CN108822769B - Insulating flame-retardant acrylic acid adhesive, preparation method thereof and termination adhesive tape - Google Patents
Insulating flame-retardant acrylic acid adhesive, preparation method thereof and termination adhesive tape Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
Abstract
The invention relates to the technical field of acrylic acid viscose, in particular to an insulating flame-retardant acrylic acid viscose, a preparation method thereof and a termination adhesive tape. The acrylic adhesive is added with the intumescent flame retardant and the synergistic flame-retardant magnesium hydroxide, and the incombustible porous silica microspheres, so that the acrylic adhesive has the functions of stabilizing a carbon layer and insulating heat, has good insulativity, flame retardance and corrosion resistance, and has good cohesiveness by adjusting the viscosity of the acrylic adhesive through the rosin resin and the terpene resin.
Description
Technical Field
The invention relates to the technical field of acrylic acid viscose, in particular to an insulating flame-retardant acrylic acid viscose, a preparation method thereof and a termination adhesive tape.
Background
The lithium battery termination adhesive tape is characterized in that a polypropylene insulating material (PP, PET and PI films) is used as a base material, and is coated with special acrylic glue for lithium battery electrolyte, wherein the thickness of the special acrylic glue is 0.016mm, 0.020mm, 0.03mm, 0.035mm, 0.04mm and 0.05mm, and the special acrylic glue is specially used for insulating, fixing and protecting lithium ion battery cores and other parts.
The termination tape requires the addition of various flame retardants, commonly used flame retardants consisting of halogen flame retardants and halogen-free flame retardants, to acrylic adhesives due to the flame retardant rating of UV-94 standard V0-2. The halogen flame retardant is easy to generate halogen gas harmful to human body during combustion and is gradually eliminated; the halogen-free flame retardant mainly comprises a phosphorus compound and a metal hydroxide. These two types of compounds are called non-pollution flame retardants, which do not volatilize and generate corrosive gases during combustion. However, the addition of the halogen-free flame retardant can cause the adhesive property of the acrylic adhesive to be remarkably reduced, while the metal hydroxide can cause the conductive property of the acrylic adhesive to be improved and the corrosion resistance to be reduced, so that the flame retardance, the adhesive property, the insulating property and the corrosion resistance cannot be comprehensively balanced easily.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the acrylic acid viscose glue with excellent flame retardance, insulating property, adhesive property and corrosion resistance, and the invention also aims to provide the preparation method of the acrylic acid viscose glue, which is simple and efficient and is beneficial to industrial production; another object of the present invention is to provide a termination tape having the acrylic adhesive of the present invention with excellent flame retardancy, insulation and adhesion, and thus suitable for insulation fixing protection of lithium ion battery cells and other parts.
The purpose of the invention is realized by the following technical scheme:
an insulating flame-retardant acrylic acid viscose comprises the following raw materials in parts by weight:
the synergistic flame-retardant microsphere is prepared by the following method:
A. adding 4-8 parts by weight of nano-cellulose into 30-40 parts by weight of ethanol water solution with volume concentration of 92% -98% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 38-48 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9-10 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano cellulose/silicon dioxide microspheres;
C. calcining the nano-cellulose/silicon dioxide microspheres, and removing the nano-cellulose to obtain porous silicon dioxide microspheres;
D. and stirring and dispersing the porous silica microspheres and the nano magnesium hydroxide in water according to the weight ratio of 2-5:1, and filtering to obtain the synergistic flame-retardant microspheres.
Wherein the diameter of the nano-cellulose is 40-80nm, the length is 1-2 μm, the long diameter of the nano-cellulose and the corresponding dosage ratio are controlled, the particle size of the porous silicon dioxide microsphere can reach 100-130nm, and the pore volume channel is 127.6-154.4cm3Has nanometer size effect and additional enhanced thermal insulation and insulation due to the porous nature.
Wherein the particle size of the nano magnesium hydroxide is 30-60 nm. By controlling the particle size of the nano magnesium hydroxide, the nano magnesium hydroxide has good embedding property on the porous silicon dioxide microspheres, and meanwhile, the nano magnesium hydroxide has a size effect and can also have a certain improvement effect on the mechanical property of the acrylic acid viscose.
Wherein, the calcining temperature in the step C is 700-900 ℃, and the calcining time is 1-3 h. Decomposing the nanocellulose into water and carbon oxides by calcination, so that the silica forms a channel of nanocellulose residues, thereby forming porous silica microspheres; by controlling the calcining temperature and time, the nanocellulose can be fully reacted, and the weight loss ratio of the calcined silica microspheres is 7.3 wt% -11.2 wt%.
Wherein the acrylic monomer consists of 20 to 50 weight percent of methyl acrylate, 10 to 20 weight percent of ethyl acrylate, 10 to 20 weight percent of 2-ethylhexyl acrylate and 30 to 40 weight percent of isooctyl acrylate. By controlling the composition of acrylic monomers, free radical polymerization is carried out under the action of an initiator to form an acrylic polymer with a stable network structure, and the acrylic polymer has good cohesiveness and electrolyte corrosion resistance.
The acid source is ammonium polyphosphate, the gas source is melamine, the carbon source is pentaerythritol, the flame retardant property of the acrylic acid viscose is obviously improved, and the influence on the mechanical property is very little.
Wherein, the initiator can directly influence whether the polymerization process of the acrylic monomer can be smoothly carried out and can also influence the polymerization reaction rate, and preferably, the initiator is prepared by mixing dimethyl azodiisobutyrate and azodiisobutyronitrile in a weight ratio of 1-3: 1-3.
Wherein the selection of the kind of the organic solvent has a great influence on the progress of the polymerization reaction and the degree of polymerization, and preferably, the organic solvent consists of toluene and ethyl acetate in a weight ratio of 1-2: 1-3.
The invention also provides a preparation method of the insulating flame-retardant acrylic acid viscose, which comprises the following steps: mixing and heating acrylic monomers, an acid source, a gas source, a carbon source, synergistic flame-retardant microspheres, an initiator and 60-80 wt% of an organic solvent to 70-90 ℃, fully reacting, cooling to 35-45 ℃, adding rosin resin, terpene resin and the rest organic solvent, and uniformly stirring to obtain the flame-retardant acrylic adhesive.
The invention also provides an insulating flame-retardant termination adhesive tape which comprises a film base material and the insulating flame-retardant acrylic adhesive coated on the film base material.
The invention has the beneficial effects that: 1. the acrylic acid viscose glue is added with the intumescent flame retardant and the synergistic flame-retardant magnesium hydroxide, and is added with the non-combustible porous silicon dioxide microspheres, so that the acrylic acid viscose glue has the functions of stabilizing a carbon layer and insulating heat, the flame retardance of the acrylic acid viscose glue reaches the V0 level of UL-94, and the limit of oxygen index is more than 30; 2. the silicon dioxide prepared by the invention has porous property, can be used as a carrier of nano magnesium hydroxide, can prevent the nano magnesium hydroxide from agglomerating, can also be used as an insulating material to block the magnesium hydroxide and prevent the magnesium hydroxide from forming a conductive path, improves the insulating property of the acrylic acid adhesive, and simultaneously can improve the corrosion resistance of the acrylic acid adhesive; 3. the viscosity of the acrylic acid viscose is adjusted by the rosin resin and the terpene resin, so that the acrylic acid viscose has good cohesiveness; 4. the preparation method of the acrylic acid viscose is simple and efficient, and is beneficial to industrial production; 5. the termination tape of the present invention has great advantages in lithium battery applications.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
An insulating flame-retardant acrylic acid viscose comprises the following raw materials in parts by weight:
the synergistic flame-retardant microsphere is prepared by the following method:
A. adding 6 parts by weight of nano-cellulose into 35 parts by weight of ethanol water solution with volume concentration of 95% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 43 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9.5 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano cellulose/silicon dioxide microspheres;
C. calcining the nano-cellulose/silicon dioxide microspheres, and removing the nano-cellulose to obtain porous silicon dioxide microspheres;
D. and stirring and dispersing the porous silica microspheres and the nano magnesium hydroxide in water according to the weight ratio of 3.5:1, and filtering to obtain the synergistic flame-retardant microspheres.
Wherein the diameter of the nano-cellulose is 60nm, the length of the nano-cellulose is 1.5 mu m, the particle size of the porous silicon dioxide microspheres is 120nm, and the pore volume of the porous silicon dioxide microspheres is 154.4cm3/g。
Wherein the particle size of the nano magnesium hydroxide is 45 nm.
Wherein the calcining temperature in the step C is 800 ℃, and the calcining time is 2 h.
Wherein the acrylic monomer consists of 35 wt% of methyl acrylate, 15 wt% of ethyl acrylate, 15 wt% of 2-ethylhexyl acrylate and 35 wt% of isooctyl acrylate.
Wherein the acid source is ammonium polyphosphate, the gas source is melamine, and the carbon source is pentaerythritol.
Wherein the initiator is prepared from dimethyl azobisisobutyrate and azobisisobutyronitrile according to a weight ratio of 1:1 in a certain proportion.
Wherein the organic solvent consists of toluene and ethyl acetate in a weight ratio of 1.5: 2.
The invention also provides a preparation method of the insulating flame-retardant acrylic acid viscose, which comprises the following steps: mixing and heating an acrylic monomer, an acid source, a gas source, a carbon source, a synergistic flame-retardant microsphere, an initiator and 70 wt% of an organic solvent to 80 ℃, fully reacting, cooling to 40 ℃, adding rosin resin, terpene resin and the rest of the organic solvent, and uniformly stirring to obtain the flame-retardant acrylic adhesive.
The invention also provides an insulating flame-retardant termination adhesive tape which comprises a film base material and the insulating flame-retardant acrylic adhesive coated on the film base material.
Example 2
An insulating flame-retardant acrylic acid viscose comprises the following raw materials in parts by weight:
the synergistic flame-retardant microsphere is prepared by the following method:
A. adding 4 parts by weight of nano-cellulose into 30 parts by weight of 92% ethanol aqueous solution by volume concentration for ultrasonic dispersion to obtain dispersion liquid;
B. adding 38 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano cellulose/silicon dioxide microspheres;
C. calcining the nano-cellulose/silicon dioxide microspheres, and removing the nano-cellulose to obtain porous silicon dioxide microspheres;
D. and stirring and dispersing the porous silica microspheres and the nano magnesium hydroxide in water according to the weight ratio of 2:1, and filtering to obtain the synergistic flame-retardant microspheres.
Wherein the diameter of the nano-cellulose is 40nm, the length of the nano-cellulose is 1 mu m, the particle size of the porous silicon dioxide microspheres is 100nm, and the pore volume of the porous silicon dioxide microspheres is 136.4cm3/g。
Wherein the particle size of the nano magnesium hydroxide is 30 nm.
Wherein the calcining temperature in the step C is 700 ℃, and the calcining time is 3 h.
Wherein the acrylic monomer consists of 20 wt% of methyl acrylate, 20 wt% of ethyl acrylate, 20 wt% of 2-ethylhexyl acrylate and 40 wt% of isooctyl acrylate.
Wherein the acid source is ammonium polyphosphate, the gas source is melamine, and the carbon source is pentaerythritol.
Wherein the initiator is prepared from dimethyl azobisisobutyrate and azobisisobutyronitrile according to a weight ratio of 1: 3 in proportion.
Wherein the organic solvent consists of toluene and ethyl acetate according to the weight ratio of 1: 1.
The invention also provides a preparation method of the insulating flame-retardant acrylic acid viscose, which comprises the following steps: mixing and heating an acrylic monomer, an acid source, a gas source, a carbon source, synergistic flame-retardant microspheres, an initiator and 60 wt% of an organic solvent to 70 ℃, fully reacting, cooling to 35 ℃, adding rosin resin, terpene resin and the rest of the organic solvent, and uniformly stirring to obtain the flame-retardant acrylic adhesive.
The invention also provides an insulating flame-retardant termination adhesive tape which comprises a film base material and the insulating flame-retardant acrylic adhesive coated on the film base material.
Example 3
An insulating flame-retardant acrylic acid viscose comprises the following raw materials in parts by weight:
the synergistic flame-retardant microsphere is prepared by the following method:
A. adding 8 parts by weight of nano-cellulose into 40 parts by weight of ethanol water solution with the volume concentration of 98% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 48 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 10 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano cellulose/silicon dioxide microspheres;
C. calcining the nano-cellulose/silicon dioxide microspheres, and removing the nano-cellulose to obtain porous silicon dioxide microspheres;
D. and stirring and dispersing the porous silica microspheres and the nano magnesium hydroxide in water according to the weight ratio of 5:1, and filtering to obtain the synergistic flame-retardant microspheres.
Wherein the diameter of the nano-cellulose is 80nm, the length of the nano-cellulose is 2 mu m, the particle size of the porous silicon dioxide microspheres is 130nm, and the pore volume of the porous silicon dioxide microspheres is 127.6cm3/g。
Wherein the particle size of the nano magnesium hydroxide is 60 nm.
Wherein the calcining temperature in the step C is 900 ℃, and the calcining time is 1 h.
Wherein the acrylic monomer consists of 50 wt% of methyl acrylate, 10 wt% of ethyl acrylate, 10 wt% of 2-ethylhexyl acrylate and 30 wt% of isooctyl acrylate.
Wherein the acid source is ammonium polyphosphate, the gas source is melamine, and the carbon source is pentaerythritol.
Wherein the initiator is prepared from dimethyl azodiisobutyrate and azodiisobutyronitrile in a weight ratio of 3:1 in a certain proportion.
Wherein the organic solvent consists of toluene and ethyl acetate according to the weight ratio of 2: 3.
The invention also provides a preparation method of the insulating flame-retardant acrylic acid viscose, which comprises the following steps: mixing and heating an acrylic monomer, an acid source, a gas source, a carbon source, synergistic flame-retardant microspheres, an initiator and 80 wt% of an organic solvent to 90 ℃, fully reacting, cooling to 45 ℃, adding rosin resin, terpene resin and the rest of the organic solvent, and uniformly stirring to obtain the flame-retardant acrylic adhesive.
The invention also provides an insulating flame-retardant termination adhesive tape which comprises a film base material and the insulating flame-retardant acrylic adhesive coated on the film base material.
Example 4
An insulating flame-retardant acrylic acid viscose comprises the following raw materials in parts by weight:
the synergistic flame-retardant microsphere is prepared by the following method:
A. adding 5 parts by weight of nano-cellulose into 32 parts by weight of ethanol water solution with volume concentration of 94% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 40 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9.3 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano cellulose/silicon dioxide microspheres;
C. calcining the nano-cellulose/silicon dioxide microspheres, and removing the nano-cellulose to obtain porous silicon dioxide microspheres;
D. and stirring and dispersing the porous silica microspheres and the nano magnesium hydroxide in water according to the weight ratio of 3:1, and filtering to obtain the synergistic flame-retardant microspheres.
Wherein the diameter of the nano-cellulose is 50nm, the length of the nano-cellulose is 1.2 mu m, the particle size of the porous silicon dioxide microspheres is 110nm, and the pore volume of the porous silicon dioxide microspheres is 143.6cm3/g。
Wherein the particle size of the nano magnesium hydroxide is 40 nm.
Wherein the calcining temperature in the step C is 750 ℃, and the calcining time is 2.5 h.
Wherein the acrylic monomer consists of 30 wt% of methyl acrylate, 18 wt% of ethyl acrylate, 18 wt% of 2-ethylhexyl acrylate and 34 wt% of isooctyl acrylate.
Wherein the acid source is ammonium polyphosphate, the gas source is melamine, and the carbon source is pentaerythritol.
Wherein the initiator is prepared from dimethyl azobisisobutyrate and azobisisobutyronitrile according to a weight ratio of 1:2 in proportion.
Wherein the organic solvent consists of toluene and ethyl acetate according to the weight ratio of 1: 2.
The invention also provides a preparation method of the insulating flame-retardant acrylic acid viscose, which comprises the following steps: mixing and heating acrylic acid monomer, acid source, gas source, carbon source, synergistic flame-retardant microsphere, initiator and 65 wt% of organic solvent to 75 ℃, fully reacting, cooling to 38 ℃, adding rosin resin, terpene resin and residual organic solvent, and uniformly stirring to obtain the flame-retardant acrylic acid adhesive.
The invention also provides an insulating flame-retardant termination adhesive tape which comprises a film base material and the insulating flame-retardant acrylic adhesive coated on the film base material.
Example 5
An insulating flame-retardant acrylic acid viscose comprises the following raw materials in parts by weight:
the synergistic flame-retardant microsphere is prepared by the following method:
A. adding 7 parts by weight of nano-cellulose into 38 parts by weight of ethanol water solution with volume concentration of 97% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 45 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9.8 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano cellulose/silicon dioxide microspheres;
C. calcining the nano-cellulose/silicon dioxide microspheres, and removing the nano-cellulose to obtain porous silicon dioxide microspheres;
D. and stirring and dispersing the porous silica microspheres and the nano magnesium hydroxide in water according to the weight ratio of 4:1, and filtering to obtain the synergistic flame-retardant microspheres.
Wherein the diameter of the nano-cellulose is 70nm, the length of the nano-cellulose is 1.7 mu m, the particle size of the porous silicon dioxide microspheres is 120nm, and the pore volume of the porous silicon dioxide microspheres is 138.4cm3/g。
Wherein the particle size of the nano magnesium hydroxide is 50 nm.
Wherein the calcining temperature in the step C is 850 ℃, and the calcining time is 1.5 h.
Wherein the acrylic monomer consists of 40 wt% of methyl acrylate, 12 wt% of ethyl acrylate, 12 wt% of 2-ethylhexyl acrylate and 36 wt% of isooctyl acrylate.
Wherein the acid source is ammonium polyphosphate, the gas source is melamine, and the carbon source is pentaerythritol.
Wherein the initiator is prepared from dimethyl azodiisobutyrate and azodiisobutyronitrile in a weight ratio of 3: 2 in proportion.
Wherein the organic solvent consists of toluene and ethyl acetate according to the weight ratio of 1: 2.
The invention also provides a preparation method of the insulating flame-retardant acrylic acid viscose, which comprises the following steps: mixing and heating acrylic acid monomer, acid source, gas source, carbon source, synergistic flame-retardant microsphere, initiator and 75 wt% of organic solvent to 85 ℃, fully reacting, cooling to 42 ℃, adding rosin resin, terpene resin and residual organic solvent, and uniformly stirring to obtain the flame-retardant acrylic acid adhesive.
The invention also provides an insulating flame-retardant termination adhesive tape which comprises a film base material and the insulating flame-retardant acrylic adhesive coated on the film base material.
Comparative example 1
This comparative example differs from example 1 in that: the insulating flame-retardant acrylic viscose glue is not added with the synergistic flame-retardant microspheres.
Example 6
The insulating flame retardant termination tapes of examples 1-5 were tested for performance. The test indexes and corresponding test conditions are as follows:
and (1) conventional adhesive force. The test method is as follows: the testing temperature is 23 +/-2 ℃, the relative humidity is 60-70%, the insulating flame-retardant termination adhesive tape with the width of 20mm is attached to a clean aluminum plate by slight finger pressure, the adhesive tape is pressed back for 3 times at the speed of 10m/min by a 2kg compression roller, the insulating flame-retardant termination adhesive tape is placed for 20min or 24h, then the insulating flame-retardant termination adhesive tape is stripped at the stripping speed of 300m/min and the stripping angle of 180 degrees, the stripping force is recorded, and the average value is calculated.
Adhesion of electrolyte. The test method is as follows: the testing temperature is 23 +/-2 ℃, the relative humidity is 60-70%, the insulating flame-retardant termination adhesive tape with the width of 20mm is slightly pressed by fingers to be attached to a clean aluminum plate, the adhesive tape is pressed back for 3 times at the speed of 10m/min by a 2kg pressing roller, the aluminum plate is placed for 24h, the aluminum plate is soaked in the electrolyte for 10min, then the insulating flame-retardant termination adhesive tape is stripped at the stripping speed of 300m/min and at the stripping angle of 180 degrees, the stripping force is recorded, and the average value is calculated.
Conventional retention. The test method is as follows: the testing temperature is 23 +/-2 ℃, the relative humidity is 60-70%, the insulating flame-retardant termination adhesive tape is slightly pressed by fingers to be attached to a clean aluminum plate, the attaching area is 20mmX20mm, the adhesive tape is pressed back for 3 times at the speed of 10m/min by a 2kg pressing roller, the aluminum plate is placed for 20min, the aluminum plate is vertical, a 1kg weight is hung at the lowest end of the insulating flame-retardant termination adhesive tape, the load is 1h, and the falling distance of the weight is recorded.
And fourthly, electrolyte retention. The test method is as follows: the testing temperature is 23 +/-2 ℃, the relative humidity is 60-70%, the insulating flame-retardant termination adhesive tape is slightly pressed by fingers to be attached to a clean aluminum plate, the attaching area is 20mmX20mm, the adhesive tape is pressed back for 3 times at the speed of 10m/min by a 2kg pressing roller, the aluminum plate is placed for 20min, the aluminum plate is soaked in the electrolyte for 10min, the aluminum plate is vertical, a 1kg weight is hung at the lowest end of the insulating flame-retardant termination adhesive tape, the weight is loaded for 1h, and the falling distance of the weight is recorded.
And fifthly, flame retardance. UL-94 flame retardant rating test and oxygen index limit test.
From the above table, the insulating flame-retardant termination adhesive tape of the invention has good adhesive force and durable adhesive force, and the flame retardant grade reaches V-0 grade due to the addition of the intumescent flame retardant, and the comparison between the example 1 and the comparative example 1 shows that the addition of the synergistic flame-retardant microspheres reduces the conventional adhesive force, but greatly improves the electrolyte corrosion resistance and the oxygen index limit of the termination adhesive tape, and the insulating flame-retardant termination adhesive tape of the invention is suitable for the packaging field of lithium batteries and has extremely high industrial value.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (2)
1. An insulating flame-retardant acrylic acid viscose glue is characterized in that: the feed comprises the following raw materials in parts by weight:
the synergistic flame-retardant microsphere is prepared by the following method:
A. adding 4-8 parts by weight of nano-cellulose into 30-40 parts by weight of ethanol water solution with volume concentration of 92% -98% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 38-48 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9-10 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano cellulose/silicon dioxide microspheres;
C. calcining the nano-cellulose/silicon dioxide microspheres, and removing the nano-cellulose to obtain porous silicon dioxide microspheres;
D. stirring and dispersing the porous silica microspheres and the nano magnesium hydroxide in water according to the weight ratio of 2-5:1, and filtering to obtain the synergistic flame-retardant microspheres;
the diameter of the nano-cellulose is 40-80nm, the length is 1-2 μm, the particle size of the porous silicon dioxide microsphere is 100-130nm, and the pore volume is 127.6-154.4cm3/g；
The particle size of the nano magnesium hydroxide is 30-60 nm;
the calcination temperature in the step C is 700-900 ℃, and the calcination time is 1-3 h;
the acrylic monomer consists of 20 to 50 weight percent of methyl acrylate, 10 to 20 weight percent of ethyl acrylate, 10 to 20 weight percent of 2-ethylhexyl acrylate and 30 to 40 weight percent of isooctyl acrylate;
the acid source is ammonium polyphosphate, the gas source is melamine, and the carbon source is pentaerythritol;
the initiator is prepared from dimethyl azodiisobutyrate and azodiisobutyronitrile in a weight ratio of 1-3: 1-3;
the organic solvent consists of toluene and ethyl acetate according to the weight ratio of 1-2: 1-3;
the preparation method of the insulating flame-retardant acrylic viscose comprises the following steps: mixing and heating acrylic monomers, an acid source, a gas source, a carbon source, synergistic flame-retardant microspheres, an initiator and 60-80 wt% of an organic solvent to 70-90 ℃, fully reacting, cooling to 35-45 ℃, adding rosin resin, terpene resin and the rest organic solvent, and uniformly stirring to obtain the flame-retardant acrylic adhesive.
2. An insulating flame retardant termination tape characterized by: comprising a film substrate and the insulating flame-retardant acrylic adhesive of claim 1 coated on the film substrate.
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| CN110128967B (en) * | 2019-06-19 | 2021-10-19 | 浙江海泰新材料有限公司 | Flame-retardant adhesive, flame-retardant adhesive tape prepared from flame-retardant adhesive and preparation method of flame-retardant adhesive tape |
| CN112048256B (en) * | 2020-08-24 | 2022-06-07 | 苏州萍升源电子科技有限公司 | Production process of flame-retardant adhesive tape |
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