CN109321175B - Battery flame-retardant adhesive, preparation method thereof and composite flame-retardant insulating blue film for battery - Google Patents
Battery flame-retardant adhesive, preparation method thereof and composite flame-retardant insulating blue film for battery Download PDFInfo
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- CN109321175B CN109321175B CN201811193149.0A CN201811193149A CN109321175B CN 109321175 B CN109321175 B CN 109321175B CN 201811193149 A CN201811193149 A CN 201811193149A CN 109321175 B CN109321175 B CN 109321175B
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
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Abstract
The invention relates to the field of power battery safety protection, in particular to a battery flame-retardant adhesive, a preparation method thereof and a composite flame-retardant insulating blue film for a battery. The battery flame-retardant adhesive comprises 20-60 parts of 2-ethylhexyl acrylate, 1-10 parts of methyl acrylate, 1-5 parts of 4-methacryloyloxyethyl trimellitic anhydride, 1-15 parts of butyl acrylate, 1-10 parts of diethyl vinylphosphate, 0.001-0.5 part of tert-butyl peroxymaleate serving as a free radical initiator, 0.001-1 part of ferric trichloride, 0.01-2 parts of triphenylphosphine, 50-250 parts of an organic solvent, 0.1-2 parts of trimethylolpropane triglycidyl ether, 0.01-0.5 part of a curing accelerator and 1-30 parts of a dye. The invention solves the problem of poor creep property of the traditional acrylate pressure-sensitive adhesive. Under the action of a catalyst, the multifunctional epoxy functional group and the anhydride of the anhydride modified acrylic acid flame-retardant pressure-sensitive adhesive are chemically crosslinked to form a three-dimensional crosslinking network, so that higher cohesion is obtained, and the creep resistance of the protective film is improved. The invention enhances the flame retardant property of the acrylate pressure-sensitive protective film.
Description
Technical Field
The invention relates to the field of power battery safety protection, in particular to a battery flame-retardant adhesive, a preparation method thereof and a composite flame-retardant insulating blue film for a battery.
Background
In the assembly production process of the power battery, a special protective film is generally used for insulating and protecting the shell of the power battery. The protective film special for the power battery generally adopts a high-molecular PET film as a base material, and special glue is coated on the base material, wherein the total thickness of the protective film is 80-120 mu m. The protective film special for the power battery generally needs to have better anti-tilting property, good viscosity, creep resistance, high electrical insulation property, good flame retardant property and the like, and no adhesive residue is left when the protective film is uncovered. The special acrylic ester protective film is a pressure-sensitive adhesive with the widest application range at present, has good viscosity and excellent weather resistance and heat resistance, and is suitable for the field of power batteries. However, many current protective films dedicated to acrylates have insufficient creep resistance, and creep easily occurs under 3000N pressure, which causes the appearance of the outer case of the power battery to be non-uniform. Meanwhile, many special protective films for acrylates have insufficient flame retardant properties. With the rapid development of new energy automobiles, the requirements on power batteries are also higher and higher. At present, the power battery is generally packaged by a common PET insulating film, and is characterized by good insulating property and good fitting property, but has the defect that the flame retardance can not reach the flame retardance UL-94-V-0 level.
Disclosure of Invention
Therefore, the first object of the present invention is to provide a battery flame retardant adhesive with good flame retardancy, high insulation, good adhesion and high creep resistance.
The above object is achieved in this way.
A battery flame-retardant adhesive comprises 20-60 parts of 2-ethylhexyl acrylate, 1-10 parts of methyl acrylate, 1-5 parts of 4-methacryloyloxyethyl trimellitic anhydride, 1-15 parts of butyl acrylate, 1-10 parts of diethyl vinylphosphate, 0.001-0.5 part of tert-butyl peroxymaleate serving as a free radical initiator, 0.001-1 part of ferric trichloride, 0.01-2 parts of triphenylphosphine, 50-250 parts of an organic solvent, 0.1-2 parts of trimethylolpropane triglycidyl ether, 0.01-0.5 part of a curing accelerator and 1-30 parts of a dye; the above are all parts by mass.
The technical scheme can be further perfected as follows.
The organic solvent is one or a mixture of two or a mixture of three of ethyl acetate, toluene and butyl acetate.
The curing accelerator is one or a mixture of two or a mixture of three of triethanolamine, dimethylaniline and 2, 4, 6-tris (dimethylaminomethyl) phenol.
The dye is one or two of indigo blue and phthalocyanine blue.
The second purpose of the invention is to provide a preparation method of the battery flame-retardant adhesive with good flame retardance, high insulativity, good viscosity and high creep resistance.
The above object is achieved in this way.
A preparation method of a battery flame-retardant adhesive comprises the steps of mixing 20-60 parts of acrylic acid-2-ethylhexyl ester, 1-10 parts of methyl acrylate, 1-5 parts of 4-methacryloyloxyethyl trimellitic anhydride, 1-15 parts of butyl acrylate, 1-10 parts of vinyl diethyl phosphate, 0.001-0.5 part of a free radical initiator tert-butyl peroxymaleate, 0.001-1 part of ferric trichloride, 0.01-2 parts of triphenylphosphine and 50-250 parts of an organic solvent, carrying out nitrogen deoxidization for 30-120 minutes, controlling the temperature to be 60-120 ℃, carrying out reverse atom transfer radical polymerization under the protection of nitrogen, carrying out polymerization for 1-20 hours, controlling the number average molecular weight to be 10000-400000, controlling the molecular weight polydispersity to be 1.1-1.5, controlling the glass transition temperature to be-45-20 ℃, reducing the reaction temperature to be 10-30 ℃, then adding 0.1-2 parts of trimethylolpropane triglycidyl ether, 0.01-0.5 part of curing accelerator and 1-30 parts of dye, and mixing to obtain the battery flame-retardant adhesive; the above are all parts by mass.
The third purpose of the invention is to provide the composite flame-retardant insulating blue film for the battery, which contains the battery flame-retardant adhesive and has good flame retardance, high insulativity, good viscosity and high creep resistance.
The above object is achieved in this way.
The utility model provides a compound fire-retardant insulating blue membrane for battery, including the fire-retardant adhesive layer of one deck battery fire-retardant gluing agent of clamp between the fire-retardant polyethylene glycol terephthalate thin layer of VTM-0 level halogen-free of fire-retardant gluing agent of VTM-0 level and second layer and isolation layer of battery fire-retardant gluing agent, then establish the isolation layer at the first layer fire-retardant gluing agent of VTM-0 level halogen-free fire-retardant polyethylene glycol terephthalate (PET) thin layer front, compound the gluing agent layer of another deck battery fire-retardant gluing agent at the second layer fire-retardant gluing agent of VTM-0 level halogen-free fire-retardant polyethylene glycol terephthalate (PET) thin layer reverse side, the rolling is cut at last, obtain the compound layer fire-retardant insulating blue membrane for battery, the fire-retardant gluing agent layer component of battery is: the method comprises the following steps: 20-60 parts of 2-ethylhexyl acrylate, 1-10 parts of methyl acrylate, 1-5 parts of 4-methacryloyloxyethyl trimellitic anhydride, 1-15 parts of butyl acrylate, 1-10 parts of diethyl vinylphosphate, 0.001-0.5 part of tert-butyl peroxymaleate serving as a free radical initiator, 0.001-1 part of ferric trichloride, 0.01-2 parts of triphenyl phosphorus, 50-250 parts of an organic solvent, 0.1-2 parts of trimethylolpropane triglycidyl ether, 0.01-0.5 part of a curing accelerator and 1-30 parts of a dye; the above are all parts by mass.
The technical scheme can be further perfected as follows.
Uniformly coating a non-silicon isolating agent on the front surface of a first layer of halogen-free flame-retardant polyethylene terephthalate film layer with the fire-retardant rating of VTM-0 and the thickness of 10-50 microns, and then, placing the film layer at 80-120 ℃ for heat preservation and solidification for 1-10 min to obtain an isolating layer with the thickness of 0.1-1 micron.
Uniformly coating the battery flame-retardant adhesive on the reverse side of a first layer of a VTM-0 level halogen-free flame-retardant polyethylene terephthalate film layer, then placing the first layer of battery flame-retardant adhesive at 80-130 ℃, preserving heat, drying and curing for 1-20 min to obtain a first layer of adhesive layer of the battery flame-retardant adhesive with the fire rating of 20-40 mu m, then pasting a second layer of halogen-free flame-retardant polyethylene terephthalate film layer with the fire rating of VTM-0 level on the outer side of the first layer of battery flame-retardant adhesive, then coating the reverse side of the second layer of battery flame-retardant adhesive with the fire rating of VTM-0 level halogen-free flame-retardant polyethylene terephthalate film layer with the fire rating of 20-40 mu m, then placing the second layer of battery flame-retardant adhesive at 80-130 ℃, preserving heat, drying and curing for 1-20 min to obtain an.
In the technical scheme, the anhydride modified acrylate pressure-sensitive adhesive is adopted, and reverse atom transfer radical polymerization (R-ARTP) polymerization is carried out to synthesize the anhydride modified acrylate flame-retardant pressure-sensitive adhesive with uniform chemical structure and narrow molecular weight distribution, and the problems of poor creep resistance and insufficient flame retardant property of an oligomer are solved by introducing the flame-retardant phosphorus-containing monomer. And further through an anhydride-epoxy crosslinking reaction, the cohesive force of the acrylic acid flame-retardant pressure-sensitive adhesive can be improved, and the creep resistance can be further improved.
The invention solves the problem of poor creep property of the traditional acrylate pressure-sensitive adhesive. The invention selects acrylic acid-2-ethylhexyl ester, butyl acrylate, anhydride functional monomer and flame retardant monomer to carry out reverse atom transfer radical polymerization (R-ARTP) polymerization, and synthesizes the anhydride modified acrylic acid flame retardant pressure sensitive adhesive with uniform chemical structure and narrow molecular weight distribution. Trimethylolpropane triglycidyl ether is used as a cross-linking agent, and under the action of a catalyst, a multifunctional epoxy functional group and anhydride of the anhydride modified acrylic acid flame-retardant pressure-sensitive adhesive are subjected to chemical cross-linking to form a three-dimensional cross-linked network, so that higher cohesive force is obtained, and the creep resistance of the protective film is improved.
The flame-retardant functional monomer and the flame-retardant film are introduced, so that the flame-retardant performance of the acrylate pressure-sensitive protective film can be further enhanced.
Drawings
FIG. 1 is a schematic structural view of a composite flame-retardant insulating blue film for a battery according to an embodiment.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The parts referred to in the following examples are parts by mass.
The first embodiment is a power battery flame-retardant adhesive and a composite layer flame-retardant insulating protective blue film for a power battery, and is prepared by the following steps.
50 parts of 2-ethylhexyl acrylate (2-EHA), 5 parts of Methyl Acrylate (MA), 2 parts of 4-methacryloyloxyethyl trimellitic anhydride (4-META), 5 parts of Butyl Acrylate (BA), 8 parts of diethyl vinylphosphate, 0.03 part of tert-butyl peroxymaleate (TBMA), a radical initiator, 0.06 part of ferric trichloride, 0.10 part of triphenylphosphine and 100 parts of toluene were mixed, oxygen was removed by nitrogen for 30 minutes, the temperature was controlled at 90 ℃ and a reverse atom transfer radical polymerization (R-ARTP) polymerization reaction was carried out under nitrogen protection for 6 hours, the number average molecular weight (Mn) was controlled to 302300 and the number of molecular weight polydispersity was controlled to 1.4. Reducing the reaction temperature to 30 ℃, and then adding 0.4 part of trimethylolpropane triglycidyl ether, 0.02 part of curing accelerator 2, 4, 6-tris (dimethylaminomethyl) phenol and 15 parts of phthalocyanine blue for mixing to obtain the power battery flame-retardant adhesive; the above are all parts by mass.
And (3) combining the figure 1, and preparing the composite layer flame-retardant insulating protective blue film for the power battery in the second step.
Uniformly coating a non-silicon isolating agent RL-600 on the front surface of a 25-micron first layer of halogen-free flame-retardant polyethylene glycol terephthalate film layer 1 with the fire-retardant rating of VTM-0, and then placing at 120 ℃ for heat preservation and solidification for 3min to obtain an isolating layer 2 with the thickness of 0.5 micron.
And (3) uniformly coating the power battery flame-retardant adhesive prepared in the step one on the reverse side of the first layer of the halogen-free flame-retardant polyethylene terephthalate film layer 1 with the fire-retardant rating of VTM-0, then placing at 120 ℃, preserving heat, drying and curing for 3min to obtain a 30-micrometer first layer of the adhesive layer 3 of the power battery flame-retardant adhesive, and further compounding a 25-micrometer second layer of the halogen-free flame-retardant polyethylene terephthalate film layer 4 with the fire-retardant rating of VTM-0.
(3) And uniformly coating the power battery flame-retardant adhesive prepared in the first step on the reverse side of the second halogen-free flame-retardant polyethylene terephthalate film layer 4 with the second fireproof grade of VTM-0, placing at 120 ℃, preserving heat, drying and curing for 3min to obtain an adhesive layer 5 of the second power battery flame-retardant adhesive with the thickness of 30 microns, and finally rolling and slitting to obtain the composite layer flame-retardant insulation protection blue film for the power battery.
The second embodiment is a power battery flame-retardant adhesive and a composite layer flame-retardant insulating protective blue film for a power battery, and is prepared by the following steps, wherein the power battery flame-retardant adhesive is synthesized in the first step.
60 parts of 2-ethylhexyl acrylate (2-EHA), 7 parts of Methyl Acrylate (MA), 3 parts of 4-methacryloyloxyethyl trimellitic anhydride (4-META), 15 parts of Butyl Acrylate (BA), 10 parts of diethyl vinylphosphate, 0.06 part of tert-butyl peroxymaleate (TBMA) as a radical initiator, 0.02 part of ferric trichloride, 0.1 part of triphenylphosphine and 100 parts of ethyl acetate are mixed, nitrogen is removed for 80 minutes, then reverse atom transfer radical polymerization (R-ARTP) is carried out for 12 hours under the protection of nitrogen, the number average molecular weight (Mn) is controlled to be 500 2123, the molecular weight polydispersity is controlled to be 1.3, the reaction temperature is reduced to 25 ℃, 0.3 part of trimethylolpropane triglycidyl ether, 0.02 part of curing accelerator dimethylaniline and 15 parts of phthalocyanine blue are added and mixed, obtaining a power battery flame-retardant adhesive; the above are all parts by mass.
And (3) combining the figure 1, and preparing the composite layer flame-retardant insulating protective blue film for the power battery in the second step.
Uniformly coating a non-silicon release agent RL-600 on the front surface of a 25-micron first layer of halogen-free flame-retardant polyethylene glycol terephthalate film layer 1 with the fire-retardant rating of VTM-0, and then placing at 120 ℃ for heat preservation and curing for 3min to obtain a 0.8-micron release layer 2.
And (3) uniformly coating the power battery flame-retardant adhesive prepared in the step one on the reverse side of the first layer of the halogen-free flame-retardant polyethylene terephthalate film layer 1 with the fire-retardant rating of VTM-0, then placing at 110 ℃, preserving heat, drying and curing for 4min to obtain an adhesive layer 3 of the first layer of the power battery flame-retardant adhesive with the thickness of 25 microns, and further compounding a second layer of the halogen-free flame-retardant polyethylene terephthalate film layer 4 with the fire-retardant rating of VTM-0.
And uniformly coating the power battery flame-retardant adhesive prepared in the first step on the reverse side of the second halogen-free flame-retardant polyethylene terephthalate film layer 4 with the fire-retardant rating of VTM-0 compounded in the second step, placing at 110 ℃, preserving heat, drying and curing for 4min to obtain an adhesive layer 5 of the second power battery flame-retardant adhesive with the thickness of 25 microns, and finally rolling and slitting to obtain the composite layer flame-retardant insulating protective blue film for the power battery.
The third embodiment is a power battery flame-retardant adhesive and a composite layer flame-retardant insulating protective blue film for a power battery, and is prepared by the following steps, namely the first step is used for synthesizing the power battery flame-retardant adhesive.
55 parts of 2-ethylhexyl acrylate (2-EHA), 9 parts of Methyl Acrylate (MA), 5 parts of 4-methacryloyloxyethyl trimellitic anhydride (4-META), 10 parts of Butyl Acrylate (BA), 8 parts of diethyl vinylphosphate, 0.1 part of tert-butyl peroxymaleate (TBMA), a radical initiator, 0.1 part of ferric trichloride, 0.2 part of triphenylphosphine and 80 parts of ethyl acetate were mixed, oxygen was removed by nitrogen for 100 minutes, then the temperature was controlled at 85 ℃ and a reverse atom transfer radical polymerization (R-ARTP) polymerization reaction was carried out under nitrogen protection for 12 hours, the number average molecular weight (Mn) was controlled to 198700 and the number of molecular weight polydispersity was controlled to 1.25. Reducing the reaction temperature to 20 ℃, and then adding 0.6 part of trimethylolpropane triglycidyl ether, 0.01 part of curing accelerator triethanolamine and 25 parts of phthalocyanine blue for mixing to obtain the power battery flame-retardant adhesive; the above are all parts by mass.
And (3) combining the figure 1, and preparing the composite layer flame-retardant insulating protective blue film for the power battery in the second step.
Uniformly coating a non-silicon release agent RL-600 on the front surface of a first layer of 30 mu m halogen-free flame-retardant polyethylene terephthalate film layer 1 with the fire-retardant rating of VTM-0, and then placing at 100 ℃ for heat preservation and solidification for 4min to obtain a 0.4 mu m release layer 2.
And (3) uniformly coating the power battery flame-retardant adhesive prepared in the step one on the reverse side of the first layer of the halogen-free flame-retardant polyethylene terephthalate film layer 1 with the fire-retardant rating of VTM-0, then placing at 100 ℃, preserving heat, drying and curing for 5min to obtain a first layer of the adhesive layer 3 of the power battery flame-retardant adhesive with the thickness of 20 microns, and further compounding a second layer of the halogen-free flame-retardant polyethylene terephthalate film layer 4 with the fire-retardant rating of VTM-0 with the thickness of 30 microns.
And uniformly coating the power battery flame-retardant adhesive prepared in the first step on the reverse side of the second halogen-free flame-retardant polyethylene terephthalate film layer 4 with the fireproof grade of VTM-0 compounded in the second step, then placing at 100 ℃, preserving heat, drying and curing for 5min to obtain an adhesive layer 5 of the second power battery flame-retardant adhesive with the thickness of 20 microns, and finally rolling and slitting to obtain the composite layer flame-retardant insulating protective blue film for the power battery.
The fourth embodiment is a power battery flame-retardant adhesive and a composite layer flame-retardant insulating protective blue film for a power battery, and is prepared by the following steps, namely the first step is used for synthesizing the power battery flame-retardant adhesive.
Mixing 40 parts of 2-ethylhexyl acrylate (2-EHA), 10 parts of Methyl Acrylate (MA), 4 parts of 4-methacryloyloxyethyl trimellitic anhydride (4-META), 15 parts of Butyl Acrylate (BA), 10 parts of diethyl vinylphosphate, 0.25 part of tert-butyl peroxymaleate (TBMA) as a radical initiator, 0.1 part of ferric trichloride, 0.2 part of triphenylphosphine and 70 parts of butyl acetate, conducting nitrogen deoxygenation for 60 minutes, controlling the temperature to 85 ℃, conducting reverse atom transfer radical polymerization (R-ARTP) polymerization for 5 hours under the protection of nitrogen, controlling the number average molecular weight (Mn) to 134800, controlling the molecular weight polydispersity to be 1.1, reducing the reaction temperature to 20 ℃, then adding 0.5 part of trimethylolpropane triglycidyl ether, 0.2 part of a curing accelerator 2, 4, 6-tris (dimethylaminomethyl) phenol and 20 parts of indigo blue, obtaining a power battery flame-retardant adhesive; the above are all parts by mass.
And (3) combining the figure 1, and preparing the composite layer flame-retardant insulating protective blue film for the power battery in the second step.
Uniformly coating a non-silicon release agent RL-600 on the front surface of a 40-micron first layer of halogen-free flame-retardant polyethylene glycol terephthalate film layer 1 with the fire-retardant rating of VTM-0, and then placing at 100 ℃ for heat preservation and curing for 3min to obtain a 0.2-micron release layer 2.
And (3) uniformly coating the power battery flame-retardant adhesive prepared in the step one on the reverse side of the first layer of the halogen-free flame-retardant polyethylene terephthalate film layer 1 with the fire-retardant rating of VTM-0, then placing at 130 ℃, preserving heat, drying and curing for 2min to obtain a first layer of the adhesive layer 3 of the power battery flame-retardant adhesive with the thickness of 20 microns, and further compounding a second layer of the halogen-free flame-retardant polyethylene terephthalate film layer 4 with the fire-retardant rating of VTM-0 with the thickness of 40 microns.
And uniformly coating the power battery flame-retardant adhesive prepared in the first step on the reverse side of the second-layer halogen-free flame-retardant polyethylene terephthalate film layer 4 with the fire-retardant rating of VTM-0 compounded in the second step, then placing at 130 ℃, preserving heat, drying and curing for 2min to obtain an adhesive layer 5 of the second-layer power battery flame-retardant adhesive with the thickness of 20 microns, and finally rolling and slitting to obtain the composite-layer flame-retardant insulating protective blue film for the power battery.
According to the invention, the adhesion, 180-degree stripping force, creep resistance test and flame retardant grade are performed on the composite layer flame-retardant insulating protective blue film for the power battery obtained in the four embodiments by referring to the current general method for testing the protective film. The initial tack was tested against the GB/T4852-2002 standard. The 180 DEG peel force is tested with reference to the GB/T2792-2014 standard. The breakdown voltage was tested with reference to the GB/T14517-93 standard. The flame retardant rating is tested according to the UL94 standard. Creep resistance the composite layer flame retardant insulating protective blue film for a power battery was placed under 3000N pressure for 24 hours and the appearance change was observed. All test data are compared in table 1 below.
As can be seen from the data in Table 1, the composite layer flame-retardant insulating protective blue film for the power battery, which is prepared by the invention, has excellent creep resistance and flame retardance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
TABLE 1 comparison of specific Performance tests for each example
Claims (5)
1. The flame-retardant adhesive for the battery is characterized in that: the curing agent comprises 20-60 parts of 2-ethylhexyl acrylate, 1-10 parts of methyl acrylate, 1-5 parts of 4-methacryloyloxyethyl trimellitic anhydride, 1-15 parts of butyl acrylate, 1-10 parts of diethyl vinylphosphate, 0.001-0.5 part of tert-butyl peroxymaleate serving as a free radical initiator, 0.001-1 part of ferric trichloride, 0.01-2 parts of triphenyl phosphorus, 50-250 parts of an organic solvent, 0.1-2 parts of trimethylolpropane triglycidyl ether, 0.01-0.5 part of a curing accelerator and 1-30 parts of a dye; the above are all parts by mass.
2. The battery flame-retardant adhesive according to claim 1, characterized in that:
the organic solvent is one or a mixture of two or a mixture of three of ethyl acetate, toluene and butyl acetate;
the curing accelerator is one or a mixture of two or a mixture of three of triethanolamine, dimethylaniline and 2, 4, 6-tris (dimethylaminomethyl) phenol;
the dye is one or two of indigo blue and phthalocyanine blue.
3. A preparation method of a battery flame-retardant adhesive is characterized by comprising the following steps: mixing 20-60 parts of 2-ethylhexyl acrylate, 1-10 parts of methyl acrylate, 1-5 parts of 4-methacryloyloxyethyl trimellitic anhydride, 1-15 parts of butyl acrylate, 1-10 parts of diethyl vinylphosphate, 0.001-0.5 part of tert-butyl peroxymaleate serving as a free radical initiator, 0.001-1 part of ferric trichloride, 0.01-2 parts of triphenylphosphine and 50-250 parts of an organic solvent, carrying out nitrogen deoxidization for 30-120 minutes, controlling the temperature to be 60-120 ℃, carrying out reverse atom transfer radical polymerization under the protection of nitrogen, carrying out polymerization for 1-20 hours, controlling the number average molecular weight to be 10000-400000, controlling the molecular weight polydispersity to be 1.1-1.5, controlling the glass transition temperature to be-45-20 ℃, reducing the reaction temperature to be 10-30 ℃, and then adding 0.1-2 parts of trimethylolpropane triglycidyl ether, 1-2 parts of triglycidyl ether, Mixing 0.01-0.5 part of curing accelerator and 1-30 parts of dye to obtain the flame-retardant adhesive for the power battery; the above are all parts by mass.
4. The composite flame-retardant insulating blue film for the battery is characterized in that: the battery flame-retardant composite layer insulation blue film comprises two layers of a VTM-0 level halogen-free flame-retardant polyethylene terephthalate film layer, two layers of an adhesive layer containing the battery flame-retardant adhesive in claim 1 and an isolation layer, wherein an adhesive layer containing the battery flame-retardant adhesive in claim 1 is clamped between the two layers of the VTM-0 level halogen-free flame-retardant polyethylene terephthalate film layer, the isolation layer is arranged on the front surface of the first layer of the VTM-0 level halogen-free flame-retardant polyethylene terephthalate (PET) film layer, the other layer of the battery flame-retardant adhesive in claim 1 is compounded on the back surface of the second layer of the VTM-0 level halogen-free flame-retardant polyethylene terephthalate (PET) film layer, and finally the battery flame-retardant composite layer insulation blue film is obtained through rolling and slitting.
5. The composite flame-retardant insulating blue film for a battery according to claim 4, wherein: uniformly coating a non-silicon release agent on the front surface of a first layer of halogen-free flame-retardant polyethylene terephthalate film layer with the fire-retardant rating of VTM-0 and the thickness of 10-50 microns, and then, placing the film layer at 80-120 ℃ for heat preservation and solidification for 1-10 min to obtain an isolation layer with the thickness of 0.1-1 micron;
then uniformly coating the battery flame-retardant adhesive of claim 1 on the reverse side of a first layer of halogen-free flame-retardant polyethylene terephthalate film layer with the fire-retardant rating of VTM-0, then placing the mixture at 80-130 ℃, preserving heat, drying and curing for 1-20 min to obtain a first adhesive layer with 20-40 μm and containing the battery flame-retardant adhesive in claim 1, sticking a second halogen-free flame-retardant polyethylene terephthalate film layer with the fire-retardant rating of VTM-0 on the outer side of the first adhesive layer containing the battery flame-retardant adhesive in claim 1, coating the back surface of the second halogen-free flame-retardant polyethylene terephthalate film layer with the fire-retardant rating of VTM-0 with 20-40 μm and containing the battery flame-retardant adhesive in claim 1, and then placing at 80-130 ℃, and preserving heat, drying and curing for 1-20 min to obtain a 20-40 mu m second adhesive layer containing the battery flame-retardant adhesive in claim 1.
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| CN102260477B (en) * | 2010-12-14 | 2012-08-08 | 上海凯鑫森产业投资控股有限公司 | Pressure-sensitive adhesive for biaxially-oriented polypropylene (BOPP) protective film and preparation method thereof |
| CN103254336A (en) * | 2012-08-01 | 2013-08-21 | 苏州大学 | Novel reverse direction ATRP polymerization method of MMA triggered by phosphine ligand |
| US11485112B2 (en) * | 2013-07-22 | 2022-11-01 | VaproShield, LLC | Building membrane with porous pressure sensitive adhesive |
| CN103665248B (en) * | 2013-12-26 | 2016-06-15 | 深圳市嘉达高科产业发展有限公司 | A kind of phosphorus-silicon type flame-retarded resin and preparation method thereof |
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Denomination of invention: Battery flame retardant adhesive and its preparation method and composite flame retardant insulating blue film for battery Effective date of registration: 20210803 Granted publication date: 20201013 Pledgee: Guangdong Shunde Rural Commercial Bank Co.,Ltd. science and technology innovation sub branch Pledgor: INNOVA ELECTRONIC MATERIALS Co.,Ltd. Registration number: Y2021980007249 |
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