CN111019589B - Two-component polyurethane adhesive, preparation method thereof and application thereof in soft package battery - Google Patents
Two-component polyurethane adhesive, preparation method thereof and application thereof in soft package battery Download PDFInfo
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- CN111019589B CN111019589B CN201911264768.9A CN201911264768A CN111019589B CN 111019589 B CN111019589 B CN 111019589B CN 201911264768 A CN201911264768 A CN 201911264768A CN 111019589 B CN111019589 B CN 111019589B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- 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
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- 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
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Abstract
The invention relates to a two-component polyurethane adhesive, which comprises the following raw materials in percentage by weight: 10-50% of castor oil derivative polyol; 10-30% of polyester polyol; 1-10% of a molecular sieve; 20-60% of a filler; 10-30% of a solid flame retardant; 0.1-5% of a silane coupling agent; 0.1-0.5% of a catalyst; the raw material formula of the component B comprises: 10-50% of isocyanate; 1-5% of a water removing agent; 1-10% of a plasticizer; 20-45% of a solid flame retardant; 5-25% of a liquid flame retardant; 1-5% of filler. Compared with the traditional two-component polyurethane structural adhesive, the two-component polyurethane adhesive has high bonding strength to the PET film/aluminum plastic film under the condition that the PET film/aluminum plastic film base material is not treated, can achieve the damage form of film tearing, improves the toughness of the product, has high elongation at break and has excellent flame retardant property.
Description
Technical Field
The invention belongs to the field of new energy automobile power batteries, and particularly relates to a two-component polyurethane adhesive, a preparation method thereof and application thereof in a soft package battery.
Background
According to the national environmental protection strategy, new energy development is advocated, and the new energy policy drives the battery industry to blow out. With the rapid development of the lithium battery, the lithium battery has the advantages of high energy density, low self-discharge rate, long cycle life, no pollution, environmental protection, light weight and the like, and becomes a reliable material for a new energy electric vehicle power battery.
The power battery system of the new energy automobile is formed by combining a plurality of batteries in a series-parallel connection mode, and can be divided into a battery pack, a battery module and a battery core according to a system level. The battery cell can be divided into an aluminum shell square battery cell, a steel shell cylindrical battery cell and a thin film soft package battery cell according to the external package form. At present, power batteries are in rapid development and change, battery technology, battery structure and material design change rapidly, and aluminum plastic film/PET film soft package batteries are widely applied to battery packaging due to superior performance and convenience.
The PET material can be easily made into various sectional materials due to the excellent mechanical property, impact strength, electrical insulation property, temperature resistance and processability, meets the structural design and is widely applied to the soft package battery industry. The aluminum-plastic film meets the requirements of high density, large capacity and large charge-discharge multiplying power, and has high mechanical property, excellent water insulation, corrosion resistance and abrasion resistance; and has the advantages of light weight, thin thickness, flexible appearance design and the like, and becomes an important material of the soft package battery.
When the battery pack is assembled into a battery module, it is necessary to perform bonding or sealing with an adhesive. However, PET film/aluminum plastic film is a difficult-to-bond material. The main industrial approach to solve the adhesion problem is to pretreat the surface of the PET film/aluminum plastic film, and these pretreatment procedures greatly increase the process cost and cause some environmental pollution. Although the epoxy structural adhesive has high bonding strength to metal, the adhesion to PET film/aluminum plastic film material is not stable, and meanwhile, the common epoxy structural adhesive has poor toughness and low tolerance to cold and hot shock and high-frequency vibration conditions. The general acrylic resin has certain advantages on the adhesion of polar materials, but has poor toughness and aging resistance and large smell. The silica gel has excellent bonding performance, but the problem of slow curing speed of single-component silica gel exists, and the double-component silica gel can generate small molecules to migrate to the battery core protective layer, so that the service life of the battery is influenced. The double-component polyurethane adhesive has the advantages of wide bonding range, adjustable hardness, flexibility, good impact resistance, safety, environmental protection, high volume resistivity and the like, and becomes the first choice.
CN 108264876A introduces a two-component acrylate structural adhesive for adhering surface untreated PET material and a preparation method thereof, the two-component acrylate structural adhesive improves toughness and adhesive force by introducing a flexible resin, an organic silicon modified resin and an organic borane system, can realize effective adhesion and rapid curing of the surface untreated PET material, and has high shear strength. The patent is applied to structural bonding of PET plastic and does not relate to application of PET films in power cells.
In patent CN 105907354B, a weather-resistant two-component polyurethane adhesive for bonding a PET (polyethylene terephthalate) supporting layer of a solar cell back plate is introduced, and can keep good bonding force on a PET material for a long time; has excellent humidity resistance and heat resistance and yellowing resistance, and can be applied to occasions with higher weather resistance requirements. However, the adhesive disclosed in the patent needs to be hot-pressed and compounded at high temperature to bond films, and is not related to the application of PET films of new energy power batteries.
CN 109593507A introduces a polyurethane adhesive for bonding a soft package battery cell, which has good bonding performance to PET and aluminum alloy materials of the soft package battery cell. The adhesive in the patent gives an initial adhesion comparable to silica gel by adding tackifying resin, but the toughness and flame retardant property of the adhesive are not deeply discussed.
Patent CN 109181621 a introduces a two-component polyurethane resin adhesive for polymer lithium ion battery flexible packaging films and a preparation method thereof, which improves the toughness and heat resistance of polyurethane adhesives, but does not make intensive studies on the above properties, and the flame retardant property of the adhesives is poor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a two-component polyurethane adhesive which has excellent adhesive property to a PET film/aluminum plastic film, good elasticity and flame retardance meeting the standard 94UL-V0 under the condition that a base material is not specially treated, a preparation method thereof and application thereof in a soft package battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
one aspect of the present invention provides a two-component polyurethane adhesive comprising an a-component and a B-component,
the formula of the component A comprises the following raw materials by weight percent based on 100 percent of the total mass of the component A:
the formula of the raw material of the component B comprises the following components in percentage by mass of 100 percent of the total mass of the component B:
the component A is compounded with other components through the combined use of the castor oil derivative polyol and the polyester polyol, so that the adhesive property of the adhesive to the PET film/aluminum plastic film is improved; according to the invention, the flame retardant in the component A and the component B is compounded, so that the flame retardant property of the product can meet 94 UL-V0; according to the invention, through compounding of the whole formula, the product has good elasticity, and can meet various dynamic loads and static loads in the running process of an automobile and deformation at different temperatures.
Preferably, the raw material formula of the component A comprises the following components in percentage by mass based on 100 percent of the total mass of the component A:
the formula of the raw material of the component B comprises the following components in percentage by mass of 100 percent of the total mass of the component B:
preferably, the raw material formula of the component A also comprises 1-5 wt% of a chain extender.
More preferably, the chain extender is one or more of 1, 4-butanediol, diethylene glycol, butylethylpropanediol, diethylpentanediol, 2-ethyl-1, 3-hexanediol and trimethylolpropane.
The invention further improves the tensile property and the adhesive property of the product by adding the chain extender.
Preferably, the functionality of the castor oil derivative polyol is 2-5, and the average hydroxyl value is 100-400 mgKOH/g; for example: polycin series produced by Vertellus materials corporation, Uric H series produced by Ito oil-making corporation of Japan, Lupranol Balance series produced by Elastogran corporation of Germany, and A series produced by Shanghai Jingtian New materials corporation.
Preferably, the polyester polyol is one or more of adipic acid polyester diol, aromatic polyester polyol, dimer polyester diol, polycaprolactone polyol, polycarbonate diol and special polyester polyol with side groups, the functionality of the polyester polyol is 2-3, and the number average molecular weight is 1000-4000 g/mol.
Preferably, the catalyst is one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dimorpholinodiethyl ether, potassium isooctanoate, zinc isooctanoate and bismuth isooctanoate.
Preferably, the molecular sieve is one or more of 3A type, 4A type and 5A type molecular sieves.
Preferably, the filler is one or more of calcium carbonate, kaolin, talcum powder and white carbon black.
Preferably, the silane coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane and anilinopropyltrimethoxysilane.
Preferably, the water removal agent is one or more of calcium oxide, triethyl orthoformate and p-toluenesulfonyl isocyanate.
Preferably, the plasticizer is one or more of dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, dioctyl adipate and phenyl alkyl sulfonate.
Preferably, the solid flame retardant is one or more of aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, antimony trioxide, zinc borate, barium metaborate and an antimony oxide-silicon oxide compound.
Preferably, the liquid flame retardant is a halogenated phosphate or a phosphate.
Further preferably, the liquid flame retardant is one or more of tris (2-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) ethylidene ether diphosphate, dimethyl methyl phosphate, triphenyl phosphate and resorcinol bis (diphenyl phosphate).
Preferably, the isocyanate is polymeric MDI.
Preferably, the raw material formula of the component B also comprises 10-40 wt% of polyurethane prepolymer, so that the toughness and the elongation of the product can be further improved.
Further preferably, the polyurethane prepolymer is prepared by reacting isophorone diisocyanate with polyether triol at 80 ℃ for 2 hours under the protection of nitrogen, and controlling the NCO content at the reaction end point to be 2-4%.
When the two-component polyurethane adhesive is used, the volume ratio of the component A to the component B is 1: 0.9-1.1, so that the component A and the component B are preferably packaged by double pipes according to the using volume, and the two-component polyurethane adhesive is convenient for users to use, does not need to be weighed and mixed when used, and is convenient to use.
The second aspect of the present invention provides a preparation method of the two-component polyurethane adhesive, wherein the preparation method of the component a comprises: adding the castor oil derivative polyol and the polyester polyol, selectively adding a chain extender, heating to 110-130 ℃, stirring and dehydrating for 1-2 hours under a vacuum condition, cooling to below 50 ℃, adding the molecular sieve, the filler, the solid flame retardant, the silane coupling agent and the catalyst into the reaction kettle, and uniformly stirring under a vacuum condition to obtain the castor oil derivative polyol;
the preparation method of the component B comprises the following steps: adding the isocyanate, selectively adding the polyurethane prepolymer, adding the water scavenger, mixing, adding the plasticizer, the solid flame retardant, the liquid flame retardant and the filler, and uniformly dispersing under a vacuum condition to obtain the flame-retardant polyurethane foam material.
The third aspect of the invention provides an application of the two-component polyurethane adhesive in a soft package battery.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
compared with the traditional two-component polyurethane structural adhesive, the two-component polyurethane adhesive has high bonding strength to the PET film/aluminum plastic film under the condition that the PET film/aluminum plastic film base material is not treated, can achieve the damage form of film tearing, improves the toughness of the product, has high elongation at break and has excellent flame retardant property.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The percentages referred to in the present invention are mass percentages.
(1) The component A comprises: a1: a castor oil derivative polyol (trade name A4105, functionality of 3.0, average hydroxyl value of about 310-320mgKOH/g, Shanghai Jing Nippon New Material science and technology Co., Ltd.). A2: polyester Polyol (Kuraray Polyol P-2011, Mn 2000, japan, korea). A3: a small-molecule chain extender (2-ethyl-1, 3-hexanediol, a hydroxyl value of 766mgKOH/g, Nippon Kyoho fermentation chemical Co., Ltd.). Molecular sieve: type 3A, shanghai has new molecular sieves limited. Aluminum hydroxide: flame retardant new materials of combined fertilizer traditional Chinese medicine. Silane coupling agent: silquest A-187, MOMENTIVE Inc. Catalyst: DBTDL T-12, air chemical engineering.
Preparation of component A: adding three polyols (A1, A2 and A3) into a reaction kettle, heating to 120 ℃, stirring and dehydrating for 2 hours under vacuum, and cooling to a temperature less than 50 ℃; and then adding the molecular sieve, the filler, the solid flame retardant, the silane coupling agent and the catalyst into the reaction kettle, uniformly stirring under a vacuum condition, and subpackaging, sealing and storing.
The proportion of the component A of each example and each comparative example is shown in the table 1, wherein the proportion of each component is mass percent.
TABLE 1
(2) And B component: b1: polymeric MDI (PM-200, Tantawa polyurethane Co., Ltd.). B2: a polyurethane prepolymer is prepared by reacting isophorone diisocyanate (IPDI, Covestro company) with polyether triol (NJ-330N, New Material Co., Ltd.) at 80 ℃ for 2 hours under the protection of nitrogen, and controlling the NCO content at the reaction end point to be 2% -4%. Water removal agent: PTSI, Covestro. Plasticizer: JAYFLEXTMDIDP, Exxonmobil chemical commerce, Inc. Aluminum hydroxide: flame retardant new materials of combined fertilizer traditional Chinese medicine. Liquid flame retardant: TPP, Jiangsu Chang Yuan chemical Co. White carbon black, R974, winning degussa corpi.
Preparation of curing agent B component: mixing polyisocyanate compound (B1), polyurethane prepolymer (B2) and water-removing agent, adding plasticizer, solid flame retardant, liquid flame retardant, filler, etc., dispersing uniformly under vacuum condition, packaging, sealing and storing.
The proportion of the component B in each example and comparative example is shown in Table 2, wherein the proportion of each component is in percentage by mass.
TABLE 2
The A-and B-components of each example and comparative example were used in a volume ratio of 1: 1, and the following properties were measured, and the results of the tests are shown in Table 3.
(1) Tensile strength test: the tensile strength and elongation at break of the dumbbell-shaped splines after curing for 7d in the standard environment were tested according to the standard GB/T528-.
(2) Shear strength test: firstly wiping dust or stains on the surfaces of a PET film and an aluminum plastic film by alcohol, putting a two-component polyurethane sample (1/1 double pipes in volume ratio) into a glue gun, slightly pushing a push rod until the two components are both glued, then installing a mixing pipe to glue at the bonding position of a plastic substrate, clamping and pressing by a clamp, fixing the bonding area (25mm multiplied by 12.5mm) and controlling the thickness of a glue layer to be 0.2 mm. The samples were prepared in a standard environment at 23 ℃/50% RH and tested for shear strength after 7 days of curing in the standard environment according to standard GB/T7124, the test results are shown in Table 3.
Destruction form: according to the shear strength test method, whether the damaged sample piece is interface damage (AF), or internal damage (CF) or film tearing (SF) at the adhesive layer bonding part is observed.
(3) And (3) testing the flame retardance: and testing the flame retardant performance by referring to UL-94 standard test.
TABLE 3
Wherein, the shear strength test results in table 3, taking "1.2 AF" as an example, mean that under 1.2MPa, in the multi-group parallel test example, 100% of the damage of the PET film-PET film at the adhesive layer bonding part is interface damage; taking "6.0/85 CF" as an example, the failure of the A1-A1 substrate sample in the adhesive part of the adhesive layer is 85% of cohesive failure of the adhesive layer in a multi-group parallel test example under 6.0 MPa; taking "2.9/SF" as an example, it means that in the multi-group parallel test example, the film tearing is 100% of the damage of the aluminum plastic film-aluminum plastic film at the adhesive layer bonding part under 2.9 MPa.
The results of the adhesion experiment of the two-component polyurethane adhesive with different optimized formulations to the plastic substrate are shown in table 3. Comparing A1/B1 and A2/B2, it can be seen that the addition of polyester polyol in the component A can effectively improve the bonding effect on PET film/aluminum plastic film and A1 base material, and the bonding strength is obviously improved. In addition, the comparison of A1/B1, A2/B1, A1/B2 and A2/B2 shows that only calcium carbonate filler exists in the formula of A1/B1, and the flame retardant property is only HB; solid fire retardant aluminum hydroxide is added into the formula A2/B1, and the fire retardant grade is improved to V2; solid flame retardant aluminum hydroxide and liquid flame retardant TPP are added into the formula A1/B2, and the flame retardant grade is improved to V1; the formula A2/B2 is compounded by solid flame retardant and liquid flame retardant, the proportion is optimized, and the flame retardance can reach UL-94V 0. Comparing A2/B2 and A2/B3, it can be seen that the addition of aliphatic isocyanate to component B results in a polyurethane prepolymer with improved toughness and elongation of more than 100% while maintaining the tensile strength of the adhesive. Comparing A2/B3 and A3/B3, it can be seen that the strength of the adhesive can be improved without affecting the adhesive property and the elongation rate of the adhesive by adding a small amount of micromolecule chain extender into the component A.
As can be seen from table 3, in the embodiment of the two-component polyurethane adhesive of a2/B3 and A3/B3, the components are organically matched by optimizing the components of the formula, so that the adhesive has good adhesive strength to a PET film and an aluminum plastic film under the condition of no treatment, the adhesive can achieve the effect of tearing the film, and the adhesive requirements of different cell materials in a new energy power soft package battery are met. By compounding the aluminum hydroxide and the liquid flame retardant, the high-performance adhesive with excellent flame retardant property can be prepared, and the application requirement of the soft package battery can be met.
The present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.
Claims (9)
1. A two-component polyurethane adhesive is characterized in that: comprises an A component and a B component,
the component A comprises the following raw materials by weight percent based on 100 percent of the total mass of the component A:
23-30% of castor oil derivative polyol;
15-25% of polyester polyol;
3-8% of a molecular sieve;
25-35% of a filler;
15-25% of a solid flame retardant;
1-3% of a silane coupling agent;
0.1-0.5% of a catalyst;
the raw material formula of the component A also comprises 1-5 wt% of a chain extender;
the component B comprises the following raw materials by weight percent based on 100 percent of the total mass of the component B:
25-27% of isocyanate;
1-5% of a water removing agent;
3-10% of a plasticizer;
25-40% of a solid flame retardant;
10-20% of a liquid flame retardant;
1-3% of a filler;
the raw material formula of the component B also comprises 10-40 wt% of polyurethane prepolymer;
the solid flame retardant is one or more of aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, antimony trioxide, zinc borate, barium metaborate and an antimony oxide-silicon oxide compound;
the liquid flame retardant is halogenated phosphate or phosphate.
2. The two-component polyurethane adhesive of claim 1, wherein: the chain extender is one or more of 1, 4-butanediol, diethylene glycol, butylethylpropanediol, diethylpentanediol, 2-ethyl-1, 3-hexanediol and trimethylolpropane.
3. The two-component polyurethane adhesive of claim 1 or 2, wherein:
the castor oil derivative polyol has a functionality of 2-5 and an average hydroxyl value of 100-400 mgKOH/g.
4. The two-component polyurethane adhesive of claim 1 or 2, wherein:
the polyester polyol is one or more of adipic acid polyester dihydric alcohol, aromatic polyester polyol, dimer polyester diol, polycaprolactone polyol, polycarbonate diol and special polyester polyol with side groups, the functionality of the polyester polyol is 2-3, and the number average molecular weight is 1000-4000 g/mol.
5. The two-component polyurethane adhesive of claim 1 or 2, wherein: the polyurethane prepolymer is prepared by reacting isophorone diisocyanate and polyether triol at 80 ℃ for 2 hours under the protection of nitrogen, and controlling the NCO content at the reaction end to be 2-4%.
6. The two-component polyurethane adhesive of claim 1 or 2, wherein:
the catalyst is one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, dimorpholinyl diethyl ether, potassium isooctanoate, zinc isooctanoate and bismuth isooctanoate;
the molecular sieve is one or more of 3A type, 4A type and 5A type molecular sieves;
the filler is one or more of calcium carbonate, kaolin, talcum powder and white carbon black;
the silane coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane and phenylaminopropyltrimethoxysilane;
the water removal agent is one or more of calcium oxide, triethyl orthoformate and p-toluenesulfonyl isocyanate;
the plasticizer is one or more of dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, dioctyl adipate and phenyl alkyl sulfonate;
the isocyanate is polymeric MDI.
7. The two-component polyurethane adhesive of claim 6, wherein: the liquid flame retardant is one or more of tris (2-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) ethylidene ether diphosphate, dimethyl methyl phosphate, triphenyl phosphate and resorcinol bis (diphenyl phosphate).
8. A method of preparing the two-component polyurethane adhesive of any of claims 1-7, wherein: the preparation method of the component A comprises the following steps: adding the castor oil derivative polyol and the polyester polyol, adding a chain extender, heating to 110-130 ℃, stirring and dehydrating for 1-2h under a vacuum condition, cooling to below 50 ℃, adding the molecular sieve, the filler, the solid flame retardant, the silane coupling agent and the catalyst into a reaction kettle, and stirring uniformly under a vacuum condition to obtain the castor oil derivative polyol;
the preparation method of the component B comprises the following steps: adding the isocyanate, adding the polyurethane prepolymer, adding the water removing agent, mixing, adding the plasticizer, the solid flame retardant, the liquid flame retardant and the filler, and uniformly dispersing under a vacuum condition to obtain the flame-retardant polyurethane foam material.
9. Use of the two-component polyurethane adhesive according to any one of claims 1 to 7 in pouch batteries.
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| WO2025024066A1 (en) * | 2023-07-27 | 2025-01-30 | Ddp Specialty Electronic Materials Us, Llc | Two-component thermally conductive adhesive with improved shelf stability |
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| CN110272710B (en) * | 2019-06-13 | 2021-08-03 | 南京威邦新材料有限公司 | Polyurethane pouring sealant suitable for electronic sensor and preparation method thereof |
| CN110423592B (en) * | 2019-07-24 | 2020-07-24 | 福耀玻璃工业集团股份有限公司 | Double-component polyurethane adhesive and preparation method thereof |
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Denomination of invention: A two-component polyurethane adhesive and its preparation method and application in soft pack batteries Effective date of registration: 20230803 Granted publication date: 20220412 Pledgee: Bank of Nanjing Limited by Share Ltd. Suzhou branch Pledgor: GELITAI NEW MATERIALS TECHNOLOGY (SUZHOU) Co.,Ltd. Registration number: Y2023980050914 |
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