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CN112143437A - Lithium battery aluminum plastic film outer layer adhesive resin and preparation and application thereof - Google Patents

Lithium battery aluminum plastic film outer layer adhesive resin and preparation and application thereof Download PDF

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Publication number
CN112143437A
CN112143437A CN202010933533.0A CN202010933533A CN112143437A CN 112143437 A CN112143437 A CN 112143437A CN 202010933533 A CN202010933533 A CN 202010933533A CN 112143437 A CN112143437 A CN 112143437A
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China
Prior art keywords
plastic film
lithium battery
aluminum plastic
adhesive
adhesive resin
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CN202010933533.0A
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Chinese (zh)
Inventor
付洪娥
王新
王玉灿
李致轩
魏田
鲁琴
刘博�
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Shenyang Research Institute of Chemical Industry Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
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Priority to CN202010933533.0A priority Critical patent/CN112143437A/en
Publication of CN112143437A publication Critical patent/CN112143437A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4294—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from polyester forming components containing polyepoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electrochemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention belongs to the field of organic synthesis, relates to a high-molecular polymerization technology, and particularly relates to an outer-layer adhesive resin of an aluminum plastic film of a lithium battery, and preparation and application thereof. The lithium battery aluminum plastic film adhesive resin is solvent type bi-component adhesive resin, which consists of polyhydroxy epoxy chain-extended polyester as a component A and polyisocyanate as a component B; the mass ratio of the component A to the component B is 1:2-20: 1. The adhesive prepared by the invention is used for bonding metal aluminum foil, PA film and PP film, and the prepared aluminum-plastic film has good flexibility, tensile property, hydrolysis resistance, heat resistance, cohesiveness and impact resistance. The adhesive product prepared by the invention can completely meet the application performance requirements of the lithium battery aluminum plastic film adhesive.

Description

Lithium battery aluminum plastic film outer layer adhesive resin and preparation and application thereof
Technical Field
The invention belongs to the field of organic synthesis, relates to a high-molecular polymerization technology, and particularly relates to an outer-layer adhesive resin of an aluminum plastic film of a lithium battery, and preparation and application thereof.
Background
Since the advent of lithium ion batteries, lithium ion batteries have been rapidly developed for their excellent performance. The packaging of the lithium battery core relates to the requirements of harsh physical and mechanical properties, chemical compatibility, resistance, barrier property, electrochemical reactivity and the like in the using process of the lithium battery core, and the harsh indexes are directly related to the performance of the interlayer adhesive. At present, the commercially available soft package lithium battery aluminum plastic film product is at least three layers, wherein the inner layer base material is a nontoxic polyolefin (PP, PE and the like) layer, the aluminum foil is used as a middle layer, the outer layer is a nylon film, and each layer is compounded by different types of adhesive auxiliaries.
Currently, the aluminum-plastic film of the high-end lithium battery is almost completely monopolized by Japan, and only a few suppliers exist in the world. In order to meet the requirement of domestic lithium battery enterprises for replacing imports, domestic enterprises have engaged in research and development work of aluminum-plastic composite film technology for lithium batteries, but products cannot be accepted by markets due to unstable performance. The performance of the adhesive used for bonding the materials of each layer of the domestic aluminum-plastic film cannot meet the application requirement, and the adhesive is one of the key factors that the domestic aluminum-plastic film is not popularized in a large quantity.
Because the inner and outer base materials are made of different materials (polyolefin, nylon and the like), the materials and the middle layer aluminum foil need to be bonded by different adhesives to be perfectly combined, and the application performances of aluminum plastic film stripping, deep punching, heat resistance and the like can meet the performance requirements.
In the prior domestic synthesis technology, no related patent publication exists for specially preparing the outer layer adhesive of the aluminum plastic film of the lithium battery. In the patent literature of the current preparation of the lithium battery aluminum plastic film adhesive, CN201810088501.8 reports a synthesis method of an adhesive for a lithium battery packaging bag, which adopts polyurethane polyester, epoxy resin and acrylic resin to be physically blended and used as an inner layer adhesive and an outer layer adhesive of a lithium battery packaging material. The peeling strength of an inner layer (Al-CPP) of an aluminum-plastic film prepared by the adhesive can reach more than 10, but the peeling strength of the adhesive as an outer layer (Al-PA) is only 6-8N/15mm, and the punching depth reaches 5 mm.
Further, the improvement of the performance of the aluminum plastic film adhesive is a problem to be solved in the research of the lithium ion battery at present.
Disclosure of Invention
The invention aims to provide an outer layer adhesive resin of an aluminum plastic film of a lithium battery, and preparation and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the lithium battery aluminum plastic film outer layer adhesive resin is solvent type bi-component adhesive resin and consists of polyhydroxy epoxy chain-extended polyester serving as a component A and polyisocyanate serving as a component B; the mass ratio of the component A to the component B is 1:2-20: 1.
The polyhydroxy polyester with epoxy chain extension is carboxyl terminated polyester obtained by mixing aromatic dibasic acid, long-chain aliphatic dibasic acid and aliphatic polyol and then carrying out esterification reaction and dehydration in vacuum at 200-240 ℃; the carboxyl-terminated polyester is subjected to chain extension and tackifying by an epoxy chain extender, and the ratio of carboxyl to epoxy groups is 1:0.8-3.0, so that the polyhydroxy epoxy chain-extended polyester with the molecular weight of 20000-type 50000, the hydroxyl value of 15-300 and the acid value of 0.1-3.0 is obtained.
The carboxyl-terminated polyester is prepared by mixing aliphatic polyhydric alcohol, long-chain aliphatic dibasic acid and aromatic dibasic acid, stirring under the protection of nitrogen, heating to 200-plus-240 ℃ within 1 hour for esterification reaction, keeping the temperature for reaction for 2-3 hours, controlling the pressure to be 0.1-0.3MPa, slowly controlling the pressure to be 10-200 Pa, and continuously reacting at the temperature of 240-plus-270 ℃ to obtain carboxyl-terminated polyester Mn of 2000-plus-10000; wherein the molar ratio of the aromatic dibasic acid to the aliphatic polyhydric alcohol to the long-chain aliphatic dibasic acid is 1-6: 1-6: 1.
further, the following steps are carried out: the carboxyl-terminated polyester is prepared by mixing aliphatic diol, aliphatic dibasic acid and aromatic dibasic acid, stirring under the protection of nitrogen, heating to 200-240 ℃ within 1 hour for esterification reaction, keeping the temperature for 2-3 hours, and controlling the pressure in the kettle to be 0.1-0.3MPa until the distilled water amount reaches a theoretical value; slowly raising the vacuum degree in the kettle to 10-200 Pa, and continuously reacting at the temperature of 240-270 ℃ to the power of a theoretical motor to obtain the carboxyl terminated polyester.
The aliphatic polyhydric alcohol is dihydric alcohol or dihydric alcohol and trihydric alcohol, wherein the aliphatic dihydric alcohol and the aliphatic trihydric alcohol are respectively C2-C12Two or three of the linear or branched di-or trihydric alcohols of (a); the aliphatic dibasic acid is C3-C18The fatty dibasic acid of (1); the aromatic dibasic acid is two or three of benzene diacid and/or naphthalene diacid.
The aliphatic diol is one, two or three of ethylene glycol, 1.2-propylene glycol, 1.3-propylene glycol, butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1.6-hexanediol, 1.2-heptanediol, 1.7-heptanediol, 1.2-octanediol, 1.8-octanediol, 1.2-nonanediol, 1.9-nonanediol, 1.2-decanediol, 1.10-decanediol, 1, 11-undecanediol and 1, 12-dodecanediol. One or two of ethylene glycol, 1, 2-propylene glycol, butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 10-decanediol, and 1, 12-dodecanediol are preferable.
The aliphatic trihydric alcohol is trihydroxypropane, glycerol, 1.2.4-butanetriol or 1.2.5-pentanetriol, preferably trimethylolpropane and 1.2.4-butanetriol.
The aliphatic dibasic acid is two or three of phthalic acid, terephthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid or naphthalene-1, 4-dicarboxylic acid. Specifically, the acid may be one or more of malonic acid, succinic acid, adipic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, and octadecanedioic acid. One or two of glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid are preferred.
The aromatic dibasic acid is two or three of benzene diacid and/or naphthalene diacid. Specifically, two or three of phthalic acid, terephthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, and naphthalene-1, 4-dicarboxylic acid may be used.
The epoxy chain extender is one or two of 1, 4-cyclohexanedimethanol glycidyl ether, 1, 4-butanediol diglycidyl ether, bisphenol A-diglycidyl ether, glycidyl ether, triglycidyl isocyanurate, N, N, N ', N ' -tetraglycidyl ester-4, 4 ' -diaminodiphenylmethane, bisphenol A polyglycidyl ether, bisphenol A epoxy resin and bisphenol F epoxy resin; wherein, the addition amount of the epoxy chain extender is based on carboxyl: the molar ratio of the epoxy groups is 1: 0.8-3.0.
Adding a catalyst in the esterification reaction, wherein the adding amount of the catalyst is 300-1200 ppm; the catalyst is antimony acetate, antimony trioxide, ethylene glycol, tetrabutyl titanate and germanium oxide.
The prepared polyhydroxy epoxy chain-extended polyester is dissolved in a solvent, wherein the solvent can be ethyl acetate, butanone and toluene, and the obtained solution with the solid content of 30-32 percent is the component A.
The polyisocyanate is an addition product of TDI and pentaerythritol, and the obtained addition product is dissolved in ethyl acetate or butanone to obtain the component B with the solid content of 80-85%.
A lithium battery aluminum plastic film adhesive resin: the adhesive resin is applied to being used as an adhesive resin of an aluminum plastic film of a lithium battery.
The lithium battery aluminum-plastic film adhesive is prepared by uniformly mixing the resin A, a curing agent B, modified nano cerium oxide and an auxiliary agent; wherein the A, B component mass ratio in the resin is 100:5-25, the modified nano cerium oxide mass accounts for 0.5-4% of the adhesive, and the auxiliary agent mass accounts for 1-2% of the adhesive.
The auxiliary agent is an organic silicon flatting agent and an anti-hydrolysis agent; wherein the mass of the organic silicon flatting agent accounts for 0.5-1% of the adhesive, and the mass of the hydrolysis resistant agent accounts for 0.5-1% of the adhesive.
Wherein the organosilicon leveling agent is one of AYK-350, HY5030 and KMT-5510; the anti-hydrolysis agent is N, N' -bis (2, 6-diisopropylphenyl) carbodiimide.
The application of the adhesive for the aluminum plastic film of the lithium battery comprises the steps of coating the adhesive for the aluminum plastic film of the lithium battery containing the adhesive resin on one side of an aluminum foil, drying at 70-100 ℃ for 1 minute, carrying out hot-pressing compounding on the obtained adhesive film and a nylon PA film at 70-90 ℃ under the pressure of 0.5MPa, coating the adhesive for the aluminum plastic film of the lithium battery on the other side of the aluminum foil, drying at 70-100 ℃ for 1 minute, carrying out hot-pressing compounding on the obtained adhesive film and a PP film at 70-90 ℃ under the pressure of 0.5MPa, and curing at 85 ℃ for 72 hours to obtain the aluminum plastic film of the lithium battery.
The invention has the advantages that:
the lithium battery adhesive resin is obtained by compounding epoxy modified polyester polyol and a polyisocyanate curing agent according to a certain proportion. The aromatic dibasic acid is used for improving the bonding performance, the long carbon chain aliphatic dibasic acid is used for improving the flexibility of the adhesive, the ratio of monomers is adjusted, and the prepared polyester can improve the toughening, hydrolysis resistance, high temperature resistance and high bonding strength performance of the adhesive; after the polyester epoxy chain extension, a component A with the characteristics of high hydroxyl content, uniform distribution in hydroxyl polymers and the like is obtained, and then the component A and the component B are compounded into a gluing agent, so that the advantage of more bonding anchoring points of the polyester adhesive material is realized; meanwhile, the branched chain dihydric alcohol is added in the molecular synthesis process, so that the adhesive product prepared by the invention has excellent hydrolysis resistance of the adhesive film, and can completely meet the application performance requirement of the aluminum plastic film of the lithium battery on the outer layer adhesive.
Detailed Description
The present invention is further illustrated in detail by the following examples. The invention is in no way limited thereto.
The adhesive resin for the aluminum plastic film of the lithium battery is composed of two components, wherein a component A is polyhydroxy epoxy modified polyester, and a component B is polyisocyanate; the resin is used as PP, PE and aluminum foil adhesive resin and is used as an inter-film bonding material of an aluminum plastic film of a lithium battery. The component A contains epoxy chain-extended polyester with polyhydroxy active groups in the molecule and has the molecular weight of 20000-50000. Component B contains TDI adducts of 3-5 isocyanate groups. Wherein, the component A is prepared by esterification reaction of aliphatic dihydric alcohol, long-chain aliphatic dibasic acid and aromatic dibasic acid in inert gas under normal pressure; then adding a catalyst for polycondensation reaction under the conditions of high temperature and high vacuum, and adding a solvent for dissolving the obtained polymer after chain extension of the obtained carboxyl terminated polyester diol by using an epoxy compound, thereby obtaining the carboxyl terminated polyester diol. The component B is an addition product of TDI and pentaerythritol. The adhesive obtained by the resin has good peeling strength, deep penetration resistance, heat resistance and water boiling resistance for PP films, PA films and aluminum foils. Can completely meet the application performance requirements of the lithium battery aluminum plastic film adhesive.
Example 1
580.5 g of terephthalic acid, 720.6 g of isophthalic acid, 317.0 g of sebacic acid, 496 g of ethylene glycol, 128.1 g of 1, 6-hexanediol, 6.5 g of 3-methylpentanediol and 1.0 g of antimony acetate catalyst are added into a 3L polymerization reactor, the temperature is raised to 240 ℃ within about one hour, the distillation rate of generated water is adjusted, the pressure in the reactor is kept between 0.2 and 0.3MPa, and the temperature at the top of the water distillation tower is lower than 140 ℃ until the distilled water amount reaches 170 g, thus finishing the esterification reaction. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 40-80Pa for about half an hour, simultaneously raising the temperature to 275 ℃, starting the polycondensation reaction, reacting for 2.5 hours under the condition, and discharging to obtain the carboxyl-terminated polyester.
The polyester obtained above was subjected to GPC measurement to find that it had a molecular weight of Mn 7800, an acid value of 13.9mgKOH/g and a hydroxyl value of 0.48 mgKOH/g.
50 g of the carboxyl-terminated polyester obtained above was put in a pressure bottle, dissolved in 131 g of ethyl acetate, and 6.19 g of bisphenol A epoxy resin E51 was added and reacted at 110 ℃ for 7 hours to obtain a solution having a solid content of 30%, namely component A. After the sample was freed of the solvent, it was tested for an acid value of 0.89mgKOH/g, a hydroxyl value of 65.2mgKOH/g and a molecular weight of Mn38000 by GPC.
Example 2
824.0 g of isophthalic acid, 317.0 g of adipic acid, 378.2 g of ethylene glycol, 98.4 g of 3-methyl 1, 5-pentanediol and 1.0 g of antimony trioxide are added into a 3L polymerization reactor, the temperature is raised to 250 ℃ within about one hour, the distillation rate of generated water is adjusted, the pressure in the reactor is kept between 0.25 and 0.3MPa, the temperature at the top of the distillation tower is kept lower than 120 ℃, until the amount of distilled water reaches 90 g, and the esterification reaction is finished. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 60Pa for about half an hour, simultaneously raising the temperature to 280 ℃, starting polycondensation reaction, reacting for 3 hours under the condition, and discharging to obtain the carboxyl-terminated polyester.
The polyester obtained above was subjected to GPC measurement to find that it had a molecular weight of Mn 8600, an acid value of 12.80mgKOH/g and a hydroxyl value of 0.28 mgKOH/g.
30 g of carboxyl terminated polyester, 8.5 g of 1, 4-butanediol diglycidyl ether and 90 g of butanone are added into a pressure-resistant bottle, and after dissolution, the mixture reacts for 5 hours at 130 ℃ to obtain a solution with the solid content of 30 percent, namely the component A. After the sample was freed of the solvent, it was tested for an acid value of 0.52mgKOH/g, a hydroxyl value of 61.1mgKOH/g, and a molecular weight Mn35000 by GPC.
Example 3
580.5 g of phthalic acid, 720.6 g of isophthalic acid, 217.0 g of adipic acid, 612.4 g of 1, 2-propanediol, 128.1 g of 1, 4-butanediol, 6.5 g of trimethylolpropane and 1.0 g of antimony acetate are added into a 3L polymerization reaction kettle, the temperature is raised to 260 ℃ within about one hour, the distillation rate of generated water is adjusted, the pressure in the kettle is kept between 0.25 and 0.3MPa, and the temperature at the top of the distillation tower is lower than 120 ℃ until the distilled water amount reaches 165 g, so that the esterification reaction is finished. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 145Pa for about half an hour, simultaneously raising the temperature to 275 ℃, starting the polycondensation reaction, reacting for 2.5 hours under the condition, and discharging to obtain the carboxyl-terminated polyester.
The polyester obtained above was subjected to GPC measurement to find that it had a molecular weight of Mn 5200, an acid value of 21.2mgKOH/g and a hydroxyl value of 0.38 mgKOH/g.
30 g of carboxyl terminated polyester, 21 g of bisphenol A polyglycidyl ether and 120 g of ethyl acetate are added into a pressure-resistant bottle, the temperature is raised to 100 ℃, and the mixture is magnetically stirred for 3.5 hours to obtain a solution with the solid content of 30 percent, namely the component A. After removing the solvent, the sample was measured for acid value of 0.81mgKOH/g, hydroxyl value of 58.9mgKOH/g, and molecular weight Mn of 42000 by GPC.
Example 4
880.0 g of terephthalic acid, 217.0 g of azelaic acid, 280.4 g of ethylene glycol, 160.5 g of neopentyl glycol and 0.8 g of antimony acetate are added into a 3L polymerization reaction kettle, the temperature is raised to 260 ℃ within about one hour, the distillation speed of generated water is adjusted, the pressure in the kettle is kept between 0.25 and 0.3MPa, the temperature at the top of the distillation tower is lower than 120 ℃ until the distilled water amount reaches 160 g, and the esterification reaction is finished. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 200Pa for about half an hour, simultaneously raising the temperature to 250 ℃, starting the polycondensation reaction, reacting for 1.5 hours under the condition, and discharging to obtain the carboxyl-terminated polyester.
The polyester obtained above was subjected to GPC measurement to find that it had a molecular weight of Mn3800, an acid value of 28.93mgKOH/g and a hydroxyl value of 0.63 mgKOH/g.
Adding 15 g of carboxyl terminated polyester, 37.8 g of bisphenol A epoxy resin E44 and 100 g of acetone into a pressure-resistant bottle, heating to 80 ℃ after dissolving, and magnetically stirring for 8 hours to obtain a solution with the solid content of 30%, namely the component A. After removing the solvent, the sample was measured for an acid value of 1.23mgKOH/g, a hydroxyl value of 78.5mgKOH/g, and a molecular weight Mn of 29000 by GPC.
Comparative example 1
580.5 g of terephthalic acid, 720.6 g of isophthalic acid, 317.0 g of sebacic acid, 746 g of ethylene glycol, 128.1 g of 1, 6-hexanediol, 6.5 g of trimethylolpropane and 1.0 g of antimony acetate are added into a 3L polymerization reactor, the temperature is raised to 240 ℃ within about one hour, the distillation rate of generated water is adjusted, the pressure in the reactor is kept between 0.25 and 0.3MPa, the temperature at the top of the distillation tower is lower than 120 ℃ until the distilled water amount reaches 170 g, and the esterification reaction is finished. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 80Pa for about half an hour, simultaneously raising the temperature to 275 ℃, starting the polycondensation reaction, reacting for 4-5 hours under the condition, slowly increasing the power, and discharging 256 g of polycondensation distillate to obtain the hydroxyl-terminated polyester.
GPC measured the molecular weight Mn 34000, hydroxyl value 3.61mgKOH/g, acid value 0.5 mgKOH/g.
Comparative example 2
320.6 g of isophthalic acid, 617.0 g of adipic acid, 296.0 g of ethylene glycol, 160.5 g of 3-methylpentanediol, 6.5 g of trimethylolpropane and 1.0 g of antimony trioxide are added into a 3L polymerization reactor, the temperature is raised to 240 ℃ within about one hour, the distillation rate of generated water is adjusted, the pressure in the reactor is kept between 0.25 and 0.3MPa, and the temperature at the top of the distillation tower is kept lower than 120 ℃ until the amount of distilled water reaches 110 g, and the esterification reaction is finished. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 80Pa for about half an hour, simultaneously raising the temperature to 275 ℃, starting the polycondensation reaction, reacting for 2.5 hours under the condition, and discharging to obtain the hydroxyl-terminated polyester.
GPC measured the molecular weight Mn42000, acid value 0.38mgKOH/g, hydroxyl value 3.12 mgKOH/g.
Comparative example 3
498 g of isophthalic acid, 531 g of 1, 6-hexanediol, 270 g of 2-methyl-1, 3-propanediol and 0.3 g of tetrabutyl titanate as a catalyst were added to a 3L polymerization reactor, and the temperature was slowly raised to 260 ℃ to carry out dehydration esterification. And finishing the esterification reaction when the water yield reaches 106 g. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 80Pa for about half an hour, simultaneously raising the temperature to 275 ℃, starting the polycondensation reaction, reacting for 2.5 hours under the condition, and discharging to obtain the hydroxyl-terminated polyester.
GPC measured molecular weight Mn 12000, acid value 0.8mgKOH/g, hydroxyl value 8.61 mgKOH/g.
Comparative example 4
13.2 g of the carboxyl-terminated polyester prepared in example 4, 31.0 g of bisphenol A epoxy resin E51 and 100 g of butanone were added to a pressure bottle, and after dissolution, the temperature was raised to 80 ℃ and magnetic stirring was carried out for 3 hours to obtain a solution containing about 30% of the solid content, namely component A. After removing the solvent, the sample was tested for an acid value of 1.23mgKOH/g, a hydroxyl value of 75.2mgKOH/g, and a molecular weight Mn16500 by GPC.
Comparative example 5
In a pressure bottle, 14.8 g of the carboxyl-terminated polyester prepared in example 4, 38.2 g of bisphenol A epoxy resin E44 and 100 g of acetone were added, and after dissolution, the temperature was raised to 100 ℃ and magnetic stirring was carried out for 15 hours to obtain a solution containing about 30% of the solid content, namely component A. After removing the solvent, the sample was measured for acid value of 1.23mgKOH/g, hydroxyl value of 78.5mgKOH/g, and molecular weight Mn of 59000 by GPC.
Application test:
preparing glue:
the products prepared in examples 1-4 and comparative examples 1,2, 4 and 5 and TDI pentaerythritol addition product (obtained by reacting TDI and pentaerythritol in a molar ratio of 4:1 in ethyl acetate solvent at 90 ℃ for 4 hours) are added with oleophylic modified nano cerium dioxide (purchased from market) accounting for 2% of the mass ratio, 0.6% of hydrolysis stabilizer N, N' -bis (2, 6-diisopropylphenyl) carbodiimide and 0.8% of leveling agent AYK-350 and evenly mixed according to the mass ratio of 10:1.4 for standby.
And (3) mixing the product in the comparative example 3, the epoxy resin NPEL128 and the curing agent TPA according to the mass ratio of 10:0.8:0.4, and dissolving the mixture in ethyl acetate to prepare an adhesive solution with solid content of 25% for later use.
Coating application:
coating the prepared adhesive on the surface of the aluminum foil, wherein the adhesive application amount is 4g/m2(folding) drying at 85 ℃ for 1 minute, coating PA film on a film coating machine, and preheating the film coating machine to 105 ℃; this operation was repeated to coat the inner PP film. Curing the composite film material for 7 days at 65 ℃, and performing deep punching, heat sealing, heat resistance, boiling resistance, peeling and the likeThe performance tests were applied and the test data are shown in table 1 below.
Evaluation method:
1. and (3) testing the peel strength: referring to the standard of GB-T2791-1995 adhesive T peel strength test method for flexible materials, an aluminum-plastic film sample is cut into a strip shape of 15mm multiplied by 20cm, one ends of a nylon layer and an aluminum foil layer which are not glued are symmetrically clamped on an upper clamp and a lower clamp of a universal testing machine respectively, the clamped parts cannot slide so as to ensure that the applied tensile force is uniformly distributed on the width of the sample, and the testing machine is started to separate the upper clamp and the lower clamp at the speed of 100 +/-10 mm/min. The peel length of the sample is at least 125 mm.
2. And (3) testing the punching depth performance:
a double-pit deep punching die is adopted, the pit depth is 5mm, and the distance between the two pits is 1 mm. After deep drawing, whether the edge of the outer layer film has abnormal phenomena such as edge warping and the like.
And (3) adopting a single-pit deep-drawing die, wherein the pit depth is 9mm, and observing whether the corners of the outer-layer film have abnormal phenomena such as layering, whitening, foaming and the like after deep drawing.
3. Heat sealability: folding the edge of the aluminum plastic film after being deeply punched, and performing heat sealing by a heat sealing machine, wherein the distance between the heat sealing position and the deeply punched edge is 1cm (upper and lower 185 ℃).
4. Boiling resistance: and (3) putting the aluminum-plastic film subjected to heat sealing into boiling water to boil for 4 hours, and observing whether the edges of the film have white marks, bubbles, delamination and the like.
5. Heat resistance: and (3) placing the aluminum-plastic film in an oven at 85 ℃, storing for 24 hours, and observing whether white marks, bubbles, delamination and other phenomena exist at the corners of the film.
The test data are shown in the following table:
TABLE 1 evaluation table of sample application properties
Figure BDA0002671105010000081
As can be seen from the above, in comparative examples 1 and 3, polyester is used as the adhesive component A, the bonding point with the curing agent B is only terminal hydroxyl, the anchoring point is single during curing, the bonding strength is limited, and the delamination phenomenon occurs during heat sealing; in comparative example 2, a polyhydroxy monomer, trimethylolpropane, was added in order to form a network polyester to increase strength, but as the amount of trimethylolpropane used was increased, the solubility of the polyester was decreased and the wettability to the film was deteriorated, resulting in lower peel strength; comparative example 4 the temperature resistance of the formed adhesive film is poor due to too low molecular weight; comparative example 5 has too high viscosity due to too high molecular weight, poor film uniformity during film coating, and degumming during film peeling. The epoxy chain-extended polyester has good bonding performance to aluminum foil, PA and PP due to the fact that hydroxyl groups are uniformly distributed in a polymer chain and generate a plurality of anchoring points with a curing agent, the peeling strength between the aluminum foil and the PA layer is larger than 9.5N, and meanwhile, a glue film has excellent ductility due to the fact that a system contains fatty long-chain acid; the high bonding strength and ductility endow the product with good flexibility, excellent tensile resistance and better hydrolysis resistance, bonding property and impact resistance. The obtained product can completely meet the application performance requirement of the lithium battery aluminum plastic film on the outer layer adhesive.

Claims (10)

1. The outer layer adhesive resin of the aluminum plastic film of the lithium battery is characterized in that: the lithium battery aluminum plastic film adhesive resin is solvent type bi-component adhesive resin, which consists of polyhydroxy epoxy chain-extended polyester as a component A and polyisocyanate as a component B; the mass ratio of the component A to the component B is 1:2-20: 1.
2. The aluminum plastic film adhesive resin for a lithium battery as claimed in claim 1, wherein: the polyhydroxy epoxy chain-extended polyester is carboxyl terminated polyester obtained by mixing aromatic dibasic acid, long-chain aliphatic dibasic acid and aliphatic polyol, and then carrying out esterification and polycondensation reaction; the carboxyl-terminated polyester is subjected to chain extension and tackifying by an epoxy chain extender, and the ratio of carboxyl to epoxy groups is 1:0.8-3.0, so that the polyhydroxy epoxy chain-extended polyester with the molecular weight of 20000-type 50000, the hydroxyl value of 15-300 and the acid value of 0.1-3.0 is obtained.
3. The aluminum plastic film adhesive resin for lithium batteries as claimed in claim 2, wherein: the carboxyl-terminated polyester is prepared by mixing aliphatic polyhydric alcohol, long-chain aliphatic dibasic acid and aromatic dibasic acid, stirring under the protection of nitrogen, heating to 200-plus-240 ℃ within 1 hour for esterification reaction, keeping the temperature for reaction for 2-3 hours, controlling the pressure to be 0.1-0.3MPa, slowly controlling the pressure to be 10-200 Pa, and continuously reacting at the temperature of 240-plus-270 ℃ to obtain carboxyl-terminated polyester Mn of 2000-plus-10000; wherein the molar ratio of the aromatic dibasic acid to the aliphatic polyhydric alcohol to the long-chain aliphatic dibasic acid is 1-6: 1-6: 1.
4. the aluminum plastic film adhesive resin for lithium batteries as claimed in claim 2, wherein: the epoxy chain extender is one or two of 1, 4-cyclohexanedimethanol glycidyl ether, 1, 4-butanediol diglycidyl ether, bisphenol A-diglycidyl ether, glycidyl ether, triglycidyl isocyanurate, N, N, N ', N ' -tetraglycidyl ester-4, 4 ' -diaminodiphenylmethane, bisphenol A polyglycidyl ether, bisphenol A epoxy resin and bisphenol F epoxy resin.
5. The aluminum plastic film adhesive resin for a lithium battery as claimed in claim 3, wherein: the aliphatic polyhydric alcohol is dihydric alcohol or dihydric alcohol and trihydric alcohol, wherein the aliphatic dihydric alcohol and the aliphatic trihydric alcohol are respectively C2-C12Two or three of the linear or branched di-or trihydric alcohols of (a); the aliphatic dibasic acid is C3-C18The fatty dibasic acid of (1); the aromatic dibasic acid is two or three of benzene diacid and/or naphthalene diacid.
6. The aluminum plastic film adhesive resin for a lithium battery as claimed in claim 3, wherein: adding a catalyst in the esterification reaction, wherein the adding amount of the catalyst is 300-1200 ppm; the catalyst is one or two of antimony acetate, antimony trioxide, ethylene glycol, tetrabutyl titanate and germanium oxide.
7. The aluminum plastic film adhesive resin for the lithium battery as recited in claim 1, wherein: the adhesive resin is applied to being used as an adhesive resin of an aluminum plastic film of a lithium battery.
8. The lithium battery aluminum plastic film adhesive is characterized in that: uniformly mixing the resin of claim 1 with a curing agent B, modified nano cerium oxide and an auxiliary agent to obtain a lithium battery aluminum plastic film adhesive; wherein the A, B component mass ratio in the resin is 100:5-25, the modified nano cerium oxide mass accounts for 0.5-4% of the adhesive, and the auxiliary agent mass accounts for 1-2% of the adhesive.
9. The aluminum plastic film adhesive for the lithium battery as recited in claim 1, wherein: the auxiliary agent is an organic silicon flatting agent and an anti-hydrolysis agent; wherein the mass of the organic silicon flatting agent accounts for 0.5-1% of the adhesive, and the mass of the hydrolysis resistant agent accounts for 0.5-1% of the adhesive.
10. The application of the aluminum plastic film adhesive for the lithium battery as recited in claim 8, wherein: the lithium battery aluminum plastic film adhesive containing the adhesive resin of claim 1 in claim 8 is coated on one side of an aluminum foil, dried at 70-100 ℃ for 1 minute, the obtained adhesive film and a nylon PA film are subjected to hot-pressing compounding at 70-90 ℃ under the pressure of 0.5MPa, then the lithium battery aluminum plastic film adhesive is coated on the other side of the aluminum foil, dried at 70-100 ℃ for 1 minute, the obtained adhesive film and a PP film are subjected to hot-pressing compounding at 70-90 ℃ under the pressure of 0.5MPa, and cured at 85 ℃ for 72 hours, so that the lithium battery aluminum plastic film is obtained.
CN202010933533.0A 2020-09-08 2020-09-08 Lithium battery aluminum plastic film outer layer adhesive resin and preparation and application thereof Pending CN112143437A (en)

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