CN111016335A - PBT aluminum-plastic composite film and production process thereof - Google Patents
PBT aluminum-plastic composite film and production process thereof Download PDFInfo
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- CN111016335A CN111016335A CN201911110151.1A CN201911110151A CN111016335A CN 111016335 A CN111016335 A CN 111016335A CN 201911110151 A CN201911110151 A CN 201911110151A CN 111016335 A CN111016335 A CN 111016335A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
Abstract
The invention discloses a PBT aluminum-plastic composite film which is characterized by comprising a middle layer, an inner layer arranged on the inner side of the middle layer and an outer layer arranged on the outer side of the middle layer, wherein the middle layer is bonded with the inner layer through a first adhesive layer, and the middle layer is bonded with the outer layer through a second adhesive layer; the middle layer is an aluminum foil layer, the inner layer is a polyolefin layer, and the outer layer is formed by a blend formed by blending poly (1, 4-naphthalene dicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to the weight ratio of 1 (5-8); the first adhesive layer and the second adhesive layer are each independently formed from an aluminum-doped hyperbranched polyurethane acrylate adhesive. The invention also discloses a production process of the PBT aluminum-plastic composite film. The PBT aluminum-plastic composite membrane disclosed by the invention has the advantages of high temperature resistance, corrosion resistance, scratch resistance, good performance stability, excellent comprehensive performance, good mechanical property and water vapor barrier property, and can obviously improve the heat resistance and safety performance of a lithium ion battery.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to a PBT aluminum-plastic composite film and a production process thereof.
Background
In recent years, with the rapid development of the fields of portable electronic products, electric automobiles, energy storage power stations and the like, lithium ion batteries become the preferred chemical power source due to the advantages of high energy density, high working voltage, small self-discharge, long cycle life and the like. With the further widening of the application range, people pay more and more attention to the normal working stability and safety of the lithium ion battery, and put forward higher requirements on the performance of an aluminum-plastic film for packaging the lithium ion battery.
The aluminum-plastic film is a core material of a lithium ion battery, belongs to the field of precision manufacturing, has higher stability to corrosive acid, alkali, salt or organic solvent and other liquid chemical substances, has the advantages of light weight, thin thickness, flexible appearance design and the like, is widely applied to the fields of 3C consumer electronics, power batteries, energy storage and the like, and needs to be in direct contact with electrolyte in the using process, so the corrosion resistance becomes one of indexes for measuring the quality of the aluminum-plastic film, the high corrosion resistance can prolong the service life of the lithium battery, and the use safety is ensured.
In the prior art, the aluminum plastic film for the lithium battery is easy to have defects such as wrinkles, pinholes and the like, which can increase the probability of aluminum foil breakage during the punching of the aluminum plastic film, and once the aluminum foil layer is damaged, the failure of the lithium battery is meant, besides, the aluminum plastic film on the market is easy to be corroded and swelled by the electrolyte of the lithium battery, so that the damage of the lithium battery product is caused; the lithium ion battery is easy to burn, and once the lithium ion battery generates heat in a short circuit, the battery wrapped by the aluminum plastic film is very likely to burn or even explode, so that great potential safety hazards exist.
The aluminum plastic film widely used at present is divided into three layers: the inner layer is a bonding layer, and is made of polyethylene or polypropylene materials mostly to play a role in sealing and bonding; the middle layer is made of aluminum foil, so that the permeation of water vapor outside the battery can be prevented, and the permeation of electrolyte inside the battery can be prevented; the outer layer is a protective layer, so that the battery has strong mechanical performance, prevents the battery from being damaged by external force, and plays a role in protecting the battery; the outer layer is generally selected from a PA (polyamide) film or a PET (polyethylene terephthalate) film. The PA film is not resistant to electrolyte used by the lithium battery, and the electrolyte easily pollutes the surface to cause the battery to be scrapped in the process of producing the lithium battery. The PET film has low strength and poor flexibility, and the produced aluminum plastic film has poor punching depth performance.
The Chinese patent with application number 201710813207.4 discloses an electrolyte-resistant aluminum-plastic film with a surface and a manufacturing method thereof, wherein a PBT material is used as an outer layer, and the obtained aluminum-plastic film has high strength, good electrolyte resistance and good punching depth performance, however, the PBT film has the defects of low notch impact strength and large molding shrinkage, the electrolyte resistance of a used binder layer needs to be further improved, and the quality problems of aluminum-plastic film delamination and the like exist.
Therefore, the aluminum-plastic composite film for the lithium battery, which has better comprehensive performance, higher corrosion resistance, excellent performance stability, high temperature resistance and scratch resistance, can obviously improve the heat resistance and safety performance of the lithium ion battery, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of packaging materials, is developed.
Disclosure of Invention
The invention mainly aims to provide the PBT aluminum-plastic composite film and the production process thereof, the production process is simple and easy to implement, low in energy consumption, high in production efficiency and finished product qualification rate, and suitable for continuous industrial production; the PBT aluminum-plastic composite membrane prepared by production has the advantages of high temperature resistance, corrosion resistance, scratch resistance, good performance stability, excellent comprehensive performance, good mechanical property and water vapor barrier property, and can obviously improve the heat resistance and safety performance of the lithium ion battery.
In order to achieve the aim, the invention provides a PBT aluminum-plastic composite film which is characterized by comprising an intermediate layer, an inner layer arranged on the inner side of the intermediate layer and an outer layer arranged on the outer side of the intermediate layer, wherein the intermediate layer is bonded with the inner layer through a first adhesive layer, and the intermediate layer is bonded with the outer layer through a second adhesive layer; the middle layer is an aluminum foil layer, the inner layer is a polyolefin layer, and the outer layer is formed by a blend formed by blending poly (1, 4-naphthalene dicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to the weight ratio of 1 (5-8).
Preferably, the thickness of the outer layer is 15-30 μm, the thickness of the middle layer is 30-50 μm, and the thickness of the inner layer is 30-50 μm.
Further, the polyolefin layer is a polyethylene layer or a polypropylene layer.
Further, the first adhesive layer and the second adhesive layer are each independently formed from an aluminum-doped hyperbranched urethane acrylate adhesive.
Further, the aluminum-doped hyperbranched polyurethane acrylate adhesive is prepared by uniformly mixing the following components in parts by weight: 20-30 parts of hyperbranched polyurethane acrylate, 1-5 parts of aluminum acrylate, 0.2-0.4 part of initiator and 70-90 parts of solvent.
Further, the solvent is one of cyclohexane, butanone and tetrahydrofuran; the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Further, the preparation method of the poly-1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester comprises the following steps: adding 1, 4-naphthalenedicarboxylic acid, 3- (trimethylsilyl) -1, 2-propylene glycol ester, a catalyst and a high-boiling point solvent into a high-pressure reaction kettle, replacing air in the kettle with nitrogen or inert gas, then carrying out esterification reaction for 3-5 hours under the conditions that the temperature is 230-; and then under the vacuum condition, controlling the temperature between 270 ℃ and 290 ℃, stirring and reacting for 18-22h, cooling to room temperature after the reaction is finished, discharging and precipitating in water, washing the precipitated product for 4-8 times by using ethanol, and then removing the ethanol by rotary evaporation to obtain the poly (1, 4-naphthalenedicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester).
Preferably, the mass ratio of the 1, 4-naphthalene dicarboxylic acid to the 3- (trimethylsilyl) -1, 2-propylene glycol ester to the catalyst to the high-boiling point solvent is 1.46:1 (0.4-0.6) to (10-15).
Preferably, the catalyst is at least one of tetrabutyl titanate, methyl benzene sulfonic acid and titanium chloride; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.
Further, the preparation method of the outer layer comprises the following steps: uniformly mixing poly (1, 4-naphthalenedicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to parts by weight, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling solidification and roll calendering at the temperature of 250 ℃ to obtain an outer layer.
The invention also aims to provide a production process of the PBT aluminum-plastic composite film, which is characterized by comprising the following steps of: and respectively coating the inner side and the outer side of the middle layer with the aluminum-doped hyperbranched polyurethane acrylate adhesive, respectively superposing the outer layer and the inner layer on the outer side and the inner side of the middle layer, pressing, and hardening to obtain the PBT aluminum-plastic composite film.
Further, the hardening treatment is as follows: hardening at 70-85 deg.C for 30-45 min, and then at room temperature for 15-24 hr.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the PBT aluminum-plastic composite film disclosed by the invention is simple and feasible in production process, low in energy consumption, high in production efficiency and finished product qualification rate, and suitable for continuous industrial production.
(2) The PBT aluminum-plastic composite film disclosed by the invention overcomes the defects that in the prior art, an aluminum-plastic film for a lithium battery is easy to generate wrinkles and pinholes, and is easy to be corroded and swelled by lithium battery electrolyte, so that a lithium battery product is damaged; the lithium ion battery can be easily combusted, once the lithium ion battery generates heat in a short circuit, the battery wrapped by the aluminum plastic film is very likely to be combusted or even explode, has the defect of large potential safety hazard, and has the advantages of high temperature resistance, corrosion resistance, scratch resistance, good performance stability, excellent comprehensive performance, good mechanical property and water vapor barrier property, and capability of obviously improving the heat resistance and the safety performance of the lithium ion battery.
(3) The adhesive is formed by an aluminum-doped hyperbranched polyurethane acrylate adhesive, the hyperbranched polyurethane acrylate structure enables the adhesive to combine the advantages of hyperbranched polyurethane and acrylate adhesive, vinyl is introduced to perform a crosslinking reaction with vinyl on aluminum acrylate in a curing and forming stage, so that the bonding strength and electrolyte corrosion resistance are improved, aluminum is introduced into an adhesive layer, the adhesive layer has a structure similar to that of an aluminum foil, and the bonding strength between the adhesive and the aluminum foil can be improved through penetration.
(4) The outer layer of the PBT aluminum-plastic composite film disclosed by the invention is formed by a blend formed by blending poly (1, 4-naphthalenedicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester) and PBT resin, the blend combines the advantages of the poly (1, 4-naphthalenedicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester) and the PBT resin, the heat resistance and the notch impact strength of the PBT resin are improved, the comprehensive performance is excellent, and the weather resistance, the flame retardance and the performance stability of the material can be improved by introducing a naphthalene ring and a silicon structure; and the two resins both contain polyester structures, have good compatibility and are not easy to phase separate.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
In the embodiment of the invention, the raw materials are all purchased commercially; the hyperbranched polyurethane acrylate is prepared in advance, and the preparation method refers to the following steps: baofen, synthesis of hyperbranched polyurethane acrylate, photopolymerization and toughening research on epoxy acrylate, 2011 (2011, 01) and pages B014-577; the PBT resin is American Tycona 1700A high molecular weight PBT Celanex; the aluminum foil is a soft aluminum foil of Henan Ming Tai aluminum industry Co., Ltd, and the model is 8021; the polypropylene layer is a casting polypropylene film layer of Jiangyin Tongli photoelectric technology limited, and the polyethylene layer is a casting polyethylene film layer of Jiangyin Tongli photoelectric technology limited.
Example 1
The PBT aluminum-plastic composite film is characterized by comprising an intermediate layer, an inner layer arranged on the inner side of the intermediate layer and an outer layer arranged on the outer side of the intermediate layer, wherein the intermediate layer is bonded with the inner layer through a first adhesive layer, and the intermediate layer is bonded with the outer layer through a second adhesive layer; the middle layer is an aluminum foil layer, the inner layer is a polyethylene layer, and the outer layer is formed by a blend formed by blending poly (1, 4-naphthalene dicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to the weight ratio of 1: 5; the thickness of the outer layer is 15 micrometers, the thickness of the middle layer is 30 micrometers, and the thickness of the inner layer is 30 micrometers; the first adhesive layer and the second adhesive layer are each independently formed from an aluminum-doped hyperbranched polyurethane acrylate adhesive.
The aluminum-doped hyperbranched polyurethane acrylate adhesive is prepared by uniformly mixing the following components in parts by weight: 20 parts of hyperbranched polyurethane acrylate, 1 part of aluminum acrylate, 0.2 part of azodiisobutyronitrile and 70 parts of cyclohexane.
The preparation method of the poly-1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester comprises the following steps: adding 14.6g of 1, 4-naphthalenedicarboxylic acid, 10g of 3- (trimethylsilyl) -1, 2-propylene glycol ester, 4g of tetrabutyl titanate and 100g of dimethyl sulfoxide into a high-pressure reaction kettle, replacing the air in the kettle with nitrogen, then carrying out esterification reaction for 3 hours at the temperature of 230 ℃ and the absolute pressure of 10KPa, ending the esterification, and releasing the pressure to the normal pressure; and then under the vacuum condition, controlling the temperature to be 270 ℃, stirring and reacting for 18h, cooling to room temperature after the reaction is finished, discharging, precipitating in water, washing the precipitated product with ethanol for 4 times, and then removing the ethanol by rotary evaporation to obtain the poly-1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester.
The preparation method of the outer layer comprises the following steps: uniformly mixing poly (1, 4-naphthalenedicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to parts by weight, adding the mixture into a double-screw extruder, performing melt extrusion at 230 ℃, cooling and solidifying, and rolling by using a roller to obtain an outer layer.
The production process of the PBT aluminum-plastic composite film is characterized by comprising the following steps: respectively coating the inner side and the outer side of the middle layer with the aluminum-doped hyperbranched polyurethane acrylate adhesive, respectively superposing the outer layer and the inner layer on the outer side and the inner side of the middle layer, pressing, and hardening to obtain the PBT aluminum-plastic composite film; the hardening treatment comprises the following steps: the mixture was cured at 70 ℃ for 30 minutes and then at room temperature for 15 hours.
Example 2
The PBT aluminum-plastic composite film is characterized by comprising an intermediate layer, an inner layer arranged on the inner side of the intermediate layer and an outer layer arranged on the outer side of the intermediate layer, wherein the intermediate layer is bonded with the inner layer through a first adhesive layer, and the intermediate layer is bonded with the outer layer through a second adhesive layer; the middle layer is an aluminum foil layer, the inner layer is a polypropylene layer, and the outer layer is formed by a blend formed by blending poly (1, 4-naphthalene dicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to the weight ratio of 1: 6; the thickness of the outer layer is 18 micrometers, the thickness of the middle layer is 35 micrometers, and the thickness of the inner layer is 35 micrometers; the first adhesive layer and the second adhesive layer are each independently formed from an aluminum-doped hyperbranched polyurethane acrylate adhesive.
The aluminum-doped hyperbranched polyurethane acrylate adhesive is prepared by uniformly mixing the following components in parts by weight: 23 parts of hyperbranched polyurethane acrylate, 2.5 parts of aluminum acrylate, 0.25 part of azobisisoheptonitrile and 75 parts of butanone.
The preparation method of the poly-1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester comprises the following steps: adding 14.6g of 1, 4-naphthalenedicarboxylic acid, 10g of 3- (trimethylsilyl) -1, 2-propanediol ester, 4.5g of methylbenzenesulfonic acid and 115g of N, N-dimethylformamide into a high-pressure reaction kettle, replacing air in the kettle with helium, then carrying out esterification reaction for 3.5 hours at 235 ℃ and 20KPa absolute pressure, ending esterification, and releasing pressure to normal pressure; and then under the vacuum condition, controlling the temperature to 275 ℃, stirring for reacting for 19h, cooling to room temperature after the reaction is finished, discharging, precipitating in water, washing the precipitated product with ethanol for 5 times, and then removing the ethanol by rotary evaporation to obtain the poly-1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester.
The preparation method of the outer layer comprises the following steps: uniformly mixing poly (1, 4-naphthalenedicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to parts by weight, adding the mixture into a double-screw extruder, carrying out melt extrusion at 235 ℃, cooling and solidifying, and rolling by using a roller to obtain an outer layer.
The production process of the PBT aluminum-plastic composite film is characterized by comprising the following steps: respectively coating the inner side and the outer side of the middle layer with the aluminum-doped hyperbranched polyurethane acrylate adhesive, respectively superposing the outer layer and the inner layer on the outer side and the inner side of the middle layer, pressing, and hardening to obtain the PBT aluminum-plastic composite film; the hardening treatment comprises the following steps: hardening was carried out at 75 ℃ for 35 minutes and then at room temperature for 18 hours.
Example 3
The PBT aluminum-plastic composite film is characterized by comprising an intermediate layer, an inner layer arranged on the inner side of the intermediate layer and an outer layer arranged on the outer side of the intermediate layer, wherein the intermediate layer is bonded with the inner layer through a first adhesive layer, and the intermediate layer is bonded with the outer layer through a second adhesive layer; the middle layer is an aluminum foil layer, the inner layer is a polypropylene layer, and the outer layer is formed by a blend formed by blending poly (1, 4-naphthalene dicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to the weight ratio of 1: 6.5; the thickness of the outer layer is 23 μm, the thickness of the middle layer is 40 μm, and the thickness of the inner layer is 40 μm; the first adhesive layer and the second adhesive layer are each independently formed from an aluminum-doped hyperbranched polyurethane acrylate adhesive.
The aluminum-doped hyperbranched polyurethane acrylate adhesive is prepared by uniformly mixing the following components in parts by weight: 25 parts of hyperbranched polyurethane acrylate, 3 parts of aluminum acrylate, 0.3 part of azodiisobutyronitrile and 80 parts of tetrahydrofuran.
The preparation method of the poly-1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester comprises the following steps: adding 14.6g of 1, 4-naphthalenedicarboxylic acid, 10g of 3- (trimethylsilyl) -1, 2-propylene glycol ester, 5g of titanium chloride and 130g of N-methylpyrrolidone into a high-pressure reaction kettle, replacing air in the kettle with neon, carrying out esterification reaction for 4 hours at 235 ℃ and the absolute pressure of 30KPa, finishing esterification, and releasing pressure to normal pressure; and then under the vacuum condition, controlling the temperature to be 280 ℃, stirring and reacting for 20h, cooling to room temperature after the reaction is finished, discharging, precipitating in water, washing the precipitated product with ethanol for 6 times, and then removing the ethanol by rotary evaporation to obtain the poly-1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester.
The preparation method of the outer layer comprises the following steps: uniformly mixing poly (1, 4-naphthalenedicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to parts by weight, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling solidification and roller calendering at 240 ℃ to obtain an outer layer.
The production process of the PBT aluminum-plastic composite film is characterized by comprising the following steps: respectively coating the inner side and the outer side of the middle layer with the aluminum-doped hyperbranched polyurethane acrylate adhesive, respectively superposing the outer layer and the inner layer on the outer side and the inner side of the middle layer, pressing, and hardening to obtain the PBT aluminum-plastic composite film; the hardening treatment comprises the following steps: cured at 78 ℃ for 38 minutes and then at room temperature for 20 hours.
Example 4
The PBT aluminum-plastic composite film is characterized by comprising an intermediate layer, an inner layer arranged on the inner side of the intermediate layer and an outer layer arranged on the outer side of the intermediate layer, wherein the intermediate layer is bonded with the inner layer through a first adhesive layer, and the intermediate layer is bonded with the outer layer through a second adhesive layer; the middle layer is an aluminum foil layer, the inner layer is a polyethylene layer, and the outer layer is formed by a blend formed by blending poly (1, 4-naphthalene dicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to the weight ratio of 1: 7; the thickness of the outer layer is 28 micrometers, the thickness of the middle layer is 47 micrometers, and the thickness of the inner layer is 45 micrometers; the first adhesive layer and the second adhesive layer are each independently formed from an aluminum-doped hyperbranched polyurethane acrylate adhesive.
The aluminum-doped hyperbranched polyurethane acrylate adhesive is prepared by uniformly mixing the following components in parts by weight: 28 parts of hyperbranched polyurethane acrylate, 4.5 parts of aluminum acrylate, 0.35 part of initiator and 87 parts of cyclohexane; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5.
The preparation method of the poly-1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester comprises the following steps: adding 14.6g of 1, 4-naphthalenedicarboxylic acid, 10g of 3- (trimethylsilyl) -1, 2-propanediol ester, 5.8g of catalyst and 145g of high-boiling point solvent into a high-pressure reaction kettle, replacing air in the kettle with argon, carrying out esterification reaction for 4.5 hours at the temperature of 238 ℃ and the absolute pressure of 40KPa, ending esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature to be 287 ℃, stirring and reacting for 21h, cooling to room temperature after the reaction is finished, discharging and precipitating in water, washing the precipitated product with ethanol for 7 times, and then removing the ethanol by rotary evaporation to obtain poly (1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester); the catalyst is formed by mixing tetrabutyl titanate, methyl benzenesulfonic acid and titanium chloride according to the mass ratio of 1:2: 3; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:1:2: 4.
The preparation method of the outer layer comprises the following steps: uniformly mixing poly (1, 4-naphthalenedicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester) and PBT resin according to parts by weight, adding the mixture into a double-screw extruder, performing melt extrusion at 245 ℃, cooling and solidifying, and rolling by using a roller to obtain an outer layer.
The production process of the PBT aluminum-plastic composite film is characterized by comprising the following steps: respectively coating the inner side and the outer side of the middle layer with the aluminum-doped hyperbranched polyurethane acrylate adhesive, respectively superposing the outer layer and the inner layer on the outer side and the inner side of the middle layer, pressing, and hardening to obtain the PBT aluminum-plastic composite film; the hardening treatment comprises the following steps: cured at 83 ℃ for 43 minutes and then at room temperature for 23 hours.
Example 5
The PBT aluminum-plastic composite film is characterized by comprising an intermediate layer, an inner layer arranged on the inner side of the intermediate layer and an outer layer arranged on the outer side of the intermediate layer, wherein the intermediate layer is bonded with the inner layer through a first adhesive layer, and the intermediate layer is bonded with the outer layer through a second adhesive layer; the middle layer is an aluminum foil layer, the inner layer is a polypropylene layer, and the outer layer is formed by a blend formed by blending poly (1, 4-naphthalene dicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to the weight ratio of 1: 8; the thickness of the outer layer is 30 micrometers, the thickness of the middle layer is 50 micrometers, and the thickness of the inner layer is 50 micrometers; the first adhesive layer and the second adhesive layer are each independently formed from an aluminum-doped hyperbranched polyurethane acrylate adhesive.
The aluminum-doped hyperbranched polyurethane acrylate adhesive is prepared by uniformly mixing the following components in parts by weight: 30 parts of hyperbranched polyurethane acrylate, 5 parts of aluminum acrylate, 0.4 part of azodiisoheptanonitrile and 90 parts of cyclohexane.
The preparation method of the poly-1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester comprises the following steps: adding 14.6g of 1, 4-naphthalenedicarboxylic acid, 10g of 3- (trimethylsilyl) -1, 2-propylene glycol ester, 6g of tetrabutyl titanate and 150g of N-methylpyrrolidone into a high-pressure reaction kettle, replacing the air in the kettle with nitrogen, carrying out esterification reaction for 5 hours at the temperature of 240 ℃ and the absolute pressure of 50KPa, finishing esterification, and releasing pressure to normal pressure; and then under the vacuum condition, controlling the temperature to be 290 ℃, stirring and reacting for 22h, cooling to room temperature after the reaction is finished, discharging, precipitating in water, washing the precipitated product with ethanol for 8 times, and then removing the ethanol by rotary evaporation to obtain the poly-1, 4-naphthalene dicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester.
The preparation method of the outer layer comprises the following steps: uniformly mixing poly (1, 4-naphthalenedicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to parts by weight, adding the mixture into a double-screw extruder, carrying out melt extrusion at 250 ℃, cooling and solidifying, and rolling by using a roller to obtain an outer layer.
The production process of the PBT aluminum-plastic composite film is characterized by comprising the following steps: respectively coating the inner side and the outer side of the middle layer with the aluminum-doped hyperbranched polyurethane acrylate adhesive, respectively superposing the outer layer and the inner layer on the outer side and the inner side of the middle layer, pressing, and hardening to obtain the PBT aluminum-plastic composite film; the hardening treatment comprises the following steps: cured at 85 ℃ for 45 minutes and then at room temperature for 24 hours.
Comparative example 1
The invention provides a PBT aluminum-plastic composite film, the formula and the production process of which are similar to those of the embodiment 1, except that the outer layer is formed by PBT resin.
Comparative example 2
The invention provides a PBT aluminum-plastic composite film, which has a formula and a production process similar to those of example 1, and is different from the preparation process of the aluminum-doped hyperbranched polyurethane acrylate adhesive in that aluminum acrylate is not added.
Comparative example 3
The invention provides an aluminum plastic film, and the formula and the manufacturing method thereof are the same as those of embodiment 1 of Chinese patent 201710813207.4.
The aluminum-plastic film samples prepared in the above examples 1-5 and comparative examples 1-3 were subjected to the related performance tests, the test results are shown in table 1, and the test methods are as follows:
(1) electrolyte resistance: dropping electrolyte (the volume of dimethyl carbonate, ethyl carbonate and diethyl carbonate is 1:1:1, and the electrolyte LiPF is contained) on the surface of each sample membrane61mol/L), the temperature is 23 ℃, the relative humidity is 50 percent, the mixture is kept still for 24 hours, and the electrolyte is wiped by water to observe the corrosion condition of the surface.
(2) Tensile strength: the test was carried out according to GB/T1040, the direction of testing being the machine direction.
(3) Adhesive property: and completely soaking the compounded aluminum-plastic film sample in the electrolyte for 24 hours, manufacturing the aluminum-plastic film sample into a sample strip with the width of 15mm, and carrying out T-shaped stripping on the outer layer and the aluminum foil layer at the testing speed of 50 mm/min.
TABLE 1
| Item | Tensile strength | Resistance to electrolyte solution | Initial adhesion | Immersion in electrolyte |
| Unit of | MPa | — | N/15mm | N/15mm |
| Example 1 | 265 | Without obvious change | 12 | 12 |
| Example 2 | 267 | Without obvious change | 13 | 13 |
| Example 3 | 270 | Without obvious change | 13 | 13 |
| Example 4 | 272 | Without obvious change | 14 | 14 |
| Example 5 | 275 | Without obvious change | 13 | 13 |
| Comparative example 1 | 250 | Without obvious change | 12 | 11 |
| Comparative example2 | 247 | Without obvious change | 10 | 8 |
| Comparative example 3 | 250 | Without obvious change | 7 | 5 |
As can be seen from table 1, the PBT aluminum-plastic composite film disclosed in the embodiment of the invention has excellent mechanical properties and electrolyte corrosion resistance, and the adhesion between layers is large, and the performance stability is better.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The PBT aluminum-plastic composite film is characterized by comprising an intermediate layer, an inner layer arranged on the inner side of the intermediate layer and an outer layer arranged on the outer side of the intermediate layer, wherein the intermediate layer is bonded with the inner layer through a first adhesive layer, and the intermediate layer is bonded with the outer layer through a second adhesive layer; the middle layer is an aluminum foil layer, the inner layer is a polyolefin layer, and the outer layer is formed by a blend formed by blending poly (1, 4-naphthalene dicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to the weight ratio of 1 (5-8); the first adhesive layer and the second adhesive layer are each independently formed from an aluminum-doped hyperbranched polyurethane acrylate adhesive.
2. The PBT aluminum-plastic composite film according to claim 1, wherein the outer layer has a thickness of 15 to 30 μm, the intermediate layer has a thickness of 30 to 50 μm, and the inner layer has a thickness of 30 to 50 μm.
3. The PBT plastic-aluminum composite film according to claim 1, wherein the polyolefin layer is a polyethylene layer or a polypropylene layer.
4. The PBT aluminum-plastic composite film according to claim 1, wherein the aluminum-doped hyperbranched polyurethane acrylate adhesive is prepared by uniformly mixing the following components in parts by weight: 20-30 parts of hyperbranched polyurethane acrylate, 1-5 parts of aluminum acrylate, 0.2-0.4 part of initiator and 70-90 parts of solvent.
5. The PBT aluminum-plastic composite film according to claim 4, wherein the solvent is one of cyclohexane, butanone and tetrahydrofuran; the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
6. The PBT plastic-aluminum composite film according to claim 1, wherein the preparation method of the poly-1, 4-naphthalenedicarboxylic acid 3- (trimethylsilyl) -1, 2-propanediol ester comprises the following steps: adding 1, 4-naphthalenedicarboxylic acid, 3- (trimethylsilyl) -1, 2-propylene glycol ester, a catalyst and a high-boiling point solvent into a high-pressure reaction kettle, replacing air in the kettle with nitrogen or inert gas, then carrying out esterification reaction for 3-5 hours under the conditions that the temperature is 230-; and then under the vacuum condition, controlling the temperature between 270 ℃ and 290 ℃, stirring and reacting for 18-22h, cooling to room temperature after the reaction is finished, discharging and precipitating in water, washing the precipitated product for 4-8 times by using ethanol, and then removing the ethanol by rotary evaporation to obtain the poly (1, 4-naphthalenedicarboxylic acid 3- (trimethylsilyl) -1, 2-propylene glycol ester).
7. The PBT aluminum-plastic composite film according to claim 6, wherein the mass ratio of the 1, 4-naphthalenedicarboxylic acid to the 3- (trimethylsilyl) -1, 2-propanediol ester to the catalyst to the high-boiling point solvent is 1.46:1 (0.4-0.6) to (10-15).
8. The PBT aluminum-plastic composite film according to claim 6, wherein the catalyst is at least one of tetrabutyl titanate, methyl benzene sulfonic acid and titanium chloride; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.
9. The PBT aluminum-plastic composite film according to claim 1, wherein the preparation method of the outer layer comprises the following steps: uniformly mixing poly (1, 4-naphthalenedicarboxylic acid) 3- (trimethylsilyl) -1, 2-propylene glycol ester and PBT resin according to parts by weight, adding the mixture into a double-screw extruder, and performing melt extrusion, cooling solidification and roll calendering at the temperature of 250 ℃ to obtain an outer layer.
10. The PBT aluminum-plastic composite film according to any one of claims 1 to 9, wherein the production process of the PBT aluminum-plastic composite film comprises the following steps: respectively coating the inner side and the outer side of the middle layer with the aluminum-doped hyperbranched polyurethane acrylate adhesive, respectively superposing the outer layer and the inner layer on the outer side and the inner side of the middle layer, pressing, and hardening to obtain the PBT aluminum-plastic composite film; the hardening treatment comprises the following steps: hardening at 70-85 deg.C for 30-45 min, and then at room temperature for 15-24 hr.
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| CN115232592A (en) * | 2022-08-30 | 2022-10-25 | 广东远东高分子科技有限公司 | Polyurethane adhesive for aluminum plastic film and preparation method thereof |
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