CN113249078A - Preparation method of polyurethane surface coating for lithium battery aluminum plastic film - Google Patents
Preparation method of polyurethane surface coating for lithium battery aluminum plastic film Download PDFInfo
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- CN113249078A CN113249078A CN202110561479.6A CN202110561479A CN113249078A CN 113249078 A CN113249078 A CN 113249078A CN 202110561479 A CN202110561479 A CN 202110561479A CN 113249078 A CN113249078 A CN 113249078A
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- 239000002985 plastic film Substances 0.000 title claims abstract description 24
- 229920006255 plastic film Polymers 0.000 title claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 title claims abstract description 21
- 238000000576 coating method Methods 0.000 title claims abstract description 21
- 239000004814 polyurethane Substances 0.000 title claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920006276 ketonic resin Polymers 0.000 claims abstract description 27
- 239000000853 adhesive Substances 0.000 claims abstract description 24
- 230000001070 adhesive effect Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 4
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 90
- 239000003292 glue Substances 0.000 claims description 82
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 33
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 3
- 238000009459 flexible packaging Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
- C08G18/548—Polycondensates of aldehydes with ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
- C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of polyurethane surface coating for a lithium battery aluminum plastic film, which is prepared by compounding an adhesive A, an adhesive B and a diluent, wherein the adhesive A is hyperbranched polyol resin, and the adhesive B is a polyisocyanate compound. The hyperbranched polyol resin is a polyhydroxy ketone-aldehyde resin modifier, the polyhydroxy ketone-aldehyde resin has better corrosion resistance because no ester bond is contained in the structure, and the cyclohexyl on the main bond ensures that the resin has heat resistance, however, the softening point of the ketone-aldehyde resin is higher (generally higher than 80 ℃) and the brittleness is stronger, and the resin can not be independently applied at normal temperature, so that the high-quality coating at normal temperature is successfully realized by introducing a proper amount of soft segments to modify the ketone-aldehyde resin, and the final product prepared by the method has the advantages of excellent initial adhesive strength, better ductility, higher peel strength, excellent chemical corrosion resistance and the like.
Description
Technical Field
The invention relates to an adhesive, in particular to a preparation method of a polyurethane surface adhesive for a lithium battery aluminum plastic film, and belongs to the technical field of adhesive materials.
Background
The packaging material used for the soft package lithium battery is an aluminum-plastic composite film, which is called an aluminum-plastic film for short and is mainly applied to the external package packaging of the battery core of the soft package lithium battery. The soft-package lithium battery packaged by the aluminum plastic film is mainly applied to the field of 3C, gradually permeates into the industry of new energy automobiles in recent years, and provides safe and stable power output for automobiles of various models. The design and manufacturing technology of the aluminum plastic film has high requirements, 90% of the domestic markets are mainly monopolized by japanese and korean enterprises such as DNP/showa electrician and kui-kui village at present, and domestic enterprises such as the new lun technology and the fogdu technology are accelerating the development and production of the aluminum plastic film, but have certain gaps compared with the japanese and korean enterprises. The thickness of the aluminum-plastic film has different specifications, and the structure of the aluminum-plastic film is mainly formed by compounding three materials, namely a CPP layer, an Al layer and a nylon layer from inside to outside. The aluminum-plastic film is produced through two kinds of hot process and dry process, and the hot process includes adhering aluminum layer and CPP layer with MPP and hot pressing at certain temperature. At high temperatures, van der Waals forces in MPP are destroyed, aging and short-circuit resistance are drastically reduced. The dry process is to add adhesive between PP and aluminum layer for direct compounding, and adopts insulating adhesive without high temperature treatment, so that the short circuit preventing performance is better than that of the hot process. And the ductility of the binder is better than that of a PP layer, and the molding is not influenced without high-temperature treatment. Aluminum plastic films are a core material of secondary batteries, and have a high technical barrier and a high profit, and the market rapidly increases at an annual average composite growth rate (CAGR) of 42%. Most of the domestic aluminum-plastic film adhesives are not related to electrolyte corrosion resistance, deep drawing performance and the like, so that the global and domestic aluminum-plastic film market is mainly monopolized by a few Japanese enterprises such as Japanese DNP printing, Japanese showa and electrician at present.
The invention content is as follows:
in order to overcome the defects of the prior art, the invention aims to provide the preparation method of the polyurethane surface coating for the lithium battery aluminum plastic film, which has the advantages of excellent initial adhesion strength, better ductility, higher peel strength, excellent chemical corrosion resistance and the like.
In order to achieve the above object, the present invention adopts the following technical solutions:
a preparation method of polyurethane surface coating for a lithium battery aluminum plastic film is prepared by compounding glue A, glue B and a diluent, wherein the glue A is hyperbranched polyol resin, and the glue B is a polyisocyanate compound, and comprises the following steps:
a. preparing glue A: preparing hyperbranched polyol resin by a one-step feeding method, respectively taking diethylene glycol, ketone-aldehyde resin and methyl acetone into a reaction vessel, stirring and dissolving, then adding IPDI, slowly heating to 100-105 ℃, keeping the temperature for 10 hours, then cooling, and then adding ethyl acetate for dilution to obtain A glue;
b. preparing glue B: respectively taking TDI, MDI-50 and ethyl acetate in a flask, adding half of trimethylolpropane when the temperature is raised to 45 ℃, wherein the exothermic reaction is carried out, properly controlling and cooling, adding the other half of trimethylolpropane after 30min, controlling the temperature, and carrying out heat preservation reaction for a period of time to obtain glue B;
c. preparing polyurethane surface coating glue: mixing the glue A, the glue B and the diluent according to a proportion and a proper working concentration.
Preferably, in the step a, the mass ratio of diethylene glycol, ketone-aldehyde resin, methyl acetone, IPDI and ethyl acetate is: 0.16:0.32:0.04:0.32:0.16.
Still preferably, in the step a, the reaction temperature and time are 100-105 ℃ and 10 hours, respectively.
Further preferably, in the step b, the mass ratio of TDI, MDI-50, ethyl acetate and trimethylolpropane is 50:21:27: 13.
Further preferably, in the step c, the compounding weight ratio of the glue A and the glue B is 2:1, the working concentration is 40-45%, and the diluent is ethyl acetate.
Still preferably, the preparation method of the polyurethane surface sizing for the lithium battery aluminum plastic film comprises the following steps:
a. preparing glue A: preparing hyperbranched polyol resin by a one-step feeding method, respectively taking diethylene glycol, ketone-aldehyde resin and methyl acetone into a reaction vessel, stirring and dissolving, then adding IPDI, slowly heating to 100-105 ℃, keeping the temperature for 10 hours, then cooling, and then adding ethyl acetate for dilution to obtain A glue;
b. preparing glue B: respectively taking TDI, MDI-50 and ethyl acetate in a flask, adding half of trimethylolpropane when the temperature is raised to 45 ℃, wherein the exothermic reaction is carried out, properly controlling and cooling, adding the other half of trimethylolpropane after 30min, controlling the temperature, and carrying out heat preservation reaction for a period of time to obtain glue B;
c. preparing polyurethane surface coating glue: mixing the glue A, the glue B and the diluent according to a proportion and a proper working concentration.
Wherein the mass ratio of diethylene glycol, ketone-aldehyde resin, methyl acetone, IPDI and ethyl acetate is as follows: 0.16:0.32:0.04:0.32: 0.16; TDI, MDI-50, ethyl acetate and trimethylolpropane in a mass ratio of 50:21:27: 13; the compounding weight ratio of the glue A and the glue B is 2:1, the working concentration is 40-45%, and the diluent is ethyl acetate.
The invention has the advantages that: the hyperbranched polyol resin is a polyhydroxy ketone-aldehyde resin modifier, the polyhydroxy ketone-aldehyde resin has better corrosion resistance because no ester bond is contained in the structure, and the cyclohexyl on the main bond ensures that the resin has heat resistance, however, the softening point of the ketone-aldehyde resin is higher (generally higher than 80 ℃) and the brittleness is stronger, and the resin can not be independently applied at normal temperature, so that the high-quality coating at normal temperature is successfully realized by introducing a proper amount of soft segments to modify the ketone-aldehyde resin, and the final product prepared by the method has the advantages of excellent initial adhesive strength, better ductility, higher peel strength, excellent chemical corrosion resistance and the like.
The specific implementation mode is as follows:
in the present invention, all the raw materials are commercially available unless otherwise specified.
Example 1
The polyurethane surface coating for the lithium battery aluminum plastic film is prepared by compounding two components of A glue and B glue, wherein the A glue is hyperbranched polyol resin, and the B glue is a polyisocyanate compound, and the preparation steps are as follows:
preparing glue A: preparing hyperbranched polyol resin by a one-step feeding method, respectively taking 160g of diethylene glycol, 320g of ketone-aldehyde resin and 40g of methyl acetone in a reaction vessel, stirring and dissolving, adding 32g of IPDI, slowly heating to 100 ℃, keeping the temperature for 10 hours, then cooling, and then adding 160g of ethyl acetate for dilution to obtain A glue;
preparing glue B: respectively putting 500g of TDI, 210g of MDI-50 and 270g of ethyl acetate in a flask, adding 75g of trimethylolpropane when the temperature is raised to 45 ℃, wherein the reaction is exothermic and needs to be properly controlled and cooled, adding 75g of trimethylolpropane after 30min, controlling the temperature, and carrying out heat preservation reaction for a period of time to obtain glue B;
preparing polyurethane surface coating glue: the glue A, the glue B and the diluent are mixed according to a proper working concentration, the compound weight ratio of the glue A to the glue B is 2:1, the working concentration is 40-45%, and the diluent is ethyl acetate.
Many examples of the present invention, examples 2 to 5 have the same preparation method and procedure as example 1, except for the difference in the raw material ratio and the parameters during the reaction, as follows:
example 2
The preparation process of this example 2 is specifically as follows:
preparing glue A: preparing hyperbranched polyol resin by a one-step feeding method, respectively taking 170g of diethylene glycol, 300g of ketone-aldehyde resin and 40g of methyl acetone in a reaction vessel, stirring and dissolving, adding 42g of IPDI, slowly heating to 105 ℃, keeping the temperature for 10 hours, then cooling, and then adding 160g of ethyl acetate for dilution to obtain A glue;
preparing glue B: respectively putting 500g of TDI, 210g of MDI-50 and 270g of ethyl acetate in a flask, adding 75g of trimethylolpropane when the temperature is raised to 45 ℃, wherein the reaction is exothermic and needs to be properly controlled and cooled, adding 75g of trimethylolpropane after 30min, controlling the temperature, and carrying out heat preservation reaction for a period of time to obtain glue B;
preparing polyurethane surface coating glue: the glue A, the glue B and the diluent are mixed according to a proper working concentration, the compound weight ratio of the glue A to the glue B is 2:1, the working concentration is 40-45%, and the diluent is ethyl acetate.
Example 3
The specific preparation procedure for this example 3 is as follows:
preparing glue A: preparing hyperbranched polyol resin by a one-step feeding method, respectively taking 140g of diethylene glycol, 340g of ketone-aldehyde resin and 40g of methyl acetone in a reaction vessel, stirring and dissolving, then adding 32g of IPDI, slowly heating to 100 ℃, keeping the temperature for 10 hours, then cooling, and then adding 160g of ethyl acetate for dilution to obtain A glue;
preparing glue B: respectively putting 500g of TDI, 210g of MDI-50 and 270g of ethyl acetate in a flask, adding 75g of trimethylolpropane when the temperature is raised to 45 ℃, wherein the reaction is exothermic and needs to be properly controlled and cooled, adding 75g of trimethylolpropane after 30min, controlling the temperature, and carrying out heat preservation reaction for a period of time to obtain glue B;
preparing polyurethane surface coating glue: the glue A, the glue B and the diluent are mixed according to a proper working concentration, the compound weight ratio of the glue A to the glue B is 2:1, the working concentration is 40-45%, and the diluent is ethyl acetate.
Example 4
The specific preparation steps of this example are as follows:
preparing glue A: preparing hyperbranched polyol resin by a one-step feeding method, respectively taking 160g of diethylene glycol, 320g of ketone-aldehyde resin and 40g of methyl acetone in a reaction vessel, stirring and dissolving, then adding 32g of IPDI, slowly heating to 100-105 ℃, keeping the temperature for 10 hours, then cooling, and then adding 160g of ethyl acetate for dilution to obtain A glue;
preparing glue B: respectively putting 500g of TDI, 210g of MDI-50 and 270g of ethyl acetate in a flask, adding 75g of trimethylolpropane when the temperature is raised to 45 ℃, wherein the reaction is exothermic and needs to be properly controlled and cooled, adding 75g of trimethylolpropane after 30min, controlling the temperature, and carrying out heat preservation reaction for a period of time to obtain glue B;
preparing polyurethane surface coating glue: the glue A, the glue B and the diluent are mixed according to a proper working concentration, the compound weight ratio of the glue A to the glue B is 3:1, the working concentration is 40-45%, and the diluent is ethyl acetate.
Example 5
The specific preparation steps of this example are as follows:
preparing glue A: preparing hyperbranched polyol resin by a one-step feeding method, respectively taking 160g of diethylene glycol, 320g of ketone-aldehyde resin and 40g of methyl acetone in a reaction vessel, stirring and dissolving, then adding 32g of IPDI, slowly heating to 100-105 ℃, keeping the temperature for 10 hours, then cooling, and then adding 160g of ethyl acetate for dilution to obtain A glue;
preparing glue B: respectively putting 500g of TDI, 210g of MDI-50 and 270g of ethyl acetate in a flask, adding 75g of trimethylolpropane when the temperature is raised to 45 ℃, wherein the reaction is exothermic and needs to be properly controlled and cooled, adding 75g of trimethylolpropane after 30min, controlling the temperature, and carrying out heat preservation reaction for a period of time to obtain glue B;
preparing polyurethane surface coating glue: the glue A, the glue B and the diluent are mixed according to a proper working concentration, the compound weight ratio of the glue A to the glue B is 1:1, the working concentration is 40-45%, and the diluent is ethyl acetate.
Performance detection
The top coating prepared in example 1-5 is successfully used for the adhesion of aluminum plastic films, and the test results were examined, as shown in Table 1, the proportion of the ketone-aldehyde resin had a large influence on the peel strength and the corrosion resistance, mainly because the hardness of the adhesive layer was excessively high to destroy the corona on the surface of the film base material as the proportion of the ketone-aldehyde resin having a higher hardness was increased, thereby affecting the peeling strength, in addition, the inner layer of the aluminum plastic film of the lithium battery is mostly a CPP layer which is a non-barrier material, and the inevitable small part of organic solvent and a small amount of acid in the electrolyte of the lithium battery enters the inside of the base material in the process of high temperature and long-time use, thereby damaging the macromolecular adhesive and delaminating, the introduction of the polyhydroxy ketone-aldehyde resin improves the corrosion resistance of the adhesive, as shown in Table 1, as the proportion of the ketone-aldehyde resin increases, the AL/CPP peel strength shows a state of almost no decay. Comparing examples 1, 4 and 5, it is found that when the ratio of the A/B glue is 2:1, the depth of the aluminum plastic film is deepest, mainly because the nylon layer and the aluminum foil layer are rigid materials, the surface corona is relatively fragile, and the excessively high ratio of the B glue causes the degree of internal crosslinking of the adhesive to be excessively high, which affects the ductility of the polymer; too low a proportion of B-size results in too low mechanical strength of the adhesive polymer, which affects the adhesive strength.
Table 1 table of test results of examples 1 to 5
In conclusion, the preparation method is environment-friendly, the hyperbranched polyol resin is a polyhydroxy ketone-aldehyde resin modifier, the polyhydroxy ketone-aldehyde resin has better corrosion resistance because no ester bond is contained in the structure, and the heat resistance is realized due to the cyclohexyl on the main bond, however, the softening point of the ketone-aldehyde resin is higher (generally higher than 80 ℃) and the brittleness is stronger, and sizing can not be independently performed at normal temperature, so that high-quality coating at normal temperature is successfully realized by introducing a proper amount of soft segments to modify the ketone-aldehyde resin, and the final product prepared by the method has the advantages of excellent initial adhesion strength, better ductility, higher peel strength, excellent chemical corrosion resistance and the like.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.
Claims (6)
1. A preparation method of polyurethane surface coating for a lithium battery aluminum plastic film is characterized by being prepared by compounding an adhesive A, an adhesive B and a diluent, wherein the adhesive A is hyperbranched polyol resin, and the adhesive B is a polyisocyanate compound, and the preparation method comprises the following steps:
a. preparing glue A:
preparing hyperbranched polyol resin by a one-step feeding method, respectively taking diethylene glycol, ketone-aldehyde resin and methyl acetone into a reaction vessel, stirring and dissolving, then adding IPDI, slowly heating to 100-105 ℃, keeping the temperature for 10 hours, then cooling, and then adding ethyl acetate for dilution to obtain A glue;
b. preparing glue B:
respectively taking TDI, MDI-50 and ethyl acetate in a flask, adding half of trimethylolpropane when the temperature is raised to 45 ℃, wherein the exothermic reaction is carried out, properly controlling and cooling, adding the other half of trimethylolpropane after 30min, controlling the temperature, and carrying out heat preservation reaction for a period of time to obtain glue B;
c. preparing polyurethane surface coating glue:
mixing the glue A, the glue B and the diluent according to a proportion and a proper working concentration.
2. The method for preparing the polyurethane surface coating adhesive for the aluminum plastic film of the lithium battery as claimed in claim 1, wherein in the step a, the mass ratio of diethylene glycol, ketone-aldehyde resin, methyl acetone, IPDI and ethyl acetate is as follows: 0.16:0.32:0.04:0.32:0.16.
3. The method as claimed in claim 1, wherein the reaction temperature and time in step a are 100-105 ℃ and 10 hours, respectively.
4. The method for preparing the polyurethane surface coating adhesive for the aluminum plastic film of the lithium battery as recited in claim 1, wherein in the step b, the mass ratio of TDI, MDI-50, ethyl acetate and trimethylolpropane is 50:21:27: 13.
5. The method for preparing the low VOC polyurethane adhesive for flexible packages according to claim 1, wherein in the step S4, the compounding weight ratio of the glue A and the glue B is 2:1, and the working concentration is 40-45%.
6. The method of preparing a low VOC polyurethane adhesive for flexible packaging according to claim 1, wherein the diluent is ethyl acetate.
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CN202110561479.6A Withdrawn CN113249078A (en) | 2021-05-22 | 2021-05-22 | Preparation method of polyurethane surface coating for lithium battery aluminum plastic film |
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CN114149781A (en) * | 2022-02-07 | 2022-03-08 | 宁波惠之星新材料科技有限公司 | TPU composite glue, protective film and preparation method thereof |
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Cited By (2)
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CN114149781A (en) * | 2022-02-07 | 2022-03-08 | 宁波惠之星新材料科技有限公司 | TPU composite glue, protective film and preparation method thereof |
CN114149781B (en) * | 2022-02-07 | 2022-04-26 | 宁波惠之星新材料科技有限公司 | TPU composite glue, protective film and preparation method thereof |
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Application publication date: 20210813 |