of Embodiments
[0023] All the scientific and technical terms used herein have the meanings commonly understood by those skilled in the art, unless otherwise defined. As used herein, the following terms have the meanings given to them below, unless otherwise stated.
[0024] As used herein, the articles "a" and "an" refer to one or more (i.e. at least one) grammatical object of the articles. For example, "an element" refers to one element or more than one element.
[0025] As used herein, the expression "comprises" also covers the expression "consists of" .
[0026] All percentages (%) refer to "weight percentage" unless otherwise stated.
[0027] Unless otherwise stated, temperature is room temperature and pressure is ambient pressure.
[0028] As used herein, "potting" refers to the process of filling a container (such as a battery casing in the context of the invention) with a liquid potting composition (such as a polyurethane potting composition in the context of the invention) . The liquid potting composition that is poured into the container is foamed and cured, thereby protecting internal components (such as battery cells in the context of the present invention) from impacts and shocks, and can absorb deformation pressure arising from the deformation of surrounding components. It should be understood that the polyurethane potting composition is freely foamed, i.e. the foam can expand freely in at least one dimension.
[0029] An "isocyanate component" and a "polyol component" (also referred to below as a "resin component" or "resin" ) are used in the preparation of a polyurethane potting material, wherein the "polyol component" is a mixture of a polyol (a-1) reactive to isocyanate, a chain extender and / or a crosslinking agent (a-2) , a blowing agent (a-3) , optionally a catalyst (a-4) , a solid flame retardant (a-5) , and optionally an additive and / or an aid (a-6) , and the"isocyanate component" is a mixture of at least one isocyanate (b-1) and optionally a second flame retardant (b-2) . The polyol component reacts with the isocyanate to form a carbamate bond; such a system is disclosed in, for example, U.S. Patent No. 4,218,543.
[0030] In commercial applications, the isocyanate component and the polyol component are stored separately; for use, they are transported to a mixing chamber and mixed (e.g. by static or impact mixing) to produce a liquid polyurethane reaction mixture. The liquid polyurethane reaction mixture is then immediately introduced into a receiving chamber of a battery product (e.g. by using a high or low pressure system) . There are no restrictions on types of suitable machines.
[0031] In the first aspect of the present invention, a polyol component is provided for the preparation of a polyurethane potting composition. The polyol component comprises the following components:
[0032] (a-1) at least one polyol reactive to isocyanate,
[0033] (a-2) a chain extender and / or a crosslinker,
[0034] (a-3) a blowing agent,
[0035] (a-4) optionally a catalyst,
[0036] (a-5) a solid flame retardant, and
[0037] (a-6) optionally an additive and / or an aid,
[0038] wherein the solid flame retardant comprises an FR-1 flame retardant and an FR-2 flame retardant, the FR-1 flame retardant is a nitrogen-containing solid flame retardant, a metal-free phosphorus-containing solid flame retardant or a combination thereof, the FR-2 flame retardant is a metal organophosphate solid flame retardant, the FR-1 flame retardant accounts for 8 to 20 weight%of the total weight of the polyol component, and the FR-2 flame retardant accounts for 5 to 25 weight%of the total weight of the polyol component.
[0039] Polyol component
[0040] Polyol (a-1) reactive to isocyanate
[0041] The polyol (a-1) reactive to isocyanate may be any polyol in the art that has at least two reactive hydrogen atoms and can be used to prepare polyurethane. For example, a polyether polyol, a polyester polyol or a mixture thereof may be used.
[0042] A preferred polyol is polyether polyol. Compared to polyester polyols, polyether polyols do not age easily in wet and hot environments. According to the present invention, the preferred polyether polyol has a number-average molecular weight Mn of 300 to 8000, preferably 3000 to 6500, and 2 ≤ functionality (Fn) ≤ 3. The preferred polyether polyol described above has a low viscosity, and consequently, the polyol component still has a low viscosity and good processability after the addition of the solid flame retardant. Practical examples of suitable commercially available polyols include 2090 (BASF) and 2048 (BASF) .
[0043] The polyether polyol is prepared by a known method from one or more alkylene oxide having 2 to 4 carbon atoms in the alkylene group, with the addition of at least one initiator containing 2 to 8 reactive hydrogen atoms, for example by anionic polymerization using an alkali metal hydroxide or alkali metal alkoxide as a catalyst, or cationic polymerization using a Lewis acid (such as antimony pentachloride or boron trifluoride etherate) as a catalyst. In addition, the catalyst used could also be a double metal cyanide -a so-called DMC catalyst.
[0044] Practical examples of suitable alkylene oxides include ethylene oxide, tetrahydrofuran, 1, 3-propylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide and 2, 3-butylene oxide. Alkylene oxides may be used alone, alternately in sequence, or in combination.
[0045] Practical examples of suitable initiators include water or diols and triols, such as ethylene glycol, propane-1, 2-diol or propane-1, 3-diol, diethylene glycol, dipropylene glycol, butane-1, 4-butanediol, glycerol and tris (hydroxymethyl) propane.
[0046] The polyol (a-1) accounts for 35 weight%to 85 weight%, preferably 40 weight%to 70 weight%of the total weight of the polyol component.
[0047] Optionally, the polyether polyol used in the preparation of the polyurethane of the invention also comprises a flame retardant polyether polyol. Flame retardant polyether polyols have phosphorus / halogen elements introduced into the polyol molecular chain, thus achieving a flame retardant effect. A preferred flame retardant polyether polyol has a number average molecular weight Mn of 300 to 8000, preferably 3000 to 6500, and 2 ≤ functionality (Fn) ≤ 4. Practical examples of suitable commercially available flame retardant polyether polyols include ZR-001 from Bluestar Dongda. Flame retardant polyether polyols used in the present invention may also be prepared by a known method. For example, they may be prepared by reacting a halogen-containing initiator with an alkylene oxide in the presence of a catalyst. The flame retardant polyether polyol accounts for 0 weight%to 40 weight%, preferably 5 weight%to 20 weight%, of the total weight of the polyether polyol.
[0048] Chain extender and / or crosslinker (a-2)
[0049] Chain extenders and / or crosslinkers (a-2) that may be used are substances with a molar mass preferably less than 500 g / mol and especially preferably 60 -400 g / mol, wherein the chain extender has 2 hydrogen atoms reactive to isocyanate, and the crosslinker has 3 hydrogen atoms reactive to isocyanate. These substances may be used alone, or preferably in the form of a mixture. Diols and / or triols with a molecular weight less than 500, especially 60 -400, especially 60 -200, are preferably used. Practical examples of those substances that may be used are aliphatic, alicyclic and / or araliphatic diols having 2 -14, preferably 2 -10 carbon atoms, e.g. ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 2-, 1, 3-and 1, 4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, tripropylene glycol, diethanolamine or triol, e.g. 1, 2, 4-or 1, 3, 5-trihydroxycyclohexane, glycerol and trimethylolpropane. The chain extender and / or crosslinker (a-4) is / are preferably selected from ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, glycerol and 1, 4-butanediol.
[0050] The chain extender and / or crosslinker (a-2) accounts for 1 to 10 weight%of the total weight of the polyol component.
[0051] Blowing agent (a-3)
[0052] The blowing agent (a-3) used in accordance with the invention preferably comprises water. The blowing agent used may also comprise other chemical and / or physical blowing agents in the art, as well as water. A chemical blowing agent is a compound that reacts with isocyanate to form a gaseous product, a practical example being water or formic acid. A physical blowing agent is a compound that has been dissolved or emulsified in a starting material used for the preparation of polyurethane and evaporates under the conditions of polyurethane formation. These substances are, for example, hydrocarbons, halogenated hydrocarbons and other compounds, such as perfluoroalkanes, e.g. perfluorohexane and CFCs, and ethers, esters, ketones and / or acetals. In a preferred embodiment, water is used as the only blowing agent (a-3) . In this case, the polyurethane foam according to the present invention is a water-foamed polyurethane foam.
[0053] The blowing agent (a-3) accounts for 0.1 to 4 weight%, preferably 0.2 to 1 weight%of the total weight of the polyol component.
[0054] Catalyst (a-4)
[0055] As the catalyst (a-4) , such compounds are known and are documented in, for example, "Kunststoffhandbuch, vol. 7, Polyurethane" , Carl Hanser Verlag, 3rd edition, 1993, Chapter 3.4.1. These substances include amine-based catalysts and catalysts based on organometallic compounds.
[0056] The following may for example by used as catalysts based on organometallic compounds: organotin compounds such as tin (II) salts of organic carboxylic acids, e.g. tin (II) acetate, tin (II) octoate, tin (II) ethylhexanoate and tin (II) laurate, and dialkyltin (IV) salts of organic carboxylic acids, e.g. dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and bismuth carboxylates, e.g. bismuth (III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octoate, or alkali metal salts of carboxylic acids, e.g. potassium acetate or potassium formate.
[0057] An amine-based catalyst is preferably used as the catalyst (a-4) , such as N, N, N', N'-tetramethyldipropylenetriamine, 2- [2- (dimethylamino) ethyl-methylamino] ethanol, N, N, N'-trimethyl-N'-2-hydroxyethyl-bis- (aminoethyl) ether, bis (2-dimethylaminoethyl) ether, N, N, N, N, N-pentamethyldiethylenetriamine, N, N, N-triethylaminoethoxyethanol, dimethylcyclohexylamine, trimethyl hydroxyethyl ethylenediamine, dimethylbenzylamine, triethylamine, triethylenediamine, pentamethyldipropylenetriamine, dimethylethanolamine, N-methylimidazole, N-ethylimidazole, tetramethylhexamethylenediamine, tris (dimethylaminopropyl) hexahydrotriazine, dimethylaminopropylamine, N-ethylmorpholine, diazabicycloundecylene and diazabicyclononene. Practical examples of suitable commercially available amine catalysts include Dabco 33LV.
[0058] The catalyst (a-4) accounts for 0 to 5 weight%, preferably 0.1 to 3.5 weight%of the total weight of the polyol component.
[0059] Solid flame retardant (a-5)
[0060] The solid flame retardant (a-5) suitable for the invention comprises an FR-1 flame retardant and an FR-2 flame retardant; the FR-1 flame retardant is a nitrogen-containing solid flame retardant, a metal-free phosphorus-containing solid flame retardant or a combination thereof, and the FR-2 flame retardant is a metal organophosphate solid flame retardant. The combination of solid flame retardants according to the present invention can achieve a higher flame retardant efficiency and flame retardant grade compared to a liquid flame retardant and a single solid flame retardant.
[0061] Specific practical examples of nitrogen-containing solid flame retardants include melamine, melamine salts, guanidine, melamine cyanurate (MCA) , melamine polyphosphate (MPP) , melamine phosphate, melamine formaldehyde, hydroxymethylated melamine, hexamethoxymethyl melamine, urea, dimethylurea, melamine pyrophosphate, dicyandiamide, guanylurea phosphate and glycine, preferably melamine and derivatives thereof (e.g. melamine cyanurate, melamine polyphosphate, melamine phosphate, etc. ) .
[0062] The metal-free phosphorus-containing solid flame retardant comprises at least one selected from the following: 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) , triphenylphosphate, ammonium polyphosphate, red phosphorus, tributyl phosphate (RBP) and mixtures thereof.
[0063] The FR-1 flame retardant accounts for 8 to 20 weight%of the total weight of the polyol component. For example, the FR-1 flame retardant may account for 8 weight%, 9 weight%, 10 weight%, 11 weight%, 12 weight%, 13 weight%, 14 weight%, 15 weight%, 16 weight%, 17 weight%, 18 weight%, 19 weight%or 20 weight%, etc. of the total weight of the polyol component. In one embodiment, the FR-1 flame retardant has a particle size D95 ≤ 60 μm, preferably ≤ 40 μm, and more preferably ≤ 25 μm.
[0064] The metal organophosphate solid flame retardant comprises at least one selected from the following: metal salts of phosphoric acid, phosphonic acid or phosphinic acid, wherein the metal is selected from iron, aluminium, magnesium, zinc, lanthanum, cerium, etc. The metal organophosphate solid flame retardant (FR-2 flame retardant) accounts for 5 to 25 weight%of the total weight of the polyol component. For example, the metal organophosphate solid flame retardant (FR-2 flame retardant) may account for 5 weight%, 6 weight%, 7 weight%, 8 weight%, 9 weight%, 10 weight%, 11 weight%, 12 weight%, 13 weight%, 14 weight%, 15 weight%, 16 weight%, 17 weight%, 18 weight%, 19 weight%, 20 weight%, 21 weight%, 22 weight%, 23 weight%, 24 weight%or 25 weight%, etc. of the total weight of the polyol component. In one embodiment, the FR-2 flame retardant has a particle size D95 ≤ 120 μm, preferably ≤ 60 μm.
[0065] Preferably, the weight ratio of the FR-2 flame retardant to the FR-1 flame retardant is 3: 1 to 1: 4. For example, the weight ratio of the FR-2 flame retardant to the FR-1 flame retardant may be 3: 1, 2: 1, 1: 1, 1: 2, 1: 3 or 1: 4, etc.
[0066] The preferred metal organophosphate solid flame retardant is an organophosphinic acid metal salt with the following formula:
[0067] R1 and R2 are the same or different and denote straight-chain or branched C1-C6 alkyl groups (more preferably C1-C4 alkyl groups) ;
[0068] M denotes Al, Mg, Ca, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na or K;
[0069] m denotes 1, 2, 3 or 4.
[0070] Preferably, the organophosphinic acid metal salt is selected from aluminium diethyl phosphinate, aluminium methylethyl phosphinate, aluminium dipropyl phosphinate, aluminium dibutyl phosphinate, aluminium ethylbutyl phosphinate, aluminium ethylhexyl phosphinate, aluminium butylhexyl phosphinate, and mixtures thereof.
[0071] Specific practical examples of metal organophosphate solid flame retardants also include iron phenylphosphate (PPFe) , aluminium phenylphosphate (PPAl) , zinc phenylphosphate (PPZn) , triphenyliron phosphate (PP3Fe2) and iron phenylphosphate (PHA-Fe) .
[0072] In a preferred embodiment, the solid flame retardant (a-5) of the invention does not comprise expandable graphite. This makes the polyurethane foam of the present invention more electrically insulating.
[0073] In one embodiment, the total amount of the solid flame retardant (a-5) is preferably 13 to 45 weight%, more preferably 25 to 40 weight%, based on the total weight of the polyol component.
[0074] Additive and / or aid (a-6)
[0075] Additives and / or aids (a-6) that may be used include but are not limited to surfactants, preservatives, colorants, antioxidants, enhancers, stabilizers and water absorbers. When preparing polyurethane foam, a small amount of surfactant is usually preferably used to stabilize the foaming reaction mixture until it cures. Such a surfactant advantageously comprises a liquid or solid organosiloxane surfactant, used in a quantity sufficient to stabilize the foaming reaction mixture. Typically, the amount of the aid, in particular the surfactant, is 0.5 to 5 weight%, based on the total weight of the polyol component.
[0076] Further information on the use and mode of action of the abovementioned aids and additives, as well as other practical examples, are provided in, for example, "Kunststoffhandbuch, Band 7, Polyurethane" [ "Plastics handbook, Volume 7, Polyurethanes" ] , Carl Hanser Verlag, 3rd edition, 1993, Chapter 3.4.
[0077] The viscosity of the polyol component according to the invention is 500 to 6000 mPa·s, and is measured according to ASTM D2196-15.
[0078] In the second aspect of the present invention, a potting composition is provided, which is obtained by reacting at least the following components:
[0079] an isocyanate component, comprising:
[0080] (b-1) at least one isocyanate, and
[0081] (b-2) optionally a second flame retardant,
[0082] the polyol component according to the first aspect of the invention.
[0083] Isocyanate component
[0084] Isocyanate (b-1)
[0085] The invention does not limit the type of polyisocyanate, which means an organic compound containing two or more active isocyanate groups per molecule, i.e., a functionality of 2 (in which case the polyisocyanate is also known as a diisocyanate) or greater than 2. Practical examples of isocyanates may include any aliphatic, alicyclic, araliphatic and aromatic bifunctional or polyfunctional isocyanate known in the art and any desired mixture thereof. The isocyanates can be monomers, prepolymers and / or polymeric isocyanates.
[0086] Suitable practical examples include aliphatic, alicyclic, araliphatic and / or aromatic isocyanates, such as tri-, tetra-, penta-, hexa-, hepta-and / or octa-methylene diisocyanate, 2-methylpentamethylene 1, 5-diisocyanate, 2-ethylbutylene 1, 4-diisocyanate, pentamethylene 1, 5-diisocyanate, butylene 1, 4-diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI) , 1, 4-and / or 1, 3-bis(isocyanatomethyl) cyclohexane (HXDI) , cyclohexane 1, 4-diisocyanate, 1-methylcyclohexane 2, 4-and / or 2, 6-diisocyanate and / or bicyclohexylmethane 4, 4′- / 2, 4′-and 2, 2′-diisocyanate, diphenylmethane 2, 2′-, 2, 4′-and / or 4, 4′-diisocyanate (MDI) , polymeric MDI, naphthylene 1, 5-diisocyanate (NDI) , toluene 2, 4-and / or 2, 6-diisocyanate (TDI) , 3, 3′-dimethyldiphenyl diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate. Especially preferred are 2, 2’-, 2, 4’-and / or 4, 4’-diisocyanate and polymeric MDI. Practical examples of suitable commercially available isocyanate compounds include M20S (from BASF) or MIPS (from BASF) .
[0087] Other possible isocyanates are given for example in "Kunststoffhandbuch, Band 7, Polyurethane" [Plastics handbook, Vol. 7, Polyurethanes] , Carl Hanser Verlag, 3rd Edition, 1993, Chapters 3.2 and 3.3.2.
[0088] In addition, the isocyanate component may also be used in the form of an isocyanate prepolymer. The isocyanate prepolymer may be obtained by reacting the abovementioned isocyanate with a polyol.
[0089] According to the present invention, preferably, the NCO content of the isocyanate is in the range of 12 to 35, based on the number of parts by weight of the isocyanate component, and Fn ≥ 2. The isocyanate accounts for 60 weight%to 100 weight%, preferably 65 weight%to 95 weight%, and more preferably 80 weight%to 95 weight%of the total weight of the isocyanate component.
[0090] Flame retardant (b-2)
[0091] The isocyanate component optionally comprises a second flame retardant. The second flame retardant comprises a liquid flame retardant selected from at least one of the following: for example, organic phosphorous-containing flame retardants, such as resorcinol bis (diphenyl) phosphate (RDP) , tris (1-chloro-2-propyl) phosphate (TCPP) and tricresyl phosphate (TCP) .
[0092] Optionally, the isocyanate component may also comprise a nitrogen-containing solid flame retardant, a metal-free phosphorus-containing solid flame retardant and / or a metal organophosphate solid flame retardant, as mentioned in the polyol component.
[0093] According to the present invention, the flame retardant (b-2) accounts for 0 weight%to 40 weight%, preferably 5 weight%to 35 weight%, and more preferably 5 weight%to 20 weight%of the total weight of the isocyanate component.
[0094] According to the present invention, the polyol component and the isocyanate component are mixed in the weight ratio 100: (30-100) , for example, 100: 30, 100: 40, 100: 50, 100: 60, 100: 70, 100: 80, 100: 90 or 100: 100, preferably 100: (40-90) .
[0095] In the third aspect of the invention, a battery product is provided, the battery product comprising:
[0096] battery cells; and
[0097] a polyurethane foam located between the battery cells, prepared in accordance with the potting composition described in the second aspect of the present invention.
[0098] The battery product may be prepared by the following steps:
[0099] 1) injecting the potting composition described in the second aspect of the invention into a cavity between battery cells;
[0100] 2) maintaining curing for 10-60 minutes at a temperature of 10-35℃, for example.
[0101] The present invention does not specifically define the type of battery cell. For example, the battery cell assembly type may be a cylindrical, soft-pack, square or blade battery. It should be understood that in addition to the battery cells, the battery product according to the present invention also comprises other components such as a BMS (battery management system) .
[0102] In step 1) , the injection may be continuous or discontinuous.
[0103] In order to fill as much of a chamber of the battery product as possible within a short period of time, the inventors of the present invention have discovered that the potting composition should have good fluidity. In accordance with the invention, the potting composition (i.e. liquid polyurethane reaction mixture) has an initial viscosity of less than 7000 mPa·s, preferably less than 5000 mPa·s, measured according to ASTM D2196-15, at a temperature of 25 ℃. The initial viscosity of the polyurethane reaction mixture is measured as follows: immediately after mixing the polyol component and the isocyanate component, the viscosity of the resulting polyurethane reaction mixture is determined at a temperature of 25℃ according to ASTM D2196-15. The inventors of the present invention have found that a potting composition with this initial viscosity has good fluidity and processability, allowing the potting composition to rapidly fill a cavity with a complex shape. At the same time, good fluidity also helps the potting composition to flow flat in a short time.
[0104] In step 2) , the potting composition is cured at a temperature of 10-35℃, preferably 15-25℃for 10-60 minutes, preferably 5-30 minutes. The temperature is chosen so that the entire curing process can be completed in a short time; this is advantageous in industry.
[0105] In an embodiment, the surface hardness of the polyurethane foam according to the invention is no higher than 80 Shore A, preferably no higher than 65 Shore A, and more preferably no higher than 55 Shore A. That is, the polyurethane foam according to the invention is a "soft foam" , which allows it to effectively absorb surrounding deformation pressure and protect the internal battery cells, etc.
[0106] In an embodiment, the dielectric strength of the polyurethane foam according to the invention is greater than 4 kV / mm; and the polyurethane potting foam has a volume resistivity greater than 1*1011 Ω·cm, preferably greater than 1*1012 Ω·cm. This indicates that the polyurethane foam of the invention has good electrical insulating properties.
[0107] In an embodiment, the polyurethane foam according to the invention has a flame retardancy of at least grade V2 or higher as measured by the UL 94 test. In one embodiment, the polyurethane potting foam has a flame retardancy of at least grade V1 or higher as measured by the UL 94 test. In one embodiment, the polyurethane potting foam has a flame retardancy of grade V0 as measured by the UL 94 test.
[0108] In an embodiment, the polyurethane foam according to the invention has a modulus of less than 25 MPa, preferably less than 20 MPa, and more preferably less than 10 MPa, measured according to ISO1798; the elongation rate of the polyurethane potting foam is greater than 5%, preferably greater than 10%, and more preferably greater than 20%; and the tensile strength of the polyurethane potting foam is 0.8-2.5 MPa, preferably 1-2 MPa.
[0109] In one embodiment, the density of the polyurethane foam according to the invention is 0.1-0.4 g / cm3, preferably 0.2-0.3 g / cm3.
[0110] It should be noted that throughout this application, the materials mentioned in the method embodiments have the same meanings as those in the product embodiments, and unless otherwise stated, each of the general, preferred, more preferred and most preferred definitions and quantities of materials described in the product section also applies to the method of preparation of the product and to the product made from the product.
[0111] Examples
[0112] The present invention is now described with reference to Examples and Comparative examples, but these Examples and Comparative examples are not intended to limit the present invention.
[0113] General instructions
[0114] The following starting materials are included in the Examples:
[0115] The following methods are used to determine properties:
[0116] Examples of preparation of potting composition
[0117] The polyol component and isocyanate component of Examples 1 -9 and Comparative examples 1 -7 are prepared by mixing the corresponding constituents according to Table 1, and stored in separate containers. In use, a liquid polyurethane reaction mixture (i.e. potting composition) is produced by delivering these two components into a mixing chamber in the mixing ratio shown in Table 1 at 150 bar and performing impact mixing. The initial viscosities of the liquid polyurethane reaction mixtures obtained in Examples 1 -9 and Comparative examples 1 -7 are also listed in Table 1.
[0118] As shown in Table 1, the initial viscosities of the liquid polyurethane reaction mixtures of Examples 1-9 are 1650-6900 mPa·s; this gives the resulting liquid polyurethane reaction mixtures the required fluidity.
[0119] In contrast, the initial viscosity of the liquid polyurethane reaction mixture of Comparative example 2 is 8600 mPa·s; this is too thick, and lacks sufficient fluidity to allow it to flow flat.
[0120] Examples of preparation of battery product
[0121] The battery product comprises a battery casing and has dimensions of 150 cm (width) ×150cm (length) × 15cm (height) . The battery cells of the battery are placed inside the battery casing, i.e. on the bottom of the battery casing. The battery product further comprises other components. The battery cells and other components of the battery divide the internal space of the battery casing into multiple receiving cavities.
[0122] A polyol component A and an isocyanate component B of Examples 1 -9 and Comparative examples 1 -7 are prepared according to the quantities shown in Table 1 below (in%by weight) . The polyol component A and isocyanate component B are mixed according to the ratio A: B shown in Table 1 below to obtain a liquid polyurethane reaction mixture. The liquid polyurethane reaction mixture is injected into the receiving cavities. The volume of the liquid polyurethane reaction mixture injected is the same in the Examples as in the Comparative examples.
[0123] The battery pack is kept at room temperature (25℃) for curing after injection. The liquid polyurethane reaction mixture gradually cures into a polyurethane foam.
[0124] The flame retardancies of the polyurethane foams obtained in Examples 1-9 and Comparative examples 1-7 are determined. As shown in Table 1, the polyurethane foams of Examples 1-9 have flame retardancies of at least grade V2 or even higher (i.e. V1 and V0) as measured by the UL 94 test. Conversely, the flame retardancy tests for the Comparative examples all failed (it should be understood that the initial viscosity of Comparative example 2 was too high (8600 mPa·s) , making effective potting impossible; therefore, its flame retardancy was not tested further) .
[0125] Specifically, in Comparative examples 1 and 4, the flame retardancy test of the polyurethane foam failed when the content of the FR-1 flame retardant was less than 8 weight%of the total weight of the polyol component. In Comparative examples 3 and 5, the flame retardancy test of the polyurethane foam failed when the content of the FR-2 flame retardant was less than 5 weight%of the total weight of the polyol component.
[0126] Comparing Examples 1-9 and Comparative examples 6-7, the flame retardancy test of the polyurethane foam failed when the polyol component did not contain an FR-2 flame retardant but did contain an inorganic phosphoric acid salt.
[0127] In addition, the mechanical properties, electrical insulating properties, etc. of the polyurethane foams obtained in Examples 1-9 were also determined. As shown in Table 2, the polyurethane foams in Examples 1-9 show high elasticity of soft material, and good electrical insulating properties.
[0128] The structures, materials, components, compositions and methods described herein are intended to serve as representative examples of the invention, and it should be understood that the scope of the invention is not limited by the scope of the examples. Those skilled in the art will recognize that the present invention may be implemented by changing the disclosed structures, materials, compositions and methods, and these changes are considered to be within the scope of the present invention. Therefore, the present invention is intended to cover such modifications and changes that fall within the scope of the appended claims and the equivalents thereof.
Claims
1.Polyol component, comprising the following components:(a-1) at least one polyol reactive to isocyanate,(a-2) a chain extender and / or a crosslinker,(a-3) a blowing agent,(a-4) optionally a catalyst,(a-5) a solid flame retardant, and(a-6) optionally an additive and / or an aid,wherein the solid flame retardant comprises an FR-1 flame retardant and an FR-2 flame retardant, the FR-1 flame retardant is a nitrogen-containing solid flame retardant, a metal-free phosphorus-containing solid flame retardant or a combination thereof, the FR-2 flame retardant is a metal organophosphate solid flame retardant, the FR-1 flame retardant accounts for 8 to 20 weight%of the total weight of the polyol component, and the FR-2 flame retardant accounts for 5 to 25 weight%of the total weight of the polyol component.2.Polyol component according to Claim 1, wherein the weight ratio of the FR-2 flame retardant to the FR-1 flame retardant is 3: 1 to 1: 4.3.Polyol component according to Claim 1 or 2, wherein the solid flame retardant accounts for 13 to 45 weight%of the total weight of the polyol component.4.Polyol component according to Claim 1 or 2, wherein the nitrogen-containing solid flame retardant comprises at least one selected from the following: melamine, melamine salts, guanidine, melamine cyanurate, melamine polyphosphate, melamine phosphate, melamine formaldehyde, hydroxymethylated melamine, hexamethoxymethyl melamine, urea, dimethylurea, melamine pyrophosphate, dicyandiamide, guanylurea phosphate and glycine, preferably melamine and derivatives thereof.5.Polyol component according to Claim 1 or 2, wherein the metal-free phosphorus-containing solid flame retardant comprises at least one selected from the following: 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) , triphenylphosphate, ammonium polyphosphate, red phosphorus, tributyl phosphate (RBP) and mixtures thereof.6.Polyol component according to Claim 1 or 2, wherein the metal organophosphate solid flame retardant comprises at least one selected from the following: metal salts of phosphoric acid, phosphonic acid or phosphinic acid, wherein the metal is selected from iron, aluminium, magnesium, zinc, lanthanum or cerium.7.Polyol component according to Claim 1 or 2, wherein the metal organophosphate solid flame retardant comprises an organophosphinic acid metal salt with the following formula: R1 and R2 are the same or different and denote straight-chain or branched C1-C6 alkyl groups (more preferably C1-C4 alkyl groups) ;M denotes Al, Mg, Ca, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na or K;m denotes 1, 2, 3 or 4,preferably, the organophosphinic acid metal salt is at least one selected from the following: aluminium diethyl phosphinate, aluminium methylethyl phosphinate, aluminium dipropyl phosphinate, aluminium dibutyl phosphinate, aluminium ethylbutyl phosphinate, aluminium ethylhexyl phosphinate, aluminium butylhexyl phosphinate, and mixtures thereof.8.Polyol component according to Claim 1 or 2, wherein the polyol reactive to isocyanate is a polyether polyol with a number average molecular weight Mn of 300 to 8000, preferably 3000 to 6500, and 2 ≤ functionality Fn ≤ 3.9.Polyol component according to Claim 1 or 2, wherein the polyol reactive to isocyanate accounts for 35 weight%to 85 weight%, preferably 40 weight%to 70 weight%of the total weight of the polyol component.10.Polyol component according to Claim 8, wherein the polyether polyol further comprises a flame retardant polyether polyol, which accounts for 0 weight%to 40 weight%, preferably 5 weight%to 20 weight%of the total weight of the polyether polyol.11.Potting composition, obtained by reacting at least the following components:an isocyanate component, comprising:(b-1) at least one isocyanate, and(b-2) optionally a second flame retardant,and the polyol component according to any one of Claims 1-10.12.Potting composition according to Claim 11, wherein the second flame retardant comprises a liquid flame retardant selected from at least one of the following: resorcinol bis(diphenyl) phosphate (RDP) , tris (1-chloro-2-propyl) phosphate (TCPP) and tricresyl phosphate (TCP) .13.Potting composition according to Claim 11 or 12, wherein the second flame retardant accounts for 0 weight%to 40 weight%, preferably 5 weight%to 35 weight%, and more preferably 5 weight%to 20 weight%of the total weight of the isocyanate component.14.Potting composition according to Claim 11 or 12, wherein the polyol component and the isocyanate component are mixed in the weight ratio 100: (30-100) , preferably 100: (40-90) .15.Potting composition according to Claim 11 or 12, wherein the polyol component and the isocyanate component, once mixed, have an initial viscosity measured according to ASTM D2196-15 of less than 7000 mPa·s, preferably less than 5000 mPa·s at a temperature of 25 ℃.16.Polyurethane foam prepared from the potting composition according to any one of Claims 11 to 15.17.Polyurethane foam according to Claim 16, wherein the polyurethane foam has a modulus of less than 25 MPa, preferably less than 20 MPa, and more preferably less than 10 MPa, measured according to ISO1798.18.Polyurethane foam according to Claim 16, wherein the polyurethane foam has a flame retardancy of at least grade V2 or higher, more preferably at least grade V1 or higher, and most preferably grade V0, as measured by the UL 94 test.19.Polyurethane foam according to Claim 16, wherein the density of the polyurethane foam is 0.1-0.4 g / cm3, preferably 0.2-0.3 g / cm3.20.Battery product, comprising:battery cells; anda polyurethane foam located between the battery cells, prepared in accordance with the potting composition of any one of Claims 11 to 15.
Citation Information
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