CN115160529A - Epoxy modified polyurethane main agent resin and single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer-layer adhesive thereof - Google Patents

Epoxy modified polyurethane main agent resin and single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer-layer adhesive thereof Download PDF

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CN115160529A
CN115160529A CN202210905627.6A CN202210905627A CN115160529A CN 115160529 A CN115160529 A CN 115160529A CN 202210905627 A CN202210905627 A CN 202210905627A CN 115160529 A CN115160529 A CN 115160529A
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modified polyurethane
epoxy
main agent
resin
epoxy modified
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CN115160529B (en
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冯俊波
黄超
李鹏宇
王卓
张电波
翟黎鹏
邵志超
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Zhongyuan University of Technology
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Abstract

The invention belongs to the technical field of lithium battery flexible packaging, and particularly relates to an epoxy modified polyurethane main agent resin and a single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer-layer adhesive thereof. The adhesive comprises the following components in percentage by mass: 10-30% of epoxy modified polyurethane main agent resin, 0.1-5% of latent curing agent, 2-5% of auxiliary agent, 0.5-3% of graphene material and 65-85% of solvent. Through the design and assembly of a high molecular structure, various high-performance functional groups are introduced into the epoxy modified polyurethane main agent resin, so that the performances of the main agent resin, such as binding power, humidity resistance, hydrolysis resistance and the like, are fundamentally improved. The graphene material is introduced, so that the improvement of the deep drawing performance, the tear strength and the chemical corrosion resistance of the aluminum plastic film can be effectively promoted. The adhesive disclosed by the invention is a single-component moisture-heat curing epoxy resin modified polyurethane adhesive, is simple in construction process, and can greatly improve the production efficiency and benefit of an aluminum-plastic film.

Description

Epoxy modified polyurethane main agent resin and single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer-layer adhesive thereof
Technical Field
The invention belongs to the technical field of lithium battery flexible packaging, and particularly relates to an epoxy modified polyurethane main agent resin and a single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer-layer adhesive thereof.
Background
Since the advent of lithium ion batteries, lithium ion batteries have been developed in a long way due to their advantages of large capacity, high charge/discharge efficiency, long cycle life, etc., and have been widely used in portable electronic products, and have been gradually extended in recent years to new energy vehicles and other large-scale energy storage devices. At present, lithium ion batteries are developed towards excellent performances such as light weight, high safety, higher energy density and the like, and can effectively solve the problems of mileage anxiety and the like of new-energy automobiles. The hard steel shell and aluminum shell package of the traditional lithium battery is gradually replaced by an aluminum plastic film with flexible design, light weight and more excellent mechanical property.
The aluminum plastic film is a core material of the lithium ion soft package battery and is a composite material formed by compounding a biaxially oriented nylon film (PA), an aluminum foil, a cast polypropylene film (PP) or polyethylene terephthalate (PET) layer by layer. The materials between the layers are different, so different types of adhesives are needed for pressing and bonding, such as epoxy resin adhesives, acrylic resin adhesives and polyurethane resin adhesives. The outer layer glue mainly bonds the nylon film and the aluminum foil, while the nylon film has higher crystallinity, and the common glue has weak bonding property and is easy to degum; the use of imported glue has a high production cost and risks of being blocked and disconnected at any time.
The outer layer of the aluminum-plastic film is contacted with the surrounding environment, the nylon molecular chain contains an amide group (-CONH-), so that the nylon film can easily absorb moisture in the air, and the barrier property of the nylon film can be greatly reduced after moisture absorption; meanwhile, the lithium battery generates a large amount of heat in the operation process, so that the temperature of the battery is increased. The common adhesive is in a wet and warm environment for a long time, hydrolysis and aging of the common adhesive are serious, degumming and layering phenomena occur, and stability and safety of the battery are seriously influenced.
At present, no patent publication related to hydrolysis-resistant and cooking-resistant single-component outer-layer adhesives specially used for preparing aluminum-plastic films is found in the existing domestic synthesis technology. Patent publication No. CN109851763A discloses a method for preparing an outer layer adhesive of a lithium battery aluminum plastic film, wherein aliphatic dihydric alcohol, aliphatic dibasic acid and aromatic dibasic acid are subjected to esterification reaction, and then aliphatic polyhydric alcohol is added for polycondensation reaction. The polyhydroxy polymer prepared by the method disclosed in this patent contains a large number of readily hydrolyzable ester groups (-COOR). Therefore, the polymer is difficult to meet the application requirements in the aspects of hydrolysis resistance and wet heat resistance, can not be used independently, and can be applied to the bonding between a nylon film (PA) and an aluminum foil by being matched with a commercially available polyisocyanate curing agent. Patent publication No. CN112143437A discloses a preparation method of an aluminum plastic film adhesive for a lithium battery, wherein the adhesive is composed of two components, namely polyhydroxy polyester (A) and polyisocyanate (B), stirring and mixing are carried out according to the proportion of A, B components before coating, the adhesive can be used, meanwhile, high-temperature long-time curing treatment is carried out in the later stage of aluminum plastic film preparation, the production efficiency is low, the energy consumption is high, the quality of the aluminum plastic film is influenced to be improved in a higher direction, and the aluminum plastic film with higher quality is obtained by the current market in the development of low-medium curing (40-60 ℃) technology.
Disclosure of Invention
Aiming at the technical problems that the current lithium battery aluminum plastic film outer layer adhesive needs two components to be mixed for use, is easy to hydrolyze and has low bonding strength, the invention provides the epoxy modified polyurethane main agent resin and the single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum plastic film outer layer adhesive thereof, the prepared adhesive fundamentally improves the problems of low bonding force and easy hydrolysis of the aluminum plastic film outer layer adhesive, can improve the performances of the aluminum plastic film such as the punching depth performance, the tear strength and the like, simplifies the aluminum plastic film preparation process, and improves the production efficiency.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of epoxy modified polyurethane main agent resin comprises the following steps:
(1) Carrying out addition reaction on polydihydric alcohol and diisocyanate under the action of a catalyst to prepare an isocyanate prepolymer;
(2) Reacting the isocyanate prepolymer prepared in the step (1) with an epoxy modifier to prepare an isocyanate-terminated polyurethane-epoxy resin segmented copolymer containing oxazolidone groups;
(3) Carrying out crosslinking reaction on the polyurethane-epoxy resin segmented copolymer prepared in the step (2) and a crosslinking agent to prepare a micro-crosslinked high-molecular polymer;
(4) And (4) carrying out modification reaction on the micro-crosslinked high molecular polymer prepared in the step (3) and a coupling agent to prepare the epoxy modified polyurethane main agent resin.
The mass ratio of diisocyanate to polyglycol in the step (1) is 1: (5-20), wherein the addition amount of the catalyst is 2-5% of the mass sum of the diisocyanate and the polyglycol, the reaction temperature of the addition reaction is 50-180 ℃, and the reaction solution is cooled to room temperature to terminate the reaction when the-NCO content in the linear isocyanate prepolymer reaches 1.5-5 wt%.
The polyglycol is one or more of polyethylene glycol phthalate glycol, poly adipic acid-1,4-butanediol ester, polytetrahydrofuran diol, poly epsilon-caprolactone diol, polyhexamethylene carbonate and hydroxyl-terminated styrene-butadiene liquid rubber; the hydroxyl value content of the polyglycol is 20-120 mgKOH/g; the diisocyanate is any one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene Diisocyanate (NDI), isophorone diisocyanate (IPDI), trimethyl-1,6-hexamethylene diisocyanate, norbornane diisocyanate, IPDI trimer and dicyclohexylmethane diisocyanate; the catalyst is any one or more than two of dibutyltin dilaurate, stannous octoate, 1-phenyl-3-methyl phosphine heterocyclic pentene-1 oxide, N-bis (2-hydroxypropyl) aniline, N ', N' -tris (dimethylaminopropyl) hexahydrotriazine, triethylenediamine and tetramethylbutanediamine.
The mass ratio of the epoxy modifier to the isocyanate prepolymer in the step (2) is (0.5-3): 1, the reaction temperature is 80-190 ℃; the epoxy modifier is any one or more than two of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, alicyclic epoxy resin and glycidyl amine epoxy resin.
The mass ratio of the cross-linking agent to the block copolymer in the step (3) is 1: (15-30), wherein the reaction temperature is 60-150 ℃; the cross-linking agent is any one or more than two of 1,3-butanediol, 1,5-pentanediol, dimethylolpropane, trimethylolpropane, glycerol, pentaerythritol, 1,3-bis ((trimethylolpropane) methylamino) propane and triethanolamine.
In the step (3), the mass ratio of the coupling agent to the micro-crosslinked high-molecular polymer is 1: (20-200), wherein the reaction temperature is 55-165 ℃; the coupling agent is any one or more than two of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and gamma-aminopropyltrimethoxysilane.
The epoxy modified polyurethane main agent resin comprises an epoxy group, an isocyanate group, a carbamate group, an isocyanurate ring and an oxazolidone group; the epoxy modified polyurethane main agent resin has the content of-NCO of 0.1-2wt% and the molecular weight Mn of 20000-150000.
The single-component intrinsic hydrolysis-resistant and cooking-resistant outer-layer adhesive for the aluminum-plastic film comprises the epoxy modified polyurethane main agent resin, and mainly comprises the following raw materials in parts by mass: 10-30% of epoxy modified polyurethane main agent resin, 0.1-5% of latent curing agent, 2-5% of auxiliary agent, 0.5-3% of graphene material and 65-85% of solvent.
The latent curing agent is any one or combination of imine and oxazolidine; preferably, the latent curing agent is any one or more of oxazolidine latent curing agent PZ-005, imine latent curing agent Alt-102, imine latent curing agent Alt-105, polyurethane latent curing agent TKTY-001 and aromatic imine latent curing agent XYlink-401.
The auxiliary agent is any one or more than two of dibutyltin dilaurate, stannous octoate, 1-phenyl-3-methyl phosphine heterocyclic pentene-1 oxide, N-bis (2-hydroxypropyl) aniline, N ', N' -tris (dimethylaminopropyl) hexahydrotriazine, triethylenediamine and tetramethylbutanediamine; the solvent is any one or more than two of cyclohexane, o-hydroxy cyclohexyl methyl ether, ethyl acetate, butyl acetate and cyclohexanone.
The graphene material is graphene oxide, contains a large amount of hydroxyl, epoxy groups, carbonyl, carboxyl and the like, can effectively adsorb other small molecules such as water and the like, and can further perform crosslinking reaction with active groups of the epoxy modified polyurethane main agent resin.
The application of the single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer layer adhesive for bonding the outer layer of the aluminum-plastic film of the lithium battery comprises the following steps: coating the outer layer adhesive of the aluminum plastic film on the surface of the aluminum foil, drying the solvent at 40-70 ℃, then unreeling and pressurizing the solvent and a nylon layer (PA) or a polyethylene terephthalate (PET) layer for hot bonding, and curing for 3-10 days at 40-80 ℃.
The invention has the beneficial effects that:
(1) The epoxy modified polyurethane main agent resin is introduced with polymers such as polyester or polyether with regular structure and high crystallinity and functional isocyanate monomers to construct a target polymer. The prepared polymer contains various functional groups, such as hydroxyl (-OH), carbamate (-NHCOO-), carbamido (-NHCONH-), and the like, so hydrogen bonds are easily formed among molecules, the acting force among the molecules is strong, and the prepared polymer has strong compatibility and wettability with nylon films and aluminum foils. Meanwhile, the epoxy modified polyurethane main agent resin contains groups such as benzene ring, isocyanurate ring and oxazolidone group, and the groups have high thermal stability, so that the epoxy modified polyurethane main agent resin has excellent thermal decomposition resistance and intrinsic flame retardant property.
(2) The epoxy resin or the functional epoxy monomer is introduced into the main resin, so that the adhesive property of the epoxy modified polyurethane main agent resin can be further effectively improved, the viscosity of the epoxy modified polyurethane main agent resin is reduced, and the construction performance of the epoxy modified polyurethane main agent resin is improved.
(3) Siloxane is introduced into the main resin, so that the wettability and the bonding force of the adhesive and an aluminum foil are increased, the surface tension of the adhesive is reduced, and the leveling property and the hydrolysis resistance of an adhesive film are improved.
(4) The graphene material is compounded in the adhesive on the outer layer of the aluminum-plastic film, so that the tear strength and the flexibility of the adhesive film are effectively improved, and the aluminum-plastic film has better punching depth performance, because the oxidized graphene material contains hydroxyl, epoxy group, carbonyl, carboxyl and the like, the oxidized graphene material can effectively adsorb other small molecules such as water and the like, can further perform crosslinking reaction with active groups of the epoxy modified polyurethane main agent resin, and is similar to a 'buckle' to play a bridge role between polymers.
(5) The imine or oxazolidine latent curing agent in the outer layer adhesive of the aluminum-plastic film is decomposed in water to release active groups, and the active groups and the rest isocyanate are further subjected to curing and crosslinking reaction, so that the aluminum-plastic film can keep good cohesiveness, stability and mechanical strength for a long time.
(6) The outer-layer adhesive of the aluminum-plastic film prepared by the invention is a single-component moisture-heat curing epoxy resin modified polyurethane adhesive, two components are not required to be mixed for use, the use method is simple, the adhesive coating process flow is further simplified, the production efficiency is improved, and the production cost is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an infrared spectrum of the epoxy modified polyurethane host resin.
FIG. 2 is a schematic view of an aluminum-plastic film composite material
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer-layer adhesive comprises, by mass, 10% of epoxy modified polyurethane main agent resin, 2% of latent curing agent, 4% of auxiliary agent, 2% of graphene oxide and 82% of solvent. Wherein the latent curing agent is an imine latent curing agent Alt-102.
The auxiliary agent is a mixture of N, N-bis (2-hydroxypropyl) aniline and tetramethyl butanediamine, and the mass ratio of the N, N-bis (2-hydroxypropyl) aniline to the tetramethyl butanediamine is 1:3.
the solvent is a mixed solution of three organic solvents, namely ethyl acetate, butyl acetate and o-hydroxy cyclohexyl methyl ether, and the mass ratio of the three organic solvents is 4:4:2.
wherein the-NCO content of the epoxy modified polyurethane main agent resin is 1.7 percent, and the molecular weight Mn is 20000-30000.
The preparation method of the epoxy modified polyurethane main agent resin comprises the following steps:
adding a mixture of 1:5, adding partial solvent to dilute the toluene diisocyanate and the poly adipic acid-1,4-butanediol ester, stirring and reacting at the temperature of 90 ℃ under the catalysis of dibutyltin dilaurate accounting for 2 percent of the total mass of reactants until the content of-NCO is 4.9 percent, and cooling to room temperature to finish the reaction to obtain an isocyanate prepolymer (prepolymer for short); then adding bisphenol F type epoxy resin with the mass of 50 percent of the prepolymer for modification, wherein the reaction temperature is 140 ℃, and when the content of a reactant-NCO reaches 2.3 percent, finishing the reaction to obtain an isocyanate-terminated polyurethane-epoxy resin block copolymer (called copolymer for short) containing oxazolidone groups; then 1,5-pentanediol with the copolymer mass of 3.3 percent is added to be mixed with the copolymer for crosslinking reaction, the reaction temperature is 60 ℃, and micro-crosslinked high molecular polymer is obtained; and finally, adding 3-mercaptopropyltriethoxysilane with the mass of 0.5 percent of that of the micro-crosslinked high molecular polymer to perform secondary modification and modification, wherein the reaction temperature is 165 ℃, and finally obtaining the epoxy modified polyurethane main agent resin.
Example 2
The single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer-layer adhesive comprises, by mass, 15% of epoxy modified polyurethane main agent resin, 3% of latent curing agent, 4% of auxiliary agent, 2% of graphene oxide and 76% of solvent. Wherein the latent curing agent is an aromatic imine latent curing agent XYlink-401.
The auxiliary agent is a mixture of N, N ', N' -tris (dimethylaminopropyl) hexahydrotriazine and N, N-bis (2-hydroxypropyl) aniline, wherein the mass ratio of the N, N ', N' -tris (dimethylaminopropyl) hexahydrotriazine to the N, N-bis (2-hydroxypropyl) aniline is 1:4.
wherein the solvent is ethyl acetate and cyclohexanone in a mass ratio of 1:1.
Wherein the-NCO content of the epoxy modified polyurethane main agent resin is 0.27 percent, and the molecular weight Mn is 50000-80000.
The preparation method of the epoxy modified polyurethane main agent resin comprises the following steps:
adding a mixture of 1:7, adding a part of solvent for dilution, carrying out a reaction under the catalysis of stannous octoate accounting for 3% of the total mass of reactants and stirring at 50 ℃ until the-NCO content of the reactants is 2.8%, and cooling to room temperature for reaction to finish to obtain an isocyanate prepolymer (prepolymer for short); then adding bisphenol A epoxy resin accounting for 120 percent of the mass of the prepolymer for modification reaction, wherein the reaction temperature is 80 ℃, and when the-NCO content in the reactant reaches about 0.6 percent, the reaction is finished to obtain the oxazolidone group-containing isocyanate-terminated polyurethane-epoxy resin segmented copolymer (for short copolymer); then adding trimethylolpropane with 5% of the mass of the copolymer to mix with the copolymer for crosslinking reaction at the reaction temperature of 110 ℃ to obtain a micro-crosslinked high-molecular polymer; and finally, adding 3-isocyanate propyl trimethoxy silane with the polymer mass of 1.5% for secondary modification at the reaction temperature of 120 ℃ to finally prepare the epoxy modified polyurethane main agent resin.
Example 3
The single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer-layer adhesive comprises, by mass, 30% of main agent resin, 0.1% of latent curing agent, 2% of auxiliary agent, 0.5% of graphene oxide and 67.4% of solvent. .
Wherein the latent curing agent is oxazolidine latent curing agent PZ-005.
Wherein the auxiliary agent comprises 1-phenyl-3-methylphosphine cyclopentene-1 oxide and N, N-bis (2-hydroxypropyl) aniline, and the mass ratio of the two is 2:5.
wherein the solvent is a mixed solution of three organic solvents of acetic acid, cyclohexane and o-hydroxy cyclohexyl methyl ether, and the mass ratio is 1:1:1.
wherein the-NCO content of the epoxy modified polyurethane main agent resin is 0.15wt%, and the average molecular weight Mn is 60000-100000.
The preparation method of the epoxy modified polyurethane main agent resin comprises the following steps:
adding a mixture of 1:15, adding a part of solvent to dilute, carrying out stirring reaction at 180 ℃ under the catalytic action of dibutyltin dilaurate accounting for 3.5 percent of the total mass of reactants until the content of-NCO reaches 2.1 percent, and cooling to room temperature to react to obtain an isocyanate prepolymer (prepolymer for short); then adding bisphenol A epoxy resin accounting for 80 percent of the mass of the prepolymer for modification reaction, wherein the reaction temperature is 190 ℃, and when the-NCO content in the reactant reaches about 0.3 percent, the reaction is finished to obtain the oxazolidone group-containing isocyanate-terminated polyurethane-epoxy resin segmented copolymer (for short copolymer); then, glycerol with the mass of 6.6% of the copolymer is added to be mixed with the copolymer for crosslinking reaction, and the reaction temperature is 150 ℃, so that a micro-crosslinked high-molecular polymer is prepared; and finally, adding 3-mercaptopropyltrimethoxysilane with the mass of 2.1% of that of the polymer for secondary modification at the reaction temperature of 55 ℃ to finally prepare the epoxy modified polyurethane main agent resin.
Example 4
The single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer-layer adhesive comprises, by mass, 17% of epoxy modified polyurethane main agent resin, 2% of latent curing agent, 3% of auxiliary agent, 2% of graphene oxide and 76% of solvent. Wherein the latent curing agent is a polyurethane latent curing agent TKTY-001.
The auxiliary agent comprises triethylene diamine, N-bis (2-hydroxypropyl) aniline and N, N ', N' -tris (dimethylaminopropyl) hexahydrotriazine, and the mass ratio of the auxiliary agent to the N, N ', N' -tris (dimethylaminopropyl) hexahydrotriazine is 1:3:2.
wherein the solvent is a mixed solution of three organic solvents of acetic acid, butyl acetate and o-hydroxy cyclohexyl methyl ether, and the mass ratio is 1:1:1.
wherein the-NCO content of the epoxy modified polyurethane main agent resin is 0.23wt%, and the molecular weight Mn is 80000-120000.
The preparation method of the epoxy modified polyurethane main agent resin comprises the following steps:
adding a mixture of 1:20 of toluene diisocyanate and polydiol, wherein the polydiol is prepared from the following components in a mass ratio of 4:1:5 poly-epsilon-caprolactone diol, polyhexamethylene carbonate (PHC) and hydroxyl-terminated styrene-butadiene liquid rubber, adding partial solvent for dilution, and adding two polymers in a mass ratio of 3:1, dibutyltin laurate and triethylene diamine are used for jointly catalyzing toluene diisocyanate to react with polydihydric alcohol, the catalyst accounts for 5 percent of the total mass of reactants, the reaction temperature is 135 ℃, and when the content of reactant-NCO reaches 1.5 percent, the reaction is finished by cooling to room temperature to obtain isocyanate prepolymer (prepolymer for short); then adding 60 percent of alicyclic epoxy resin by mass of the prepolymer for modification reaction, wherein the reaction temperature is 110 ℃, and when the-NCO content in reactants reaches about 0.5 percent, the reaction is finished to obtain the oxazolidone group-containing isocyanate-terminated polyurethane-epoxy resin segmented copolymer (called copolymer for short); then adding pentaerythritol with 4.5 percent of the mass of the copolymer and the copolymer to mix for crosslinking reaction at the reaction temperature of 90 ℃ to prepare a micro-crosslinked high molecular polymer; finally, gamma-aminopropyl trimethoxy silane with the mass of 1.8 percent of the polymer is added for secondary modification and modification, the reaction temperature is 60 ℃, and finally the epoxy modified polyurethane main agent resin is prepared.
Example 5
The single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer layer adhesive comprises, by mass, 20% of epoxy modified polyurethane main agent resin, 4% of latent curing agent, 3% of auxiliary agent, 3% of graphene oxide and 73% of solvent. Wherein the latent curing agent is an imine latent curing agent Alt-102.
Wherein the auxiliary agent comprises triethylene diamine and N, N ', N' -tri (dimethylaminopropyl) hexahydrotriazine, and the mass ratio of the triethylene diamine to the N, N ', N' -tri (dimethylaminopropyl) hexahydrotriazine is 5:3.
wherein the solvent is a mixed solution of three organic solvents of cyclohexane, cyclohexanone and o-hydroxy cyclohexyl methyl ether, and the mass ratio is 4:4:2.
wherein the-NCO content of the epoxy modified polyurethane main agent resin is 0.39wt%, and the molecular weight Mn is 90000-120000.
The preparation method of the epoxy modified polyurethane main agent resin comprises the following steps:
adding a mixture of 1:1:15 toluene diisocyanate: isophorone diisocyanate: poly adipic acid-1,4-butanediol ester, under the catalysis of dibutyltin dilaurate with the total mass of 3.5 percent of reactants and the temperature of 115 ℃, stirring and reacting until the content of-NCO reaches 3.5 weight percent, cooling to room temperature and finishing the reaction to obtain an isocyanate prepolymer (prepolymer for short); then adding bisphenol F epoxy resin accounting for 150% of the mass of the prepolymer to carry out modification reaction, wherein the reaction temperature is 110 ℃, and when the-NCO content in the reactant reaches about 0.8%, the reaction is finished to obtain an isocyanate-terminated polyurethane-epoxy resin block copolymer (copolymer for short) containing oxazolidone groups; then 1,5-pentanediol with 5% of the mass of the copolymer is added to be mixed with the copolymer for crosslinking reaction, the reaction temperature is 80 ℃, and the micro-crosslinked high molecular polymer is prepared; finally, 3-mercaptopropyltriethoxysilane accounting for 1 percent of the mass of the polymer and 1.7 percent of 3-mercaptopropyltrimethoxysilane accounting for 1 percent of the mass of the polymer are added for secondary modification, the reaction temperature is 95 ℃, and finally the epoxy modified polyurethane main agent resin is prepared.
Comparative example 1
Comparative example 1 differs from example 1 in that: and no auxiliary agent is added into the outer layer adhesive of the aluminum-plastic film, and the balance is solvent.
Comparative example 2
Comparative example 2 differs from example 2 in that: graphene materials are not added into the outer-layer adhesive of the aluminum-plastic film, and the balance is solvent.
Comparative example 3
Comparative example 3 differs from example 2 in that: the latent curing agent is not added into the outer layer adhesive of the aluminum-plastic film, and the balance is solvent.
Comparative example 4
Adding a mixture of 1:5, adding partial solvent to dilute, stirring and reacting under the catalysis of dibutyltin dilaurate accounting for 2% of the total mass of reactants and at the temperature of 90 ℃ until the content of-NCO is 1.5%, cooling to room temperature to finish the reaction, and obtaining the isocyanate prepolymer. The epoxy modified polyurethane main agent resin in example 1 was replaced with an isocyanate prepolymer to prepare an outer adhesive of an aluminum-plastic film as a comparative sample.
Comparative example 5
Adding a mixture of 1:5, adding partial solvent to dilute the toluene diisocyanate and the poly adipic acid-1,4-butanediol ester, stirring and reacting at the temperature of 90 ℃ under the catalysis of dibutyltin dilaurate accounting for 2 percent of the total mass of reactants until the content of-NCO is 4.9 percent, and cooling to room temperature to finish the reaction to obtain an isocyanate prepolymer (prepolymer for short); then adding bisphenol F epoxy resin accounting for 50% of the mass of the prepolymer for modification, controlling the reaction temperature to be 140 ℃, and obtaining the polyurethane-epoxy resin block copolymer which contains oxazolidone group and is blocked by isocyanate after the reaction is finished when the content of reactant-NCO reaches 2.3%. The polyurethane-epoxy resin block copolymer was used to replace the epoxy modified polyurethane base resin in example 1 to prepare an outer adhesive of an aluminum plastic film as a comparative sample.
Application example
The application of the single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer layer adhesive in the embodiment 1 is used for bonding the outer layer of the aluminum-plastic film of the lithium battery, as shown in fig. 2, the outer layer adhesive is coated on the surface of an aluminum foil, a solvent is dried at 70 ℃, then the aluminum foil is unreeled and pressurized to be bonded with a nylon layer (PA), and the aluminum-plastic film outer layer adhesive is cured for 3 days at 80 ℃.
Test example
First, infrared spectrum tests are performed on the epoxy modified polyurethane main agent resins prepared in examples 1 to 5, and the results are shown in fig. 1, and by analyzing characteristic peaks in an infrared spectrogram for synthesizing the epoxy modified polyurethane main agent resin, it can be concluded that the epoxy modified polyurethane main agent resin contains functional groups such as isocyanate groups, carbamate groups, isocyanurate rings, epoxy groups, oxazolidone groups, and the like, and meanwhile, a plurality of types of polydiols, epoxy modifiers, and coupling agents are introduced during synthesis of the epoxy modified polyurethane main agent resin, so that the epoxy modified polyurethane main agent resin also correspondingly contains functional groups such as ether bonds, benzene rings, and the like in the infrared spectrogram. The test and analysis result of the infrared spectrogram of the epoxy modified polyurethane main agent resin is consistent with the expectation of constructing the epoxy modified polyurethane main agent resin through molecular design, and the epoxy modified polyurethane main agent resin shows excellent performances of bonding strength, hydrolysis resistance, cooking resistance and the like under the coordination of various functional groups and various components.
And then, evaluating the outer layer adhesive of the aluminum-plastic film described in the examples 1-5 and the comparative examples 1-5, bonding nylon (PA) and aluminum foil by using the outer layer adhesive to prepare a composite film, and curing under the same condition. The peel force test and other performance tests were then performed according to GB/T7122-1996. The performance test results are shown in table 1:
TABLE 1
Figure BDA0003772358620000091
As can be seen from the above Table 1, the adhesives in examples 1-5 have good adhesive properties to nylon (PA) and aluminum foil, and the initial peel force is more than 13.5N; the single pit punching depth is 9.5mm, and the aluminum-plastic film has no layering and white marks, which shows that the aluminum-plastic film prepared by compounding the adhesives in the examples 1-5 has excellent punching depth performance; the aluminum plastic film has no phenomena of degumming, delamination and foaming after being subjected to a damp-heat test, and shows excellent damp-heat resistance. After 7-day electrolyte resistance test, compared with the initial stripping force, the stripping force of the aluminum plastic films in examples 1-3 is not changed greatly, and the 7-day electrolyte resistance stripping force of examples 4 and 5 is slightly improved, which indicates that the adhesive has excellent corrosion resistance and chemical resistance. The epoxy modified polyurethane main agent resin contains the residual-NCO, and is matched with an accelerator, a latent curing agent and a graphene material to form the single-component moist heat curing epoxy resin modified polyurethane adhesive, and the adhesive can be further crosslinked and cured in a moist heat environment, so that the adhesive film is endowed with better hydrolysis resistance, adhesion and long-term stability.
In comparative examples 1-3, no accelerator, latent curing agent or graphene is added to the adhesive, so that the initial peeling force is significantly reduced, and the electrolytic solution peeling resistance is also greatly reduced in 7 days, which proves that the hydroxyl (-OH), carbamate (-NHCOO-), ureido (-NHCONH-) and other groups in the epoxy modified polyurethane main agent resin can react with the active groups in the accelerator, the latent curing agent or graphene, so that the mechanical property and the boiling resistance of the epoxy modified polyurethane main agent resin are improved. Therefore, the latent curing agent, the auxiliary agent and the graphene material are added in the formula of the adhesive under the coordination of the epoxy modified polyurethane main agent resin, so that the adhesive film bonding performance, hydrolysis resistance, cooking resistance and tear resistance can be remarkably improved, and the obtained adhesive product can completely meet the application performance requirements of the lithium battery aluminum plastic film on the outer layer adhesive.
As can be seen from the comparative example 4, the currently commonly used polyurethane adhesive is completely unqualified in the humidity and heat resistance, and the initial stripping force and the 7-day electrolyte resistance stripping force are far lower than those of the adhesive prepared by the invention; while the initial peel force, penetration property and wet heat resistance of comparative example 5 were improved as compared with comparative example 4, and further, the viscosities of the adhesives prepared in comparative example 5 and examples 1 to 5 were reduced as compared with comparative example 4 during the preparation of the samples. On one hand, the main agent resin of the epoxy modified polyurethane in the embodiment 5 contains groups such as benzene ring, isocyanurate ring and oxazolidone group, and the groups have high thermal stability, so that the main agent resin of the epoxy modified polyurethane has excellent thermal decomposition resistance and intrinsic flame retardant property; on the other hand, the adhesive property of the epoxy modified polyurethane main agent resin can be further effectively improved through epoxy resin modification, the viscosity of the epoxy modified polyurethane main agent resin is reduced, and the workability of the epoxy modified polyurethane main agent resin is improved. Compared with the comparative samples 4 and 5, the epoxy modified polyurethane master resin is endowed with rich crosslinking groups through epoxy modification, crosslinking and coupling agent modification of the epoxy modified polyurethane master resin, and the epoxy modified polyurethane master resin is compounded with materials such as a latent curing agent, an auxiliary agent, a graphene material and the like, so that the synergistic effect of the epoxy modified polyurethane master resin and the latent curing agent can obviously improve the bonding performance, the hydrolysis resistance, the cooking resistance and the tear resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A preparation method of epoxy modified polyurethane main agent resin is characterized by comprising the following steps:
(1) Carrying out addition reaction on polydiol and diisocyanate under the action of a catalyst to prepare an isocyanate prepolymer;
(2) Reacting the isocyanate prepolymer prepared in the step (1) with an epoxy modifier to prepare an isocyanate-terminated polyurethane-epoxy resin segmented copolymer containing oxazolidone groups;
(3) Carrying out crosslinking reaction on the polyurethane-epoxy resin segmented copolymer prepared in the step (2) and a crosslinking agent to prepare a micro-crosslinked high-molecular polymer;
(4) And (4) carrying out modification reaction on the micro-crosslinked high molecular polymer prepared in the step (3) and a coupling agent to prepare the epoxy modified polyurethane main agent resin.
2. The method for preparing the epoxy modified polyurethane main agent resin according to claim 1, wherein the mass ratio of the diisocyanate to the polyglycol in the step (1) is 1: (5-20), wherein the addition amount of the catalyst is 2-5% of the mass sum of the diisocyanate and the polyglycol, the reaction temperature of the addition reaction is 50-180 ℃, and the reaction solution is cooled to room temperature to terminate the reaction when the-NCO content in the linear isocyanate prepolymer reaches 1.5-5 wt%.
3. The method for preparing the epoxy modified polyurethane main agent resin according to claim 1, wherein the polyglycol is one or more of polydiethylene glycol phthalate, poly adipic acid-1,4-butanediol ester, polytetrahydrofuran diol, poly epsilon-caprolactone diol, polyhexamethylene carbonate and hydroxy terminated styrene-butadiene liquid rubber; the hydroxyl value content of the polyglycol is 20-120 mgKOH/g; the diisocyanate is any one or more than two of toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, norbornane diisocyanate, IPDI trimer and dicyclohexylmethane diisocyanate; the catalyst is any one or more than two of dibutyltin dilaurate, stannous octoate, 1-phenyl-3-methyl phosphine heterocyclic pentene-1 oxide, N-bis (2-hydroxypropyl) aniline, N ', N' -tris (dimethylaminopropyl) hexahydrotriazine, triethylenediamine and tetramethyl butanediamine.
4. The preparation method of the epoxy modified polyurethane main agent resin according to claim 1, wherein the mass ratio of the epoxy modifier to the isocyanate prepolymer in the step (2) is (0.5-3): 1, the reaction temperature is 80-190 ℃; the epoxy modifier is any one or more than two of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, alicyclic epoxy resin and glycidyl amine epoxy resin.
5. The method for preparing the epoxy modified polyurethane main agent resin according to claim 1, wherein the mass ratio of the cross-linking agent to the block copolymer in the step (3) is 1: (15-30), wherein the reaction temperature is 60-150 ℃; the cross-linking agent is any one or more than two of 1,3-butanediol, 1,5-pentanediol, dimethylolpropane, trimethylolpropane, glycerol, pentaerythritol, 1,3-bis ((trimethylolpropane) methylamino) propane and triethanolamine.
6. The preparation method of the epoxy modified polyurethane main agent resin according to claim 1, wherein the mass ratio of the coupling agent to the micro-crosslinked high molecular polymer in the step (3) is 1: (20-200), wherein the reaction temperature is 55-165 ℃; the coupling agent is any one or more than two of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and gamma-aminopropyltrimethoxysilane.
7. The epoxy modified polyurethane main agent resin obtained by the method of any one of claims 1 to 6, wherein the epoxy modified polyurethane main agent resin comprises an epoxy group, an isocyanate group, a carbamate group, an isocyanurate ring and an oxazolidone group; the epoxy modified polyurethane main agent resin has the content of-NCO of 0.1-2wt% and the molecular weight Mn of 20000-150000.
8. The single-component intrinsic hydrolysis-resistant and cooking-resistant aluminum-plastic film outer-layer adhesive is characterized by comprising the epoxy modified polyurethane main agent resin of claim 7, and mainly comprises the following raw materials in parts by mass: 10-30% of epoxy modified polyurethane main agent resin, 0.1-5% of latent curing agent, 2-5% of auxiliary agent, 0.5-3% of graphene material and 65-85% of solvent.
9. The one-component intrinsic hydrolysis-resistant cooking-resistant aluminum-plastic film outer layer adhesive as claimed in claim 8, wherein the latent curing agent is any one or a combination of imines and oxazolidines; the auxiliary agent is any one or more than two of dibutyltin dilaurate, stannous octoate, 1-phenyl-3-methyl phosphine heterocyclic pentene-1 oxide, N-bis (2-hydroxypropyl) aniline, N ', N' -tris (dimethylaminopropyl) hexahydrotriazine, triethylenediamine and tetramethylbutanediamine; the solvent is any one or more than two of cyclohexane, o-hydroxy cyclohexyl methyl ether, ethyl acetate, butyl acetate and cyclohexanone.
10. The use of the one-component intrinsic hydrolysis-resistant, steam-resistant aluminum plastic film outer layer adhesive of claim 9 for bonding the outer layer of an aluminum plastic film of a lithium battery, comprising the steps of: coating the outer layer adhesive of the aluminum-plastic film on the surface of the aluminum foil, drying the solvent at 40-70 ℃, and then unreeling and pressurizing the aluminum-plastic film and the nylon layer or the polyethylene terephthalate layer for hot bonding.
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崔志强;饶秋华;李瑜;谢云飞;: "环氧树脂增韧固化剂的合成与性能研究", 热固性树脂, no. 02 *

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