CN115819678A - Preparation method of lithium battery aluminum plastic film inner layer adhesive - Google Patents
Preparation method of lithium battery aluminum plastic film inner layer adhesive Download PDFInfo
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- CN115819678A CN115819678A CN202211630302.8A CN202211630302A CN115819678A CN 115819678 A CN115819678 A CN 115819678A CN 202211630302 A CN202211630302 A CN 202211630302A CN 115819678 A CN115819678 A CN 115819678A
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- lithium battery
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- 239000000853 adhesive Substances 0.000 title claims abstract description 46
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 46
- 239000002985 plastic film Substances 0.000 title claims abstract description 31
- 229920006255 plastic film Polymers 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 20
- 229920000098 polyolefin Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 150000001451 organic peroxides Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 5
- 238000004080 punching Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- -1 aliphatic cycloalkane Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- VKJLDXGFBJBTRQ-UHFFFAOYSA-N 1,2-dimethylcyclopropane Chemical compound CC1CC1C VKJLDXGFBJBTRQ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- YSLKXMCOTLLYSD-UHFFFAOYSA-N 2-ethyl-1,4-dimethylcyclohexane Chemical compound CCC1CC(C)CCC1C YSLKXMCOTLLYSD-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- LZUPUANFEYMWMO-UHFFFAOYSA-N 5-methylhexan-3-ylcyclohexane Chemical compound C1(CCCCC1)C(CC)CC(C)C LZUPUANFEYMWMO-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Adhesives Or Adhesive Processes (AREA)
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. The polyolefin, the unsaturated acid and the initiator are subjected to melt polymerization in an inert gas to obtain a polymer solid with a grafting ratio of 1.5-3.0%. The product is dissolved in a solvent to prepare a polymer solution. The invention has simple and convenient operation process, reasonable molecular weight distribution, stable product quality and application performance, difficult crystallization of the product, good flexibility and tensile resistance, and better electrolyte resistance, caking property 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 a preparation method of an inner layer adhesive of an aluminum plastic film of a lithium battery.
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 prior 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:
TW201942299.A reports a synthesis method of a polyolefin adhesive, which is characterized in that maleic anhydride modified polyolefin is carried out in a solution, a propane-butadiene copolymer, an initiator, maleic anhydride and a solvent are added into a polymerization kettle, the temperature is raised to a certain temperature, solid powder is precipitated in the solvent after reaction for a certain time, and the powder is dried and dissolved, mixed with a curing agent and then coated with 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 uses a large amount of solvent, easily causes pollution to the environment and has higher cost.
The domestic prior patent technology can not meet the problem of environmental pollution in the synthesis of the inner layer glue of the aluminum plastic film of the lithium battery
Disclosure of Invention
The invention aims to provide a preparation method of an inner layer adhesive of an aluminum plastic film of a lithium battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of an inner layer adhesive of an aluminum plastic film of a lithium battery comprises the step of carrying out melt polymerization reaction on polyolefin, unsaturated acid and an initiator in inert gas so as to obtain polymer solid with a grafting rate of 1.5-3.0%.
The polymer solids are dissolved in a solvent to produce a polymer solution, which is then mixed with a curing agent.
Adding polyolefin into a reaction kettle, stirring under the protection of nitrogen, heating to 150-170 ℃ at the speed of 30-60 ℃/h, and continuously adding a solvent 1 solution containing an initiator and unsaturated acid into the reaction kettle to obtain a polymer solid with the grafting rate of 1.5-3.0%; and dissolving the product in a solvent 1 to prepare a polymer solution, and mixing the polymer solution with a curing agent to obtain the lithium battery aluminum-plastic film inner layer adhesive.
The initiator and the unsaturated acid were continuously added to the reaction system over 1 hour.
The mass ratio of the polyolefin to the unsaturated acid to the initiator to the solvent 1 is 10.
The polyolefin is a copolymer of ethylene and alpha-olefin; wherein the molar ratio of ethylene to alpha-olefin is 97-75/3-25 (preferably 95-85/5-15); the alpha-olefin can be one or more of propylene, 1-butene, 1-heptene, 1-octene and 4-methyl-1-pentene;
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 0.25-0.35.
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 to 0.2, more preferably 0.05 to 0.1.
The solvent 1 is one or more of aliphatic cycloalkane and cycloalkane; the cycloalkane may be one or more selected from ethylcyclohexane, 2-methyl-4-cyclohexylhexane, 1,4-dimethyl-2-ethylcyclohexane, 1,2-dimethylcyclopropane and cyclohexane
The lithium battery aluminum-plastic film inner layer adhesive prepared by the method is prepared by dissolving a polymer with the grafting rate of 1.5-3.0% prepared by the method in a solvent to prepare a polymer solution, and then mixing the polymer solution with a curing agent.
The polymer and curing agent are mixed in an acid value of solute and NCO molar ratio of 1:1-2.
Further, the obtained polymer and a commercially available polyisocyanate curing agent are mixed according to the molar ratio of the acid value of a solute to NCO of 1:1-2, 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 covering and bonding operation of a PP layer, adhering and curing operation of an outer layer film and the like are carried out, and finally the qualified lithium battery aluminum plastic film which has the punching depth of more than 7mm, is not delaminated, has the initial peeling force of more than or equal to 15N and is placed in an electrolyte at 85 ℃ for 24 hours, and has no change in peeling force is obtained.
The application of the adhesive is to serve as the adhesive of the inner layer of the aluminum-plastic film of the lithium battery.
The invention has the following advantages:
according to the lithium battery aluminum plastic film inner layer adhesive, acid modified copolyolefin is used as a raw material and is blended with a curing agent, so that the adhesive shows good adhesion and electrolyte resistance with a polyolefin resin base material and a metal base material, 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 modes of the initiator and the anhydride are adjusted, so that the sublimation of the maleic anhydride is reduced, the catalytic activity is ensured, the degradation rate of the polyolefin is reduced, and the molecular weight is controlled while the grafting rate is ensured;
2. the acid modified ethylene-octene copolymer prepared by melt grafting further improves the bonding capability, electrolyte resistance and impact resistance of the product and reduces environmental pollution. 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
An ethylene-1-octene copolymer (Tm: 75 ℃, ethylene/1-octene =94/6 molar ratio) (100 parts by mass) was charged into a reaction vessel, air in the reaction system was replaced with nitrogen, the temperature was raised to 150 ℃ under nitrogen protection, and after the solid material was completely melted, a cyclohexane (8 parts by mass) solution containing maleic anhydride (2.6 parts by mass) and di-t-butyl peroxide (initiator, 1 part by mass) was charged into the reaction vessel at a rate of 10mL/min by a syringe pump, and the reaction was maintained for 1 hour. Thus obtaining the maleic anhydride modified ethylene-1-octene copolymer.
Example 2
An ethylene-1-octene copolymer (Tm: 75 ℃, ethylene/1-octene =94/6 molar ratio) (100 parts by mass) was charged into a reaction vessel, air in the reaction system was replaced with nitrogen, the temperature was raised to 150 ℃ under nitrogen protection, after the solid material was completely melted, a cyclohexane solution containing maleic anhydride (2.6 parts by mass) and di-t-butyl peroxide (initiator, 1 part by mass) was charged into the reaction vessel at a rate of 10mL/min by a syringe pump, and the reaction was carried out for 2 hours while maintaining the temperature. Thus obtaining the maleic anhydride modified ethylene-1-octene copolymer.
Comparative example 1
The preparation method adopts a solution method, and specifically comprises the following steps: an ethylene-1-octene copolymer (Tm: 75 ℃, ethylene/1-octene =94/6 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. And (3) carrying out centrifugal separation on the solution containing the reaction product, and separating and removing low molecular weight products, polymaleic anhydride and the like contained in the product.
The maleic anhydride-modified ethylene-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 mixture was dried at 30 ℃ for 8 hours under reduced pressure to obtain a maleic anhydride-modified ethylene-1-octene copolymer.
The adhesive products obtained in the above examples and comparative examples are mixed with a commercially available polyisocyanate curing agent according to the molar ratio of the acid value of the solute to NCO of 1:2, and then coated on the surface of an aluminum foil, the thickness of the dried adhesive layer is 6 μm, then the hot coating and bonding 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 deep 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: 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 clamping 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 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 punching.
3. Electrolyte resistance: cutting an aluminum plastic film sample into the size of 100mm multiplied by 15mm, soaking in electrolyte [ ethylene carbonate/diethyl carbonate/dimethyl carbonate =1/1/1 (volume ratio) 100g and adding lithium hexafluorophosphate 13g ] at 85 ℃ for 24h, taking out an aluminum plastic film sample strip, washing with deionized water, wiping off water with 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
As can be seen from the above, the adhesive prepared by the invention adopts the acid modified polyolefin as the raw material, and after the acid modified polyolefin is blended with the curing agent, the adhesive shows good adhesion with polyolefin resin base materials and metal base materials and electrolyte resistance, the grafting rate of the maleic anhydride modified ethylene-1-octene copolymer prepared by melt grafting is basically the same as that of the maleic anhydride modified ethylene-1-octene copolymer prepared by the solution method (comparative example 1), the peeling strength and the electrolyte resistance are basically consistent, and the adhesive can completely replace the solution method to prepare POE-g-MAH. Most of the commercially available POE-g-MAH is prepared by twin-screw extrusion, and the grafting rate is low, and the initial stripping and electrolyte resistance are poor. The embodiment of the invention has the advantages that the preparation conditions are specified, and the corresponding amount of each substance is matched, so that the obtained product has good flexibility, excellent tensile resistance and stable application performance. 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 (9)
1. A preparation method of an inner layer adhesive of an aluminum plastic film of a lithium battery is characterized by comprising the following steps: the polyolefin, the unsaturated acid and the initiator are subjected to melt polymerization in an inert gas to obtain a polymer solid with a grafting ratio of 1.5-3.0%.
2. The process according to claim 1, wherein: the polymer solids are dissolved in a solvent to produce a polymer solution, which is then mixed with a curing agent.
3. The process according to claim 1, wherein: adding polyolefin into a reaction kettle, stirring under the protection of nitrogen, heating to 150-170 ℃ at the speed of 30-60 ℃/h, and continuously adding a solvent 1 solution containing an initiator and unsaturated acid into the reaction kettle to obtain a polymer solid with the grafting rate of 1.5-3.0%; and (3) dissolving the product in a solvent 1 to prepare a polymer solution, and then mixing the polymer solution with a curing agent to obtain the inner layer adhesive of the aluminum-plastic film of the lithium battery.
4. The process according to claim 3, wherein: the initiator and the unsaturated acid were continuously added to the reaction system over 1 hour.
5. The process according to claim 3, wherein: the mass ratio of the polyolefin to the unsaturated acid to the initiator to the solvent 1 is (10).
6. The process according to claim 3, wherein: the polyolefin is a copolymer of ethylene and alpha-olefin; wherein the molar ratio of the ethylene to the alpha-olefin is 97-75/3-25; the alpha-olefin can be one or more of propylene, 1-butene, 1-heptene, 1-octene and 4-methyl-1-pentene;
the unsaturated acid is one or more of alpha, beta-unsaturated carboxylic acid and anhydride thereof;
the initiator is organic peroxide;
the solvent 1 is one or more of aliphatic cyclane and cyclane.
7. The lithium battery aluminum plastic film inner layer adhesive prepared by the method of claim 1 is characterized in that: the polymer with the grafting rate of 1.5-3.0 percent prepared by the method is dissolved in a solvent to prepare a polymer solution, and then the polymer solution is mixed with a curing agent.
8. The use of the adhesive of claim 1 as claimed in claim 7, wherein: the polymer and curing agent are combined in an acid value of solute and NCO molar ratio of 1:1-2.
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.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117050235A (en) * | 2023-08-16 | 2023-11-14 | 达高工业技术研究院(广州)有限公司 | Adhesive resin, preparation method thereof, composite adhesive and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018221037A1 (en) * | 2017-05-29 | 2018-12-06 | 東洋紡株式会社 | Polyolefin-based adhesive agent composition |
| US20190326564A1 (en) * | 2016-12-22 | 2019-10-24 | Showa Denko K.K. | Adhesive, laminate obtained using same, battery case material, and battery case and production method therefor |
| CN111918944A (en) * | 2018-03-30 | 2020-11-10 | 东洋纺株式会社 | Polyolefin adhesive composition |
| CN114032053A (en) * | 2021-11-30 | 2022-02-11 | 沈阳化工研究院有限公司 | Lithium battery aluminum plastic film inner layer adhesive and preparation method thereof |
| CN114292363A (en) * | 2021-12-16 | 2022-04-08 | 佛山(华南)新材料研究院 | High-fluidity maleic anhydride grafted polyethylene and preparation method thereof |
| CN115074060A (en) * | 2022-07-08 | 2022-09-20 | 新纶新能源材料(常州)有限公司 | Aluminum-plastic film inner layer adhesive and aluminum-plastic film inner layer bonding process |
-
2022
- 2022-12-19 CN CN202211630302.8A patent/CN115819678A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190326564A1 (en) * | 2016-12-22 | 2019-10-24 | Showa Denko K.K. | Adhesive, laminate obtained using same, battery case material, and battery case and production method therefor |
| WO2018221037A1 (en) * | 2017-05-29 | 2018-12-06 | 東洋紡株式会社 | Polyolefin-based adhesive agent composition |
| CN111918944A (en) * | 2018-03-30 | 2020-11-10 | 东洋纺株式会社 | Polyolefin adhesive composition |
| CN114032053A (en) * | 2021-11-30 | 2022-02-11 | 沈阳化工研究院有限公司 | Lithium battery aluminum plastic film inner layer adhesive and preparation method thereof |
| CN114292363A (en) * | 2021-12-16 | 2022-04-08 | 佛山(华南)新材料研究院 | High-fluidity maleic anhydride grafted polyethylene and preparation method thereof |
| CN115074060A (en) * | 2022-07-08 | 2022-09-20 | 新纶新能源材料(常州)有限公司 | Aluminum-plastic film inner layer adhesive and aluminum-plastic film inner layer bonding process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117050235A (en) * | 2023-08-16 | 2023-11-14 | 达高工业技术研究院(广州)有限公司 | Adhesive resin, preparation method thereof, composite adhesive and application thereof |
| CN117050235B (en) * | 2023-08-16 | 2024-02-06 | 达高工业技术研究院(广州)有限公司 | Adhesive resin, preparation method thereof, composite adhesive and application thereof |
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