CN114032053B - Lithium battery aluminum plastic film inner layer adhesive and preparation method thereof - Google Patents
Lithium battery aluminum plastic film inner layer adhesive and preparation method thereof Download PDFInfo
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- CN114032053B CN114032053B CN202111440355.9A CN202111440355A CN114032053B CN 114032053 B CN114032053 B CN 114032053B CN 202111440355 A CN202111440355 A CN 202111440355A CN 114032053 B CN114032053 B CN 114032053B
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/121—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
- H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
- H01M50/1243—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure characterised by the internal coating on the casing
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- 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
Abstract
The invention belongs to the field of organic synthesis, relates to a high-molecular modification technology, and particularly relates to a preparation method of an inner-layer adhesive for an aluminum plastic film of a lithium battery. Polyolefin, unsaturated acid, solvent 1 and initiator are subjected to solution polymerization reaction in inert gas under normal pressure under the action of an antioxidant, solvent 2 is added into the reactant for dissolution, and solvent 3 is added for precipitation of a graft, so that polymer solid powder with the molecular weight of 10000-35000 and the grafting rate of 2.5-4.0% is obtained. The product was dissolved in solvent 4 to prepare a polymer solution. The invention has the advantages of simple and convenient operation process, reasonable molecular weight distribution, stable product quality and application performance, difficult crystallization of the product, good flexibility, excellent stretching resistance, and better electrolyte resistance, cohesiveness and impact resistance. The adhesive product prepared by the invention can completely meet the application performance requirement of the lithium battery aluminum plastic film on the inner layer adhesive.
Description
Technical Field
The invention belongs to the field of organic synthesis, relates to a high-molecular modification technology, and particularly relates to an inner-layer adhesive for an aluminum-plastic film of a lithium battery and a preparation method 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 packaging, 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 replacing import of domestic lithium battery enterprises, domestic enterprises have been engaged in research and development work of aluminum-plastic composite film technology for lithium batteries, but the 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 layer base material is 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, electrolyte resistance and the like can meet the performance requirements.
In the existing domestic synthesis technology, no related patent publication exists for specially preparing the inner layer adhesive of the aluminum-plastic film of the lithium battery. At present, the patent literature for preparing the aluminum plastic film adhesive of the lithium battery comprises the following steps:
CN202010268184.5 reports a synthesis method of an adhesive for an aluminum plastic film, which shows that firstly maleic anhydride modified polyolefin is grafted with bisphenol A epoxy resin E44 to obtain a component A; the component B is polyolefin grafted triglycidyl p-aminophenol modified by maleic anhydride; the product C is prepared by copolymerizing hydroxyl-terminated polybutadiene and hexamethylene diisocyanate. And blending the three components, mixing the three components with a curing agent, and coating the adhesive. The information disclosed in the patent indicates that the synthesized inner-layer adhesive is an aluminum-plastic film inner-layer adhesive, has excellent electrolyte resistance, and can still maintain more than 70% of initial stripping force after being soaked in an electrolyte at 85 ℃ for 20 days. However, the synthesis of the adhesive is complex, the solvent dosage is large, the adhesive can only meet the electrolyte resistance, and the application performances such as extension and stretching are difficult to meet the performance requirements of lithium batteries on aluminum plastic films.
Cn106459703.A discloses a polyolefin adhesive composition, which is prepared from acid-modified chlorinated polyolefin, glycidyl amine type epoxy resin, and glycidyl ether type epoxy resin, and is mixed with a curing agent and then coated. The adhesive does not cause thickening or gelation even after long-term storage, can maintain good pot life characteristics, and can realize good adhesion and chemical resistance between a polyolefin resin substrate and a metal substrate at the same time even when the adhesive is adhered and aged at a low temperature of 80 ℃ or lower, which has little influence on thermal shrinkage of the polyolefin substrate. However, the adhesive cannot meet the application performances of electrolyte resistance at 85 ℃ and the like
In conclusion, the prior patent technology in China cannot simultaneously meet the requirements of the inner layer adhesive of the aluminum-plastic film of the lithium battery on the impact strength, the electrolyte resistance and the like.
Disclosure of Invention
The invention aims to provide an inner layer adhesive for an aluminum plastic film of a lithium battery and a preparation method thereof.
In order to realize the purpose, the invention adopts the technical scheme that:
an inner layer adhesive of an aluminum plastic film of a lithium battery comprises a polymer and a curing agent, wherein the polymer is a polymer which takes polyolefin as a raw material and is subjected to polymerization reaction in the presence of unsaturated acid to obtain the polymer with the molecular weight of 10000-35000 and the grafting ratio of 2.5-4.0%; preferably 10000-30000 of molecular weight, 2.5-3.5% of grafting rate, most preferably 10000-25000 of molecular weight, and 2.5-3% of grafting rate.
A preparation method of an inner layer adhesive of an aluminum plastic film of a lithium battery comprises the steps of carrying out solution polymerization reaction on polyolefin, unsaturated acid, an initiator and a solvent 1 in an inert gas under normal pressure under the action of an antioxidant, adding a solvent 2 into a reactant for dissolving, and adding a solvent 3 into the reactant for precipitating a graft so as to obtain polymer solid powder with the molecular weight of 10000-35000 and the grafting rate of 2.5-4.0%.
The polymer solid powder is dissolved in a solvent 4 to prepare a polymer solution, and then mixed with a curing agent.
Further, mixing polyolefin, an initiator and unsaturated acid in a solvent 1, adding an antioxidant, stirring under the protection of nitrogen, heating to 120-180 ℃ at the speed of 30-60 ℃/h for solution polymerization, keeping the temperature for reaction for 1-6 h, adding a solvent 2 for dilution, cooling to room temperature, adding a solvent 3 for precipitation, and obtaining polymer solid powder with the target molecular weight of 10000-35000 and the grafting rate of 2.5-4.0%; the product was dissolved in solvent 4 to prepare a polymer solution.
The polyolefin, the initiator and the unsaturated acid are added into the reaction system in 2-3 batches.
The mass ratio of the polyolefin to the unsaturated acid to the initiator to the solvent 1 is (2-7).
The polyolefin is a copolymer of propylene and alpha-olefin; wherein the molar ratio of propylene to alpha-olefin is 97-75/3-25 (preferably 95-85/5-15); the alpha-olefin can be one or more selected from ethylene, propylene, 1-butene, 1-heptene, 1-octene and 4-methyl-1-pentene, and is preferably selected from ethylene and 1-octene.
The unsaturated acid is one or more of alpha, beta-unsaturated carboxylic acid and anhydride thereof; the alpha, beta-unsaturated carboxylic acid and its anhydride can be selected from one or more of maleic acid, itaconic acid, citraconic acid and their anhydrides. Preferably maleic acid and anhydride thereof, and the mass ratio of the unsaturated acid to the polyolefin is 0.2-0.5.
The antioxidant is p-tert-butylphenol, 2, 4-dimethyl-6-tert-butylphenol or pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate); preferably p-tert-butylphenol; the addition amount of the antioxidant is 0.1-2.0% of the mass of the reactant. Preferably 0.3 to 1.8%, more preferably 0.5 to 1.5%. Wherein the mass of the reactant is the sum of the mass of the polyolefin, the maleic anhydride and the benzoyl peroxide.
The initiator is organic peroxide; the organic peroxide can be one or more selected from methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, azodiisopropylnitrile, tert-butyl peroxybenzoate and tert-butyl peroxide. Benzoyl peroxide, tert-butyl peroxide, dicumyl peroxide are preferred. The mass ratio of the organic peroxide to the polyolefin is 0.05-0.2, more preferably 0.1-0.2.
The solvent 1 and the solvent 2 can be the same or different and are selected from benzene; wherein, the addition amounts of the solvent 1 and the solvent 2 are the same;
the solvent 3 is an organic solvent as an extractant.
The solvent 1 is benzene, one or two of toluene, xylene and the like can be selected, and the addition amount is 4-10 times of the mass of polyolefin; the solvent 2 is the same as the solvent 1, and the adding amount is the same as the mass of the solvent 1; the solvent 3 is used as an extracting agent, and can be one or more of acetone, butanone, methanol, ethanol and the like. The solvent 4 is aliphatic cyclane, and the cyclane can be one or more of ethylcyclohexane, 2-methyl-4-cyclohexylhexane, 1, 4-dimethyl-2-ethylcyclohexane, 1, 2-dimethylcyclopropane and cyclohexane.
The application of the adhesive is characterized in that the adhesive is applied to an adhesive used as an inner layer of an aluminum-plastic film of a lithium battery.
The application of the adhesive for the inner layer of the aluminum-plastic film of the lithium battery is characterized in that a polymer solution with the molecular weight of 10000-35000 and the grafting ratio of 2.5-4.0% is mixed with a curing agent and then coated on the surface of a matrix aluminum foil, and a glue layer is formed after drying and is subjected to hot coating and bonding with a PP layer.
The adhesive is prepared by mixing the polymer and the curing agent according to the molar ratio of the acid value of the solute to NCO of 1-2.
Further, the obtained polymer and a commercial polyisocyanate curing agent are mixed according to the molar ratio of the acid value of a solute to NCO of 1-2, then the mixture is coated on the surface of an aluminum foil, the thickness of a dried adhesive layer is preferably 3-7 mu m, then hot coating and bonding operation of a PP layer, coating and curing operation of an outer layer film and the like are carried out, and finally a qualified product of the aluminum plastic film of the lithium battery with the punching depth of more than 7mm, no delamination and initial stripping force of 12-13N is obtained, and the qualified product is placed in an electrolyte at 85 ℃ for 24 hours and has no change in stripping force.
The invention has the following advantages:
the acid-modified co-polypropylene is used as a raw material of the lithium battery aluminum plastic film inner layer adhesive, and after the acid-modified co-polypropylene is blended with a curing agent, the adhesive shows good adhesion and electrolyte resistance with a polyolefin resin substrate and a metal substrate, can be coated at a low temperature, has adhesive application performances such as tensile strength and the like, and ensures the quality and the using effect of an adhesive product; the method comprises the following steps:
1. in the preparation process, the addition stages of the initiator and the anhydride are adjusted, so that the initiator and the anhydride exert catalytic activity to the maximum extent, the polyolefin degradation rate is reduced, the reaction is promoted, the grafting rate is ensured, and the molecular weight is controlled;
2. in the preparation process, the reaction raw materials are added stage by stage, so that the raw materials can be fully reacted at the optimal reaction temperature, and an adhesive product with stable performance is obtained;
3. the invention adopts the acid modified propylene-octene copolymer as the raw material, further improves the bonding capability, electrolyte resistance and shock resistance of the product. The adhesive product prepared by the invention can completely meet the application performance requirement of the lithium battery aluminum plastic film on the inner 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 invention has the advantages of simple operation process, reasonable molecular weight distribution, stable product quality and application performance, good product flexibility, excellent tensile resistance, and better electrolyte resistance, cohesiveness and impact resistance. The adhesive product prepared by the invention can completely meet the application performance requirement of the lithium battery aluminum plastic film on the inner layer adhesive.
The following examples are given to prepare polymers based on polyolefins in proportions of other components.
Example 1
A propylene-1-octene copolymer (Tm: 75 ℃ C., propylene/1-octene =90/10 mol ratio) (100 parts by mass), xylene (400 parts by mass), maleic anhydride (10 parts by mass), benzoyl peroxide (5 parts by mass) and p-tert-butylphenol (1 part by mass) were charged into a reaction flask, and after the air in the reaction system was replaced with nitrogen, the temperature was raised to 90 ℃ under the protection of nitrogen, and after the solid matter was completely dissolved, the temperature was raised to 120 ℃ at a rate of 60 ℃/h, and a heat-insulating reaction was carried out for 1h. Maleic anhydride (5 parts by mass) and benzoyl peroxide (5 parts by mass) dissolved in xylene (50 parts by mass) were added to a reaction flask via a dropping funnel within 10min, and after further stirring for 30min, the reaction solution was cooled to 100 ℃, added to xylene (500 parts by mass) and acetone (200 parts by mass) previously heated to 45 ℃ while stirring, cooled to 40 ℃, and further stirred and cooled to 25 ℃, so that the reaction product was precipitated. And (3) carrying out centrifugal separation on the solution containing the reaction product (the bottom solid is selected by centrifugal separation, the molecular weight is gradually reduced due to the fracture of a polyolefin chain segment along with the increase of the grafting rate, and the grafting rate is measured by a chemical titration method for dried solid powder), and separating low molecular weight products, polymaleic anhydride and the like contained in the product.
The maleic anhydride-modified propylene-1-octene copolymer which had been centrifuged and taken out was put into acetone (1000 parts by mass) which was stirred at a high speed, and after stirring for 1 hour, the solution was centrifuged to separate a low molecular weight product in the copolymer and polymaleic anhydride, and the operation was repeated twice to purify the copolymer. After purification, the reaction mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified propylene-1-octene copolymer.
Example 2
A propylene-1-octene copolymer (Tm: 75 ℃, propylene/1-octene =90/10 molar ratio) (100 parts by mass), xylene (350 parts by mass), maleic anhydride (10 parts by mass), benzoyl peroxide (5 parts by mass) and p-tert-butylphenol (1 part by mass) were charged into a reaction flask, and after the air in the reaction system was replaced with nitrogen, the temperature was raised to 90 ℃ under the protection of nitrogen, and after the solid matter was completely dissolved, the temperature was raised to 120 ℃ at a rate of 60 ℃/h, and a heat-preservation reaction was carried out for 1h. Maleic anhydride (5 parts by mass) and benzoyl peroxide (5 parts by mass) dissolved in xylene (50 parts by mass) were added to a reaction flask via a dropping funnel within 10min, and after further stirring for 30min, the reaction solution was cooled to 100 ℃, added to xylene (400 parts by mass) and acetone (200 parts by mass) previously heated to 45 ℃ while stirring, cooled to 40 ℃, and further stirred and cooled to 25 ℃, so that the reaction product was precipitated. The solution containing the reaction product is centrifuged to separate low molecular weight products, polymaleic anhydride, and the like contained in the product.
The maleic anhydride-modified propylene-1-octene copolymer which had been centrifuged and taken out was put into acetone (1000 parts by mass) which was stirred at a high speed, and after stirring for 1 hour, the solution was centrifuged to separate a low molecular weight product in the copolymer and polymaleic anhydride, and the operation was repeated twice to purify the copolymer. After purification, the reaction mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified propylene-1-octene copolymer.
Comparative example 1
A reaction flask was charged with a propylene-1-ethylene copolymer (Tm: 75 ℃ C., propylene/1-ethylene =90/10 molar ratio) (100 parts by mass), xylene (400 parts by mass), maleic anhydride (10 parts by mass), benzoyl peroxide (5 parts by mass), and p-tert-butylphenol (1 part by mass), the air in the reaction system was replaced with nitrogen, the temperature was raised to 90 ℃ under nitrogen protection, the reaction temperature was raised to 120 ℃ at a rate of 60 ℃/h after the solid materials were completely dissolved, and the reaction was carried out for 1 hour with heat preservation. Maleic anhydride (5 parts by mass) and benzoyl peroxide (5 parts by mass) dissolved in xylene (50 parts by mass) were added to a reaction flask via a dropping funnel within 10min, and after further stirring for 30min, the reaction solution was cooled to 100 ℃, added to xylene (500 parts by mass) and acetone (200 parts by mass) heated in advance to 45 ℃ while stirring, cooled to 40 ℃, further stirred and cooled to 25 ℃, and the reaction product was precipitated. The solution containing the reaction product is centrifuged to separate low molecular weight products, polymaleic anhydride, and the like contained in the product.
The maleic anhydride-modified propylene-1-ethylene copolymer which had been centrifuged and taken out was put into acetone (1000 parts by mass) which had been stirred at a high speed, and after stirring for 1 hour, the solution was centrifuged to separate a low molecular weight product and polymaleic anhydride in the copolymer, and the operation was repeated twice to purify the copolymer. After purification, the reaction mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified propylene-1-ethylene copolymer.
Comparative example 2
A propylene-1-butene copolymer (Tm: 75 ℃, propylene/1-butene =90/10 molar ratio) (100 parts by mass), xylene (400 parts by mass), maleic anhydride (10 parts by mass), benzoyl peroxide (5 parts by mass) and p-tert-butylphenol (1 part by mass) were charged into a reaction flask, and after the air in the reaction system was replaced with nitrogen, the reaction system was heated to 90 ℃ under the protection of nitrogen, and after the solid matter was completely dissolved, the reaction system was heated to 120 ℃ at a rate of 60 ℃/h, and a heat-preservation reaction was carried out for 1h. Maleic anhydride (5 parts by mass) and benzoyl peroxide (5 parts by mass) dissolved in xylene (50 parts by mass) were added to a reaction flask via a dropping funnel within 10min, and after further stirring for 30min, the reaction solution was cooled to 100 ℃, added to xylene (500 parts by mass) and acetone (200 parts by mass) previously heated to 45 ℃ while stirring, cooled to 40 ℃, and further stirred and cooled to 25 ℃, so that the reaction product was precipitated. The solution containing the reaction product is centrifuged to separate low molecular weight products, polymaleic anhydride, and the like contained in the product.
The maleic anhydride-modified propylene-1-butene copolymer which had been centrifuged and taken out was put into acetone (1000 parts by mass) which was stirred at a high speed, and after stirring for 1 hour, the solution was centrifuged to separate a low molecular weight product and polymaleic anhydride in the copolymer, and the operation was repeated twice to purify the copolymer. After purification, the mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified propylene-1-butene copolymer.
Comparative example 3
A propylene-1-ethylene-1-butene copolymer (Tm: 75 ℃, propylene/1-ethylene/1-butene =90/10/5 molar ratio) (100 parts by mass), xylene (400 parts by mass), maleic anhydride (10 parts by mass), benzoyl peroxide (5 parts by mass) and p-tert-butylphenol (1 part by mass) were charged into a reaction flask, and after the air in the reaction system was replaced with nitrogen, the temperature was raised to 90 ℃ under the protection of nitrogen, and after the solid matter was completely dissolved, the temperature was raised to 120 ℃ at a rate of 60 ℃/h, and a heat-preservation reaction was carried out for 1h. Maleic anhydride (5 parts by mass) and benzoyl peroxide (5 parts by mass) dissolved in xylene (50 parts by mass) were added to a reaction flask via a dropping funnel within 10min, and after further stirring for 30min, the reaction solution was cooled to 100 ℃, added to xylene (500 parts by mass) and acetone (200 parts by mass) previously heated to 45 ℃ while stirring, cooled to 40 ℃, and further stirred and cooled to 25 ℃, so that the reaction product was precipitated. The solution containing the reaction product is centrifuged to separate low molecular weight products, polymaleic anhydride, and the like contained in the product.
The maleic anhydride-modified propylene-1-ethylene-1-butene copolymer which had been centrifuged and taken out was put into acetone (1000 parts by mass) which was stirred at a high speed, and after stirring for 1 hour, the solution was centrifuged to separate a low molecular weight product in the copolymer and polymaleic anhydride, and the like, and this operation was repeated twice to purify the copolymer. After purification, the mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified propylene-1-ethylene-1-butene copolymer.
Comparative example 4
A propylene-1-octene copolymer (Tm: 75 ℃, propylene/1-octene =80/20 molar ratio) (100 parts by mass), xylene (500 parts by mass), maleic anhydride (10 parts by mass), benzoyl peroxide (5 parts by mass), and p-tert-butylphenol (1 part by mass) were charged into a reaction flask, and after the air in the reaction system was replaced with nitrogen, the temperature was raised to 90 ℃ under the protection of nitrogen, and after the solid matter was completely dissolved, the temperature was raised to 120 ℃ at a rate of 60 ℃/h, and a heat-preservation reaction was carried out for 1h. Maleic anhydride (5 parts by mass) and benzoyl peroxide (5 parts by mass) dissolved in xylene (50 parts by mass) were added to a reaction flask via a dropping funnel within 10min, and after further stirring for 30min, the reaction solution was cooled to 100 ℃, added to xylene (500 parts by mass) and acetone (200 parts by mass) previously heated to 45 ℃ while stirring, cooled to 40 ℃, and further stirred and cooled to 25 ℃, so that the reaction product was precipitated. The solution containing the reaction product is centrifuged to separate low molecular weight products, polymaleic anhydride, and the like contained in the product.
The maleic anhydride-modified propylene-1-octene copolymer which had been centrifuged and taken out was put into acetone (1000 parts by mass) which was stirred at a high speed, and after stirring for 1 hour, the solution was centrifuged to separate a low molecular weight product and polymaleic anhydride in the copolymer, and the operation was repeated twice to purify the copolymer. After purification, the reaction mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified propylene-1-octene copolymer. .
Comparative example 5
A propylene-1-octene copolymer (Tm: 75 ℃, propylene/1-octene =90/10 molar ratio) (100 parts by mass), xylene (400 parts by mass), maleic anhydride (25 parts by mass), benzoyl peroxide (5 parts by mass), and p-tert-butylphenol (1 part by mass) were charged into a reaction flask, and after the air in the reaction system was replaced with nitrogen, the temperature was raised to 90 ℃ under the protection of nitrogen, and after the solid matter was completely dissolved, the temperature was raised to 120 ℃ at a rate of 60 ℃/h, and a heat-preservation reaction was carried out for 1h. Maleic anhydride (5 parts by mass) and benzoyl peroxide (5 parts by mass) dissolved in xylene (50 parts by mass) were added to a reaction flask via a dropping funnel within 10min, and after further stirring for 30min, the reaction solution was cooled to 100 ℃, added to xylene (500 parts by mass) and acetone (200 parts by mass) heated in advance to 45 ℃ while stirring, cooled to 40 ℃, further stirred and cooled to 25 ℃, and the reaction product was precipitated. The solution containing the reaction product is centrifuged to separate low molecular weight products, polymaleic anhydride, and the like contained in the product.
The maleic anhydride-modified propylene-1-octene copolymer which had been centrifuged and taken out was put into acetone (1000 parts by mass) which was stirred at a high speed, and after stirring for 1 hour, the solution was centrifuged to separate a low molecular weight product and polymaleic anhydride in the copolymer, and the operation was repeated twice to purify the copolymer. After purification, the reaction mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified propylene-1-octene copolymer.
Comparative example 6
A propylene-1-octene copolymer (Tm: 75 ℃, propylene/1-octene =90/10 molar ratio) (100 parts by mass), xylene (400 parts by mass), maleic anhydride (10 parts by mass), benzoyl peroxide (5 parts by mass), and p-tert-butylphenol (1 part by mass) were charged into a reaction flask, and after the air in the reaction system was replaced with nitrogen, the temperature was raised to 90 ℃ under the protection of nitrogen, and after the solid matter was completely dissolved, the temperature was raised to 120 ℃ at a rate of 60 ℃/h, and a heat-preservation reaction was carried out for 2h. Maleic anhydride (5 parts by mass) and benzoyl peroxide (10 parts by mass) dissolved in xylene (50 parts by mass) were added to a reaction flask via a dropping funnel within 10min, and after further stirring for 30min, the reaction solution was cooled to 100 ℃, added to xylene (500 parts by mass) and acetone (200 parts by mass) previously heated to 45 ℃ while stirring, cooled to 40 ℃, and further stirred and cooled to 25 ℃, so that the reaction product was precipitated. The solution containing the reaction product is centrifuged to separate low molecular weight products, polymaleic anhydride, and the like contained in the product.
The maleic anhydride-modified propylene-1-octene copolymer which had been centrifuged and taken out was put into acetone (1000 parts by mass) which was stirred at a high speed, and after stirring for 1 hour, the solution was centrifuged to separate a low molecular weight product in the copolymer and polymaleic anhydride, and the operation was repeated twice to purify the copolymer. After purification, the reaction mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified propylene-1-octene copolymer.
Comparative example 7
A propylene-1-octene copolymer (Tm: 75 ℃, propylene/1-octene =90/10 molar ratio) (100 parts by mass), xylene (450 parts by mass), maleic anhydride (15 parts by mass), benzoyl peroxide (10 parts by mass), and p-tert-butylphenol (1 part by mass) were charged into a reaction flask, and after the air in the reaction system was replaced with nitrogen, the temperature was raised to 90 ℃ under the protection of nitrogen, and after the solid matter was completely dissolved, the temperature was raised to 120 ℃ at a rate of 60 ℃/h, and a heat-preservation reaction was carried out for 1h. The reaction solution was cooled to 100 ℃, added to xylene (500 parts by mass) and acetone (200 parts by mass) previously heated to 45 ℃ while stirring, cooled to 40 ℃, further stirred and cooled to 25 ℃, and the reaction product was precipitated. The solution containing the reaction product is centrifuged to separate low molecular weight products, polymaleic anhydride, and the like contained in the product.
The maleic anhydride-modified propylene-1-octene copolymer which had been centrifuged and taken out was put into acetone (1000 parts by mass) which was stirred at a high speed, and after stirring for 1 hour, the solution was centrifuged to separate a low molecular weight product and polymaleic anhydride in the copolymer, and the operation was repeated twice to purify the copolymer. After purification, the reaction mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified propylene-1-octene copolymer.
Comparative example 8
A propylene-1-octene copolymer (Tm: 75 ℃, propylene/1-octene =90/10 molar ratio) (100 parts by mass), xylene (400 parts by mass), maleic anhydride (15 parts by mass), benzoyl peroxide (5 parts by mass), and p-tert-butylphenol (1 part by mass) were charged into a reaction flask, and after the air in the reaction system was replaced with nitrogen, the temperature was raised to 90 ℃ under the protection of nitrogen, and after the solid matter was completely dissolved, the temperature was raised to 120 ℃ at a rate of 60 ℃/h, and a heat-preservation reaction was carried out for 1h. Adding the mixture dissolved in xylene (50 parts by mass) and benzoyl peroxide (5 parts by mass) into a reaction bottle through a dropping funnel within 10min, further stirring for 30min, cooling the reaction liquid to 100 ℃, adding the reaction liquid into xylene (500 parts by mass) and acetone (200 parts by mass) which are preheated to 45 ℃ in advance while stirring, cooling to 40 ℃, further stirring and cooling to 25 ℃, and precipitating a reaction product. The solution containing the reaction product is centrifuged to separate low molecular weight products, polymaleic anhydride, and the like contained in the product.
The maleic anhydride-modified propylene-1-octene copolymer which had been centrifuged and taken out was put into acetone (1000 parts by mass) which was stirred at a high speed, and after stirring for 1 hour, the solution was centrifuged to separate a low molecular weight product in the copolymer and polymaleic anhydride, and the operation was repeated twice to purify the copolymer. After purification, the reaction mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified propylene-1-octene copolymer.
The adhesive products obtained in the above examples and comparative examples and a commercial polyisocyanate curing agent are mixed according to the molar ratio of the acid value of the solute to NCO of 1, coated on the surface of an aluminum foil, the thickness of the dried adhesive layer is 6 μm, then the hot-coating adhesion operation of a nylon layer and the coating and curing operation of an inner layer film are carried out, finally the application performance tests such as drawing and stripping are carried out, and the test data are shown in the following table 1.
* The evaluation method comprises the following steps:
1. and (3) testing the peel strength: according 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 long 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 tension 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 125mm.
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 1mm. Whether the edge of the inner layer film has the abnormal phenomena of layering, whitening and the like after the deep drawing.
3. Electrolyte resistance: cutting an aluminum plastic film sample into a size of 100mm multiplied by 15mm, soaking the sample in electrolyte (ethylene carbonate/diethyl carbonate/dimethyl carbonate =1/1/1 (volume ratio) 100g and adding 13g of lithium hexafluorophosphate) at 85 ℃ for 24h, taking out the aluminum plastic film sample strip, washing the sample strip with deionized water, wiping off water by using wiping paper to fully dry the water, and evaluating the electrolyte resistance by utilizing a T-shaped stripping test
The test data are shown in the following table:
TABLE 1 evaluation table of sample application properties
It can be seen from the above that, the adhesive prepared by the invention adopts acid modified co-polypropylene as a raw material, and after being blended with a curing agent, the adhesive shows good adhesion and electrolyte resistance with a polyolefin resin substrate and a metal substrate, the data shows that the ethylene-propylene co-polypropylene grafted maleic anhydride has poor impact resistance, which may be caused by short chain segments of the ethylene-propylene co-polypropylene and high product hardness, the stripping strength of the propylene-butylene copolymer and the ethylene-propylene-butylene terpolymer grafted maleic anhydride is low, the electrolyte resistance is poor, the grafting rate is low under the same conditions, which may be caused by poor adhesion with an aluminum foil layer, the solvent concentration of comparative example 4 is reduced, the collision probability of free radicals is reduced, and therefore, the grafting rate is low; comparative example 5 the amount of anhydride added was increased and the initiator initiated too much anhydride, resulting in a decrease in the number of free radicals on the tertiary carbon of the initiating olefin segment; comparative example 6 the addition of the initiator was increased and the reaction was too severe; the comparative example 7 is one-time feeding, is not added in stages, is not sufficient in reaction, and has the effect influenced by the fact that the initiator is decomposed all the time in the temperature rising process. The adhesive product prepared by the invention can completely meet the application performance requirement of the lithium battery aluminum plastic film on the inner layer adhesive.
Claims (10)
1. The utility model provides a lithium cell plastic-aluminum membrane inlayer gluing agent, includes polymer and curing agent, its characterized in that: the polymer is a polymer which takes polyolefin as a raw material and is subjected to polymerization reaction in the presence of unsaturated acid to obtain the polymer with the molecular weight of 10000 to 35000 and the grafting ratio of 2.5 to 4.0 percent;
the preparation method of the polymer comprises the following steps:
mixing polyolefin, an initiator and unsaturated acid in a solvent 1, adding an antioxidant, stirring under the protection of nitrogen, heating to 120 to 180 ℃ at the speed of 30 to 60 ℃/h to perform solution polymerization, keeping the temperature to react for 1 to 6h, adding a solvent 2 to dilute, cooling to room temperature, adding a solvent 3 to precipitate to obtain polymer solid powder with the target molecular weight of 10000 to 35000 and the grafting ratio of 2.5 to 4.0%; dissolving the product in a solvent 4 to prepare a polymer solution;
the mass ratio of the polyolefin to the unsaturated acid to the initiator to the solvent 1 is 2 to 7, and is from 0.05 to 0.2;
the polyolefin is a copolymer of propylene and alpha-olefin; wherein the molar ratio of the propylene to the alpha-olefin is 97 to 75/3 to 25; the alpha-olefin is 1-octene.
2. The preparation method of the internal layer adhesive of the aluminum plastic film of the lithium battery in claim 1 is characterized by comprising the following steps: the preparation method of the polymer in the inner layer adhesive of the aluminum plastic film of the lithium battery comprises the steps of carrying out solution polymerization reaction on polyolefin, unsaturated acid, an initiator and a solvent 1 in an inert gas under normal pressure under the action of an antioxidant, adding a solvent 2 into a reactant, dissolving, adding a solvent 3, and precipitating a graft to obtain polymer solid powder with the molecular weight of 10000 to 35000 and the grafting ratio of 2.5 to 4.0%.
3. The process according to claim 2, wherein: the polymer solid powder is dissolved in a solvent 4 to prepare a polymer solution, and then mixed with a curing agent.
4. The process according to claim 2, wherein: mixing polyolefin, an initiator and unsaturated acid in a solvent 1, adding an antioxidant, stirring under the protection of nitrogen, heating to 120 to 180 ℃ at the speed of 30 to 60 ℃/h to perform solution polymerization, keeping the temperature to react for 1 to 6h, adding a solvent 2 to dilute, cooling to room temperature, adding a solvent 3 to precipitate to obtain polymer solid powder with the target molecular weight of 10000 to 35000 and the grafting ratio of 2.5 to 4.0%; the product was dissolved in solvent 4 to prepare a polymer solution.
5. The process according to claim 2 or 4, wherein: the polyolefin, the initiator and the unsaturated acid are added into the reaction system in 2-3 batches.
6. The process according to claim 2 or 4, wherein: the mass ratio of the polyolefin to the unsaturated acid to the initiator to the solvent 1 is 2 to 7, and is from 0.05 to 0.5.
7. The method of claim 6, wherein: the polyolefin is a copolymer of propylene and alpha-olefin; wherein the molar ratio of the propylene to the alpha-olefin is 97 to 75/3 to 25; the alpha-olefin is 1-octene;
the unsaturated acid is one or more of alpha, beta-unsaturated carboxylic acid and anhydride thereof;
the antioxidant is p-tert-butylphenol, 2, 4-dimethyl-6-tert-butylphenol or pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate); the initiator is an organic peroxide.
8. The process according to claim 2 or 4, wherein: the solvent 1 and the solvent 2 can be the same or different and are selected from benzene; wherein, the addition amounts of the solvent 1 and the solvent 2 are the same; the solvent 3 is an organic solvent as an extractant.
9. The application of the adhesive as claimed in claim 1, wherein the adhesive comprises the following components in parts by weight: the adhesive is applied to the inner layer of the aluminum-plastic film of the lithium battery.
10. Use according to claim 9, characterized in that: the adhesive is prepared by mixing the polymer and the curing agent according to claim 1 according to the molar ratio of the acid value of the solute to NCO of 1.
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